Compositions comprising (A) an oligomer or polymer containing at least one carboxylic acid group in the molecule; (B) at least one compound of formulas (I, II, III, IV, V or VI), wherein R1 inter alia is phenyl or alkyl; R2 is for example C2-C12alkonoyl which is unsubstituted or substituted or is benzoyl; R3, R4, R5, R6 and R7 independently of one another are for instance hydrogen, C1-C12alkyl, cyclohexyl or phenyl which is unsubstituted or substituted, or are benzyl, benzoyl, C2-C12alkanoyl or phenoxycarbonyl; R8 is for example hydrogen or C1-C12alkyl or a group (B); M is for example C1-C12alkylene, cyclohexylene or phenylene; M1 inter alia is a direct bond or C1-C12alkylenoxy; and Ar is a 5- or 6-membered aromatic heterocyclic ring; (C) a photopolymerizable reactive or unreactive diluent; and (D) as a thermosetting component an epoxy compound containing at least two epoxy groups in one molecule; are highly suitable as resists which are alkaline developable.

The invention pertains to compositions comprising O-acyloxime photoinitiators and the use of these compositions especially in imaging technique.
From U.S. Pat. Nos. 3,558,309, 4,202,697, 4,255,513, 4,590,145 it is known that oxime ester derivatives are photoinitiators. In JP Kokai Hei 8-272095 solder resist ink compositions comprising inter alia 1-phenyl-1,2-propanedione-2-O-benzoyl oxime and 1-phenyl-1,2-propanedione-2-O-ethoxycarbonyl oxime as photoinitiators are disclosed. In JP Kokai Hei 8-339081 in a similar composition 1-phenyl-1,2-propanedione-2-O-ethoxycarbonyl oxime is employed.
In photopolymerization technology there still exists a need for compositions suitable in particular as imaging formulations which are reactive, alkaline developable, easy to handle, exhibit good resolution properties and meet the high requirements of the industry regarding properties like, for example, thermal stability and storage stability.
Surprisingly it was found, that photosensitive thermosetting liquid compositions comprising
(A) an oligomer or polymer containing at least one carboxylic acid group in the molecule;
(B) at least one compound of the formula I, II, III, IV, V or VI
wherein R1 is phenyl which is unsubstituted or substituted by one or more C1-C6alkyl, phenyl, halogen, OR8, SR9 or NR10R11, or R1 is C1-C20alkyl, C2-C20alkenyl, C2-C20alkynyl or C2-C20-alkyl optionally interrupted by one or more xe2x80x94Oxe2x80x94 and/or optionally substituted by one or more hydroxyl groups, or R1 is C2-C20alkanoyl or benzoyl which is unsubstituted or substituted by one or more C1-C6alkyl, phenyl, OR8, SR9 or NR10R11, or R1 is C2-C12alkoxycarbonyl optionally interrupted by one or more xe2x80x94Oxe2x80x94 and/or optionally substituted by one or more hydroxyl groups, or R1 is phenoxycarbonyl which is unsubstituted or substituted by C1-C6alkyl, halogen, phenyl, OR8 or NR10R11, or R1 is xe2x80x94CONR10R11, CN, NO2, C1-C4-haloalkyl, S(O)mC1-C6alkyl, unsubstituted or C1-C12alkyl-substituted S(O)mxe2x80x94C6-C12aryl, SO2Oxe2x80x94C1-C6alkyl, SO2Oxe2x80x94C6-C10aryl, or diphenyl-phosphinoyl, or R1 together with R3 or R1 together with R7 may form 5 or 6 membered rings including one or more COxe2x80x94 and/or oxime-groups;
m is 1 or 2;
R2 is C2-C12alkanoyl which is unsubstituted or substituted by one or more halogen or CN, or R2 is C3-C12alkenoyl, or benzoyl which is unsubstituted or substituted by one or more C1-C6alkyl, phenyl, halogen CN, OR8, SR9 or NR10R11, or R2 is C2-C12alkoxycarbonyl or phenoxycarbonyl which is unsubstituted or substituted by C1-C6alkyl or halogen;
R3, R4, R5, R6 and R7 independently of one another are hydrogen, halogen, C1-C12alkyl, cyclopentyl, cyclohexyl or phenyl which is unsubstituted or substituted by one or more OR8, SR9 or NR10R11, or R3, R4, R5, R6 and R7 are benzyl, benzoyl, C2-C12alkanoyl, C2-C12alkoxycarbonyl optionally interrupted by one or more xe2x80x94Oxe2x80x94 and/or optionally substituted by one or more hydroxyl groups or R3, R4, R5, R6 and R7 are phenoxycarbonyl or a group OR8, SR9, SOR9, SO2R9, NO2, CN, CONR10R11, or NR10R11, wherein the substituents OR8, SR9 and NR10R11 may form 5- or 6-membered rings via the radicals R8, R9, R10 and/or R11 with further substituents on the phenyl ring or with one of the carbon atoms of the phenyl ring;
R8 is hydrogen, C1-C12alkyl or C2-C6alkyl which is substituted by xe2x80x94OH, xe2x80x94SH, xe2x80x94CN, C1-C4alkoxy, C3-C6alkenoxy, xe2x80x94OCH2CH2CN, xe2x80x94OCH2CH2COO(C1-C4alkyl), xe2x80x94OCOxe2x80x94C1-C4alkyl, xe2x80x94OCO-phenyl, COOH or COO(C1-C4alkyl), or R8 is C2-C6alkyl which is interrupted by one or more xe2x80x94Oxe2x80x94, or R8 is xe2x80x94(CH2CH2O)nH, C2-C8alkanoyl, C2-C12alkenyl, C3-C6alkenoyl, cyclohexl or phenyl which is unsubstituted or substituted by halogen, C1-C12alkyl or C1-C4alkoxy, or R8 is phenyl-C1-C3alkyl or Si(C1-C8alkyl)r(phenyl)3xe2x88x92r or R8 is a group
n is 1-20;
r is 1, 2 or 3;
R9 is hydrogen, C1-C12alkyl, C2-C12alkenyl, cyclohexyl, C2-C6alkyl which is substituted by xe2x80x94OH, xe2x80x94SH, xe2x80x94CN, C1-C4alkoxy, C3-C6alkenoxy, xe2x80x94OCH2CH2CN, xe2x80x94OCH2CH2COO(C1-C4alkyl), xe2x80x94OCOxe2x80x94C1-C4alkyl, xe2x80x94OCO-phenyl, COOH or COO(C1-C4alkyl) or R9 is C2-C12alkyl which is interrupted by one or more xe2x80x94Oxe2x80x94 or xe2x80x94Sxe2x80x94 or R9 is phenyl which is unsubstituted or substituted by halogen, C1-C12alkyl or C1-C4alkoxy, or R9 is phenyl-C1-C3alkyl or a group
R10 and R11 independently of each other are hydrogen, C1-C12alkyl, C2-C4hydroxyalkyl, C2-C10alkoxyalkyl, C2-C5alkenyl, C5-C12cycloalkyl, phenyl-C1-C3alkyl, phenyl which is unsubstituted or substituted by C1-C12alkyl or C1-C4alkoxy, or R10 and R11 are C2-C3alkanoyl, C3-C6alkenoyl or benzoyl, or R10 and R11 together are C2-C6alkylene optionally interrupted by xe2x80x94Oxe2x80x94 or xe2x80x94NR8xe2x80x94, or R10 and R11 together are C2-C6alkylene which can be substituted by hydroxyl, C1-C4alkoxy, C2-C4alkanoyloxy or benzoyloxy, or, when R10 is hydrogen, R11 may be a group
R12, R13, R14, R15, R16, R17, R18 and R19 independently of one another are hydrogen, halogen, C1-C12alkyl, cyclopentyl, cyclohexyl or phenyl which is unsubstituted or substituted by one or more OR8, SR9 or NR10R11, or R12, R13, R14, R15, R16, R17, R18 and R19 are benzyl benzoyl, C2-C12alkanoyl, C2-C12alkoxycarbonyl optionally interrupted by one or more xe2x80x94Oxe2x80x94 and/or optionally substituted by one or more hydroxyl groups or R12, R13, R14, R15, R16, R17, R18 and R19 are phenoxycarbonyl or a group OR8, SR9, SOR9, SO2R9, NO2, CN, CONR10R11, or NR10R11, wherein the substituents OR8, SR9 and NR10R11 may form 5- or 6-membered rings via the radicals R8, R9, R10 and/or R11 with further substituents on the phenyl ring or with one of the carbon atoms of the phenyl ring or, when M4 is a direct bond, R15 and R16 together are ethylene or ethynylene;
t is 0 or 1;
M is C1-C12alkylene, cyclohexylene, phenylene, xe2x80x94COOxe2x80x94(C2-C12alkylene)xe2x80x94OOCxe2x80x94, xe2x80x94COOxe2x80x94(CH2CH2O)nxe2x80x94OCxe2x80x94 or xe2x80x94COxe2x80x94(C2-C12-alkylene)xe2x80x94COxe2x80x94;
M1 is a direct bond or C1-C12alkylenoxy, optionally interrupted by 1 to 5 xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 and/or xe2x80x94NR10xe2x80x94;
M2 is a direct bond or C1-C12alkylene-Sxe2x80x94, optionally interrupted by 1 to 5 xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 and/or xe2x80x94NR10xe2x80x94;
M3 is a direct bond, a piperazino group, or C1-C12alkylene-NR10xe2x80x94, optionally interrupted by 1 to 5xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 and/or xe2x80x94NR10xe2x80x94;
M4 is a direct bond, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94CH2xe2x80x94, xe2x80x94NR10xe2x80x94, or a group
Ar is a 5- or 6-membered aromatic heterocyclic ring, which is unsubstituted or substituted by one or more C1-C6alkyl, phenyl, halogen, OR8, SR9, NR10R11, CN, C2-C6alkanoyl or benzoyl;
wherein 1-phenyl-1,2-propanedione-2-o-benzoyl oxime and 1-phenyl-1,2-propanedione-2-o-ethoxycarbonyl oxime are excluded;
(C) a photopolymerizable reactive or unreactive diluent; and
(D) as a thermosetting component an epoxy compound containing at least two epoxy groups in one molecule; exhibit an unexpectedly good performance.
Substituted radicals phenyl are substituted one to four times, for example one, two or three times, especially two or three times. Substituents on the phenyl ring are preferably in positions 4 or in 3,4-, 3,4,5-, 2,6-, 2,4- or 2,4,6-configuration on the phenyl ring, in particular in 4- or 3,4-configuration.
C1-C20alkyl is linear or branched and is, for example, C1-C18-, C1-C14-, C1-C12-, C1-C8-, C1-C6- or C1-C4alkyl or C4-C12-, C4-C8alkyl or, in particular, R1 is C6-C20 alkyl or C6-C12alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl and icosyl.
C1-C12alkyl, C2-C12alkyl, C1-C8alkyl, C1-C6alkyl, C2-C6alkyl and C1-C4alkyl have the same meanings as given above for C1-C20alkyl up to the corresponding number of C-atoms.
C2-C20alkyl which is interrupted by one or more xe2x80x94Oxe2x80x94 is for example interrupted 1-9, 1-5, 1-3 or once or twice by xe2x80x94Oxe2x80x94. Two O-atoms are separated by at least two methylene groups, namely ethylene. The alkyl groups are linear or branched. For example the following structural units will occur, xe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94CH2CH3, xe2x80x94[CH2CH2O]yxe2x80x94CH3, wherein y=1-9, xe2x80x94(CH2xe2x80x94CH2O)7CH2CH3, xe2x80x94CH2xe2x80x94CH(CH3)xe2x80x94Oxe2x80x94CH2xe2x80x94CH2CH3 or xe2x80x94CH2xe2x80x94CH(CH3)xe2x80x94Oxe2x80x94CH2xe2x80x94CH3. C2-C6alkyl which is interrupted by 1 or 2xe2x80x94Oxe2x80x94 is for example xe2x80x94CH2CH2xe2x80x94Oxe2x80x94CH2CH2xe2x80x94OCH2CH3 or xe2x80x94CH2CH2xe2x80x94Oxe2x80x94CH2CH3. C2-C12alkyl and C2-C6alkyl which is interrupted by xe2x80x94Oxe2x80x94 can have the same meanings as given above for C2-C20alkyl up the corresponding number of C- and O-atoms.
C2-C4hydroxyalkyl means C2C4alkyl, which is substituted by one or two hydroxy groups. The alkyl radical is linear or branched. Examples are 2-hydroxyethyl, 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxybutyl, 4-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 2,3-dihydroxypropyl, or 2,4-dihydroxybutyl.
C5-C12Cycloalkyl is for example cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, especially cyclopentyl and cyclohexyl, preferably cyclohexyl.
C1-C4alkoxy is linear or branched, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, isobutyloxy, tert-butyloxy.
C2-C10alkoxyalkyl is C2-C10alkyl, which is interrupted by one O-atom. C2-C10alkyl has the same meanings as given above for C1-C20alkyl up to the corresponding number of C-atoms. Examples are methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxymethyl, propoxyethyl, propoxypropyl.
C2-C12alkanoyl is linear or branched and is, for example, C2-C8-, C2-C6- or C2-C4alkanoyl or C4-C12- or C4-C8alkanoyl. Examples are acetyl, propionyl, butanoyl, isobutanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl or dodecanoyl, preferably acetyl. C2-C8alkanoyl, C2-C6alkanoyl and C2-C4alkanoyl have the same meanings as given above for C2-C20alkanoyl up to the corresponding number of C-atoms.
C2-C4alkanoyloxy is linear or branched, for example acetyloxy, propionyloxy, butanoyloxy, isobutanoyloxy, preferably acetyloxy. C2-C12alkoxycarbonyl is a linear or branched and is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, n-butyloxycarbonyl, isobutyloxycarbonyl, 1,1-dimethylpropoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl, especially methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, n-butyloxycarbonyl or iso-butyloxycarbonyl, preferably methoxycarbonyl. C2-C6alkoxycarbonyl and C2-C4alkoxycarbonyl have the same meanings as given above for C2-C12alkoxycarbonyl up to the corresponding number of C-atoms.
C2-C12alkoxycarbonyl which is interrupted by one or more xe2x80x94Oxe2x80x94 is linear or branched. The number of atoms is from 1 to 5, for example 1 to 4, 1 to 3, 1 or 2. Two O-atoms are separated by at least two methylene groups, namely ethylene.
Phenoxycarbonyl is
Substituted phenoxycarbonyl radicals are substituted one to four times, for example one, two or three times, especially two or three times. Substituents on the phenyl ring are preferably in positions 4 or in 3,4-, 3,4,5-, 2,6-, 2,4- or 2,4,6-configuration on the phenyl ring, in particular in 4- or 3,4-configuration.
Phenyl-C1-C3alkyl is for example benzyl, phenylethyl, xcex1-methylbenzyl or xcex1,xcex1-dimethylbenzyl, especially benzyl.
C2-C20alkenyl radicals may be mono or polyunsaturated and are for example C2-C12-, C2-C6-alkenyl, e.g. allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 3-butenyl, 2-butenyl, 1,3-pentadien-yl, 5-hexenyl, 7-octenyl or dodecenyl, tetradecenyl, pentadecenyl, hexadecenyl, octadecenyl and icosenyl especially allyl.
C2-C20alkynyl radicals are for example C2-C12-, C2-C6-alkynyl and may be mono or polyunsaturated and are for example ethynyl, propargyl, 1-butynyl, 3-butynyl, 2-butynyl, 5-hexynyl, 7-octynyl or dodecynyl, tetradecynyl, pentadecynyl, hexadecynyl, octadecynyl or icosynyl.
C3-C6alkenoxy radicals may be mono or polyunsaturated and are for example allyloxy, methallyloxy, butenyloxy, pentenoxy, 1,3-pentadienyloxy, 5-hexenyloxy.
C3-C6alkenoyl radicals may be mono or polyunsaturated and are for example propenoyl, 2-methyl-propenoyl, butenoyl, pentenoyl, 1,3-pentadienoyl, 5-hexenoyl.
C1-C12alkylenoxy is linear or branched and is C1-C8-, C1-C6- or C1-C4alkylenoxy, for example methylenoxy, ethylenoxy, propylenoxy, isopropylenoxy, n-butylenoxy, sec-butylenoxy, isobutylenoxy, tert-butylenoxy, pentylenoxy, hexylenoxy, heptylenoxy, 2,4,4-trimethylpentylenoxy, 2-ethylhexylenoxy, octylenoxy, nonylenoxy, decylenoxy or dodecylenoxy.
C1-C12alkylen-Sxe2x80x94 has the same meanings as given for C1-C12alkylenoxy, wherein the O-atom is exchanged by a sulfur atom.
C1-C12alkylen-NR10xe2x80x94 has the same meanings as given for C1-C12alkylenoxy, wherein the O-atom is exchanged by a xe2x80x94NR10xe2x80x94.
Halogen is fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine, preferably fluorine and chlorine.
C6-C12aryl is for example phenyl, 1-naphthyl, 2-naphthyl, preferably phenyl.
If the radicals R10 and R11 together are C2-C6alkylene optionally interrupted by xe2x80x94Oxe2x80x94or xe2x80x94NR8xe2x80x94, they form a ring together with the N-atom to which they are bonded. Examples for such rings are morpholino, piperidino, especially morpholino.
If the substituents OR8, SR9 and NR10R11 on a phenyl ring form 5- or 6-membered rings via the radicals R8, R9, R10 and/or R11 with further substituents on the phenyl ring or with one of the carbon atoms of the phenyl ring, structures comprising two or four rings (inclusive the phenyl ring) are obtained. Examples are
If R1 together with R3 or R1 together with R7 form 5 or 6 membered rings including one or more COxe2x80x94 and/or oxime-groups, for example structures of the following kind are built
If R15 and R16 together are ethylene or ethynylene, for example, the following structures are built
Ar as 5- or 6-membered heterocyclic ring comprises O-, S- or N-atoms as heteroatoms and is for example furyl, thienyl, pyrrolyl, oxinyl, dioxinyl or pyridyl. The heterocyclic ring may be substituted by one or more, for example one or two branched or unbranched C1-C6alkyl as methyl, ethyl, propyl, butyl, pentyl or hexyl, in particular C1-C4alkyl. Examples are dimethylpyridyl, dimethylpyrrolyl or methylfuryl.
Examples for compounds of formula VI are
Preferred are compositions, wherein in the compound of formula I and III, R1 is phenyl which is unsubstituted or substituted by one or more C1-C6alkyl, phenyl, halogen, OR8, SR9 or NR1R11 or R1 is C6-C20alkyl or C2-C20alkyl optionally interrupted by one or more xe2x80x94Oxe2x80x94 and/or optionally substituted by one or more hydroxyl groups.
R1 preferably is phenyl which is unsubstituted or substituted by one or more C1-C6alkyl, phenyl, halogen, OR8, SR9 or NR10R11, or R1 is C6-C20alkyl which is unsubstituted or substituted by one or more C1-C6alkyl, phenyl, OR8, SR9 or NR10R11.
Preferred are compositions comprising compounds of formulae I and III, particularly of formula I. Preferred are further compounds, wherein R3 and R7 are hydrogen. R1 is preferably C1-C12alkyl, in particular C6-C12alkyl. R2 is preferably tolyl or benzoyl or acetyl.
Oxime esters of formulae I, II, III, IV and V are prepared by methods described in the literature, for example by reaction of the corresponding oximes (R2=H) with an acyl chloride or an anhydride in an inert solvent such as for example tetrahydrofuran or dimethylformamide in the presence of a base, for example a tertiary amine, such as triethylamine, or in a basic solvent such as pyridine.
For compounds of formula V in the above scheme the group
is exchanged by a heterocyclic radical.
Such reactions are well known to those skilled in the art, and are generally carried out at temperatures of xe2x88x9215 to +50xc2x0 C., preferably 0 to 20xc2x0 C.
The compounds of formulae II and IV can be obtained analogously by using the appropriate oximes as starting materials:
R1-R7 and M have the meanings given above.
The oximes required as starting materials can be obtained by a variety of methods described in standard chemistry textbooks (for instance in J. March, Advanced Organic Chemistry, 4th Edition, Wiley lnterscience, 1992), or in specialized monographs, for example, S. R. Sandier and W. Karo, Organic functional group preparations, Vol. 3, Academic Press. One of the most convenient methods is, for example, the reaction of ketones with hydroxylamine or its salt in polar solvents like ethanol or aqueous ethanol. In that case, a base such as sodium acetate is added to control the pH of the reaction mixture. It is well known that the rate of the reaction is pH-dependent, and the base can be added at the beginning or continuously during the reaction. Basic solvents such as pyridine can also be used as base and/or solvent or cosolvent. The reaction temperature is generally the refluxing temperature of the mixture, usually 60-120xc2x0 C. Another convenient synthesis of oximes is the nitrosation of xe2x80x9cactivexe2x80x9d methylene groups with nitrous acid or an alkyl nitrite. Both alkaline conditions, as described for example in Organic Syntheses coll. Vol. VI (J. Wiley and Sons, New York, 1988), pp 199 and 840, and acidic conditions, as described, for example, in Organic Synthesis coll. vol V, pp 32 and 373, coll. vol. 111, pp 191 and 513, coll. vol.II, pp. 202, 204 and 363, are suitable for the preparation of the oximes used as starting materials in the invention. Nitrous acid is usually generated from sodium nitrite. The alkyl nitrite can be for example methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, isoamyl nitrite. Every oxime ester group can exist in two configurations, (Z) or (E). It is possible to separate the isomers by conventional methods, but it is also possible to use the isomeric mixture as photoinitiating species.
The compounds of the formulae I, II, III, IV and V can be used as photoinitiators for the photopolymerization of ethylenically unsaturated compounds or of mixtures which comprise such compounds.
Component (A) in the composition according to the invention is an oligomer or polymer, which contains at least one free carboxylic acid group in the molecule.
Particularly preferred are compositions wherein the oligomer or polymer (A) contains at least two ethylenically unsaturated polymerizable groups.
The component (A) may be of moderate (oligomeric) or high (polymeric) molecular mass. Examples for this component are oligomers or polymers obtained by reaction of a saturated or unsaturated polybasic acid anhydride with a product of the reaction of an epoxy compound and an unsaturated monocarboxylic acid. As epoxy compounds which are employed for the preparation the most interesting ones are novolak type epoxies.
The aforementioned resin curable by an activated energy ray is obtained by causing a reaction product of a novolak type epoxy compound (as described afterward) and an unsaturated monocarboxylic acid to react with a dibasic acid anhydride such as phthalic anhydride or an aromatic polycarboxylic acid anhydride such as trimellitic acid anhydride or pyromellitic acid anhydride. In this case, the resin proves particularly suitable when, in the production thereof, the amount of the aforementioned acid anhydride used for the reaction exceeded 0.15 mol per each of the hydroxyl groups possessed by the reaction product of the novolak type epoxy compound and the unsaturated carboxylic acid.
The acid value of the resin so obtained suitably falls in the range of 45 to 160 mg KOH/g, preferably 50 to 140 mg KOH/g.
When the number of ethylenically unsaturated bonds present in the molecular unit of the resin curable by the activated energy ray is small, the photosetting proceeds slowly and it is desirable to use a novolak type epoxy compound as a raw material. For the purpose of lowering the viscosity of the ink, it is possible to use bis-phenol A type epoxy compounds instead.
The novolak type epoxy compounds are represented by phenol novolak type epoxy resins and cresol novolak type epoxy resins. Compounds as are produced by causing epichlorohydrin to react with a pertinent novolak resin by the conventional method can be used. Typical examples of the aforementioned acid anhdyride are dibasic acid anhydrides such as for example maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyl-dneomethylenetetrahydrophthalic anhydride, chlorendic anhydride, and methyltetrahydrophthalic anhydride; aromatic polycarboxylic anhydrides such as for example trimellitic anhydride pyromellic anhydride, and benzophenone-tetracarboxylic dianhydride: and polycarboxylic anhydride derivatives such as 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride.
Further examples for component (A) are reaction products obtained by adding epoxy group containing acrylic acid ester or methacrylic acid ester compounds to a part of the carboxyl groups of a copolymer resulting of the reaction of acrylate or methacrylate with acrylic acid or methacrylic acid.
The copolymer of acrylic acid ester and/or methacrylic acid ester and acrylic acid and/or methacrylic acid is obtained by copolymerizing one or two or more of acrylic acid esters and/or methacrylic acids represented by the general formula (1) and (2)
wherein
Ra is a hydrogen atom or a methyl group, Rb is an aliphatic hydrocarbon group having 1 to 6 carbon atoms,
and acrylic acid and/or methacrylic acid represented by the general formula (2);
wherein Ra has the same meaning as given above,
according to routine methods such as solution polymerization.
Preferably the molar ratio between the acrylic acid ester and/or methacrylic acid ester and the acrylic acid and/or methacrylic acid is from 30:70 to 70:30.
The ester group of each of the acrylic acid ester and/or methacrylic acid ester may be appropriately selected from various aliphatic groups containing 1 to 6 carbon atoms.
The reaction product is obtained by adding to the copolymer thus obtained acrylic acid ester and/or methacrylic acid ester having a terminal epoxy group, represented by the following general formula (3);
wherein
Ra has the same meaning as described above;
Rc is an aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 12 carbon atoms.
In order to obtain the reaction product suitable for the present invention, a compound of formula (3) is added to the aforementioned monomers of formula (1) and (2) at a ratio of 10 to 40 mol %, to provide the copolymer with ultraviolet curability.
The reaction product thus obtained is preferably has an average molecular weight in the range of 20,000 to 70,000; the softening point suitably is in the range from 35xc2x0 C. to 130xc2x0 C., and the acid value is 50 to 150.
Further examples for component (A) are resins having xcex1,xcex2-unsaturated double bonds on the side chains, and having an acid value of 50-200. The photopolymerizable resin, for example, is constituted of 70-95% by weight of an ethylenically unsaturated acid component and a copolymerizable component thereof. It is an addition product formed between a carboxyl group-containing resin having an acid value (the acid value is expressed by milligram number of potassium hydroxide necessary for neutralizing 1 gram of resin) of no less than 500, preferably no less than 600 and in particular no less than 620, and having a number average molecular weight of 1,000-100,000, preferably 3,000-70,000, and an unsaturated compound having an xcex1,xcex2-unsaturated double bond and an epoxy group. The content of the ethylenically unsaturated acid component in the carboxyl group-containing resin of the photopolymerizabe resin is 70-95% by weight, due to which the photopolymerizable resin (A) does not become insoluble in water or dilute alkaline aqueous solution even after an unsaturated compound having an xcex1,xcex2-unsaturated double bond and an epoxy group is added thereto, and retains its solubility. Examples of such resins are described in JP 8-339081-A.
The carboxyl group-containing resin (A), for example, is produced by dissolving 70-95% by weight, preferably 78-88% by weight and in particular 80-85% by weight, of an ethylenically unsaturated acid monomer and 5-30% by weight, preferably 22-12% by weight and in particular 15-20% by weight, of a copolymerizable monomer in a suitable unreactive solvent and thermally polymerizing the solution at 45-120xc2x0 C. in the presence of a thermal polymerization initiator. Thus, a carboxyl group-containing resin having an acid value of no less than 500 and a number average molecular weight of 1,000-100,000 can be produced in a high safety and a high stability.
Specific examples of the ethylenically unsaturated monomer suitable for production of the carboxyl group-containing resin (A) include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, angelic acid, tiglic acid, 2-ethylacrylic acid, 3-propylacrylic acid, 3-isopropylacrylic acid, succinic acid mono-hydroxyethylacrylate, phthalic acid mono-hydroxyethylacrylate, dihydrophthalic acid mono-hydroxyethylacrylate, tetrahydrophthalic acid mono-hydroxyethylacrylate, hexahydrophthalic acid monohydroxyethyl-acrylate, acrylic acid dimer, acrylic acid trimer, xcfx89-carboxy-polycaprolactone monoacrylate and xcfx89-carboxy-polycaprolactone monomethacrylate. Among these monomers, preferred are acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, angelic acid, tiglic acid, 2-ethylacrylic acid, 3-propylacrylic acid, 3-isopropylacrylic acid, xcfx89-carboxy-polycaprolactone monoacrylate, xcfx89-carboxy-polycaprolactone monomethacrylate, and the like; and particularly preferred are acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, angelic acid, tiglic acid, 2-ethylacrylic acid, 3-propylacrylic acid, 3-isopropylacrylic acid, xcfx89-carboxy-polycaprolactone monoacrylate, and xcfx89-carboxy-polycaprotactone monomethacrylate. These monomers may be used either alone or in mixture of two or more.
Suitable copolymerizable monomers are acrylic esters, methacrylic esters, vinyl monomers, styrene type monomers and cyclic ester monomers. Specific examples thereof include 2-hydroxymethyl acrylate, 2-hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, ethyleneglycol monomethyl ether acrylate, ethyleneglycol monomethyl ether methacrylate, ethyleneglycol monoethyl ether acrylate, ethyleneglycol monoethyl ether methacrylate, glycerol acrylate, glycerol methacrylate, dipentaaerythritol pentamethacrylate, dipentaerythritol pentaacrylate, dimethylaminoethyl acrylate, dimethylamino-ethyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydro-furfuryl methacrylate, acrylic acid amide, methacrylic acid amide, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl-methacrylate, benzyl acrylate, benzyl methacrylate, acrylic acid carbitol, methacrylic acid carbitol, xcex5-caprolactone-modified tetrafurfuryl acrylate, xcex5-caprolactone-modified tetrafurfuryl methacrylate, diethyleneglycol ethoxyl acrylate, isodecyl acrylate, isodecyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, tridecyl acrylate, tridecyl methacrylate, stearyl acrylate, stearyl methacrylate and the like. These monomers may be used either alone or in mixtures of two or more.
Suitable thermal polymerization initiators are for example, 2,2xe2x80x2-azobis-(2,4-dimethylvaleronitrile) (usable temperature 45-70xc2x0 C.), 2,2xe2x80x2-azobis(isobutyronitrile) (usable temperature 60-90xc2x0 C.), 2,2xe2x80x2-azobis(2-methylisobutyronitnile) (usable temperature 60-95xc2x0 C.), tert-butyl peroctoate (usable temperature 75-100xc2x0 C.), 1,1xe2x80x2-azobis(cyclohexane-1-carbonitrile) (usable temperature 80-110xc2x0 C.) or 1-[(1-diazo-1-methylethyl)azo]-formamide (usable temperature 95-120xc2x0 C.). At least one of the cited compounds is used.
The carboxyl group-containing resin produced according to the aforementioned method is then modified into a photopolymerizable resin whose carboxyl group is esterified and whose side chains have xcex1,xcex2-unsaturated double bonds, through an esterification with an unsaturated compound having an xcex1,xcex2-unsaturated double bond and a epoxy group. Examples of suitable compounds having an xcex1,xcex2-unsaturated double bond and an epoxy group, are given below. At least one member selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, compounds of the formula 4, 5, 6, as defined below, is used.
wherein R1xe2x80x2 is hydrogen or methyl and nxe2x80x2 is an integer of 1-10;
wherein R2xe2x80x2 is hydrogen or methyl and nxe2x80x3 is an integer of 1-3.
Among these compounds, compounds having alicyclic epoxy groups are particularly preferred, because these compounds have a high reactivity with carboxyl group-containing resins, accordingly the reaction time can be shortened. These compounds further do not cause gelation in the process of reaction and make it possible to carry out the reaction stably. On the other hand, glycidyl acrylate and glycidyl methacrylate are advantageous from the viewpoint of sensitivity and heat resistance because they have a low molecular weight and can give a high conversion of esterification.
The photopolymerizable resin obtained by the above-mentioned method has xcex1,xcex2-unsaturated double bonds on its side chains. Its acid value is 50-200, preferably 70-150, and in particular 85-120. Its number average molecular weight is 7,000-10,000, and its glass transition point (hereinafter referred to as Tg) is 30-120xc2x0 C. When the photopolymerizable resin is used as a solder resist, an acid value of no less than 70 is preferable, because other additive ingredients may further be added to the composition.
An inert organic solvent is used at the time of carrying out the esterification and preparing the photosensitive resin composition.
Commercially available unsaturated compounds (A), as described before are, for example EB3800, EB9692, EB9694, EB9695, EB9696 (UCB Chemicals), KAYARAD TCR1025 (Nippon Kayaku Co.,LTD.), NEOPOL8319 (U-Pica), EA-6340 (Shin Nakamura Chemical Co., Ltd.), ACA200M, ACA250 (Daicel Industries, Ltd.).
Preferred is a composition, wherein the oligomer or polymer (A) is a resin obtained by the reaction of a saturated or unsaturated polybasic acid anhydride with a product of the reaction of an epoxy compound and an unsaturated monocarboxylic acid, or is an addition product formed between a carboxyl group-containing resin and an unsaturated compound having an xcex1,xcex2-unsaturated double bond and an epoxy group.
Examples of reactive or unreactive diluents (C) which are suitable in the compositions according to the invention are photopolymerizable vinyl type monomers and/or an organic solvents. Representative examples of the photopolymerizable vinyl type monomers are hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, etc.; mono- or diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol, etc.; acrylamides such as N,N-dimethylacrylamide, N-methylolacrylamide, etc.; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate, etc.; polyvalent acrylates of polyvalent alcohols or ethylene oxide or propylene oxide adducts thereof such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, etc.; phenoxy acrylate, bisphenol A diacrylate and acrylates of ethylene oxide or propylene oxide adducts of these phenols, etc.; acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc.; and melamine acrylate, and/or methacrylates corresponding to the above acrylates, etc.
On the other hand, examples for suitable organic solvents are ketones such as ethyl methyl ketone, cyclohexanone, etc.; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, etc.; glycol ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, benzyl cellosolve, phenyl cellosolve, methylcarbitol, butylcarbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, triethylene glycol monoethyl ether, etc.; esters such as ethyl acetate, butyl acetate and esterified products of the above glycol ethers such as cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate; alcohols such as ethanol, propanol, n-butanol, n-hexanol, n-heptanol, n-octanol, ethylene glycol, propylene glycol, etc.; aliphatic hydrocarbons such as octane, decane, etc.; a petroleum type solvent such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. and others. The organic solvent is used for diluting the resin so that it can be coated easily.
The diluents (C) as described above are used singly or as a mixture of two or more of them. The suitable amount is from 5 to 300 parts by weight, preferably 10 to 150 parts by weight, based on 100 parts by weight of component (A).
The above described diluent is used to dilute the components of the mixture so that they can be coated easily. Another purpose, if a photopolymerizable vinyl type monomer is used, is to strengthen the photopolymerizability. Further, if an organic solvent is used as diluent, the diluent supports to dissolve and dilute the photosensitive prepolymer, whereby the prepolymer can be coated in a liquid state and then dried to form a film. Therefore, depending on the diluent used, an exposure system of either a contact system in which a photomask is contacted with the coating film or a non-contact system (e.g. laser beam writing) may be used.
Preferably component (C) is a monomer with more than two acrylate or methacrylate groups.
As thermosetting component (D) compounds having epoxy groups are employed. There may be used a solid or liquid known epoxy compound, and said epoxy compound is used depending on required characteristics. For example, when the plating resistance is to be improved, a liquid epoxy resin is used, and when water resistance is required, an epoxy resin having a large number of methyl groups on a benzene ring or a cycloalkyl ring is employed. A preferred epoxy resin, is a bisphenol S type epoxy resin such as BPS-200 produced by Nippon Kayaku Co., Ltd., EPX-30 produced by ACR Co., Epiculon EXA-1514 produced by Dainippon Ink and Chemicals Inc., etc.; a bisphenol A type epoxy resin such as Epiculon N-3050, N-7050, N-9050 produced by Dainippon Ink and Chemicals Inc., XAC-5005, GT-7004, 6484T, 6099 produced by Ciba Specialty Chemicals Inc., etc. ; a bisphenol F type epoxy resin such as YDF-2004, YDF2007 produced by Tohto Kasei Co., etc.; a diglycidyl phthalate resin such as Blemmer DGT produced by Nippon Oil and Fats Co., Ltd., etc.; a heterocyclic epoxy resin such as TEPIC produced by Nissan Chemical Industries, Ltd., Araldite PT810 produced by Ciba Specialty Chemicals Inc., etc.; a bixylenol type epoxy resin such as YX-4000 produced by Yuka Shell Co., etc.; a biphenol type epoxy resin such as YL-6056 produced by Yuka Shell Co., etc.; a tetraglycidyl xylenoylethane resin such as ZX-1063 produced by Tohto Kasei Co., etc.; a novolak type epoxy resin such as EPPN-201, EOCN-103, EOCN-1020, EOCN-1025 and BRRN produced by Nippon Kayaku Co., Ltd., ECN-278, ECN-292 and ECN-299 produced by Asahi Chemical Industry Co., Ltd., GY-1180, ECN-1273 and ECN-1299 produced by Ciba Specialty Chemicals Inc., YDCN-220L, YDCN-220HH, YDCN-702, YDCN-704, YDPN-601 and YDPN-602 produced by Tohto Kasei Co., Epiculon-673, N-680, N-695, N-770 and N-775 produced by Dainippon Ink and Chemicals Inc., etc.; a novolak type epoxy resin of bisphenol A such as EPX-8001, EPX-8002, EPPX-8060 and EPPX-8061 produced by Asahi Chemical Industry Co., Ltd., Epiculon N-880 produced by Dainippon Ink and Chemicals Inc., etc.; a chelate type epoxy resin such as EPX-49-69 and EPX-49-30 produced by Asahi Denka Kogyo K. K., etc.; a glyoxal type epoxy resin such as YDG-414 produced by Tohto Kasei Co., etc., an amino group-containing epoxy resin such as YH-1402 and ST-110 produced by Tohto Kasei Co., YL-931 and YL-933 produced by Yuka Shell Co., etc.; a rubber-modified epoxy resin such as Epiculon TSR-601 produced by Dainippon Ink and Chemicals Inc., EPX-84-2 and EPX-4061 produced by Asahi Denka Kogyo K. K., etc.; a dicyclopentadiene phenolic type epoxy resin such as DCE-400 produced by Sanyo-Kokusaku Pulp Co., Ltd., etc.; a silicone-modified epoxy resin such as X-1359 produced by Asahi Denka Kogyo K. K., etc.; an xcex5-caprolactone-modified epoxy resin such as Plague G-402 and G-710 produced by Dicel Chemical Industries, Ltd., etc. and others. Further, partially esterified compounds of these epoxy compounds (e.g. esterified by (meth)acrylates) can be used in combination.
The suitable amount of component (D) to be used according to the present invention is 10 to 150 parts by weight, preferably 20 to 80 parts by weight, based on 100 parts by weight of component (A).
Preferably component (D) is a bisphenol A, bisphenol S, bisphenol F or novolak type epoxy compound.
In some cases it may be advantageous to use sensitizer compounds in combination with the compounds of the formula I, II, III, IV, V and VI. Another object of the invention therefore resides in a composition which additionally to the components (A), (B), (C) and (D) comprises at least one photosensitizer compound (E), and/or further additives (F).
Photopolymerization can also be accelerated by adding further photosensitizer compounds (E) which shift or broaden the spectral sensitivity. These are, in particular, aromatic carbonyl compounds, for example benzophenone, thioxanthone, anthraquinone and coumarin derivatives, e.g. 3-acylcoumarins, 3-(aroylmethylene)thiazolines, camphor quinone, but also eosine, rhodamine and erythrosine dyes, as well as all compounds which can be used as co-initiators as described above.
Further suitable examples of such photosensitizers are
1 .Thioxanthones
Thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-dodecylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 1-methoxycarbonylthioxanthone, 2-ethoxycarbonylthioxanthone, 3-(2-methoxyethoxycarbonyl)-thioxanthone, 4-butoxycarbonylthioxanthone, 3-butoxycarbonyl-7-methylthioxanthone, 1-cyano-3-chlorothioxanthone, 1-ethoxycarbonyl-3-chlorothioxanthone, 1-ethoxycarbonyl-3-ethoxythioxanthone, 1-ethoxycarbonyl-3-aminothioxanthone, 1-ethoxycarbonyl-3-phenyisulfurylthioxanthone, 3,4-di-[2-(2-methoxyethoxy)ethoxycarbonyl]-thioxanthone, 1-ethoxycarbonyl-3-(1-methyl-1-morpholinoethyl)-thioxanthone, 2-methyl-6-dimethoxymethyl-thioxanthone, 2-methyl-6-(1,1-dimethoxybenzyl)-thioxanthone, 2-morpholinomethylthioxanthone, 2-methyl-6-morpholinomethylthioxanthone, N-allylthioxanthone-3,4-dicarboximide, N-octylthioxanthone-3,4-dicarboximide, N-(1,1,3,3-tetramethylbutyl)-thioxanthone-3,4-dicarboximide, 1-phenoxythioxanthone, 6-ethoxycarbonyl-2-methoxythioxanthone, 6-ethoxycarbonyl-2-methylthioxanthone, thioxanthone-2-carboxylic acid polyethyleneglycol ester, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthon-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride;
2. Benzophenones
benzophenone, 4-phenyl benzophenone, 4-methoxy benzophenone, 4,4xe2x80x2-dimethoxy benzophenone, 4,4xe2x80x2-dimethyl benzophenone, 4,4xe2x80x2-dichlorobenzophenone 4,4xe2x80x2-dimethylaminobenzophenone, 4,4xe2x80x2-diethylaminobenzophenone, 4-methyl benzophenone, 2,4,6-trimethylbenzophenone, 4-(4-methylthiophenyl)-benzophenone, 3,3xe2x80x2-dimethyl-4-methoxy benzophenone, methyl-2-benzoylbenzoate, 4-(2-hydroxyethylthio)-benzophenone, 4-(4-tolylthio)-benzophenone, 4-benzoyl-N,N,N-trimethylbenzenemethanaminium chloride, 2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1-propanaminium chloride monohydrate, 4-(13-acryloyl-1,4,7,10,13-pentaoxatridecyl)-benzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyl)oxy]ethyl-benzenemethanaminium chloride;
3. Coumarins
Coumarin 1, Coumarin 6, Coumarin 7, Coumarin 337, Coumarin 500, 3-benzoyl coumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-5,7-di(propoxy)-coumarin, 3-benzoyl-6,8-dichloro-coumarin, 3-benzoyl-6-chloro-coumarin, 3,3xe2x80x2-carbonyl-bis[5,7-di(propoxy)-coumarin], 3,3xe2x80x2-carbonyl-bis(7-methoxycoumarin), 3,3xe2x80x2-carbonyl-bis(7-diethylamino-coumarin), 3-isobutyroylcoumarin, 3-benzoyl-5,7-dimethoxy-coumarin, 3-benzoyl-5,7-diethoxy-coumarin, 3-benzoyl-5,7-dibutoxy-coumarin, 3-benzoyl-5,7-di(methoxyethoxy)-coumarin, 3-benzoyl-5,7-di(allyl-oxy)-coumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3-isobutyroyl-7-dimethylaminocoumarin, 5,7-dimethoxy-3-(1-naphthoyl)-coumarin, 5,7-dimethoxy-3-(1-naphthoyl)-coumarin, 3-benzoylbenzo[f]coumarin, 7-diethylamino-3-thienoylcoumarin, 3-(4-cyanobenzoyl)-5,7-dimethoxycoumarin;
4. 3-(aroylmethylene)-thiazolines
3-methyl-2-benzoylmethylene-xcex2-naphthothiazoline, 3-methyl-2-benzoylmethylene-benzothiazoline, 3-ethyl-2-propionylmethylene-xcex2-naphthothiazoline;
5. Other carbonyl compounds
acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, benzil, 2-acetylnaphthalene, 2-naphthaldehyde, 9,10-anthraquinone, 9-fluorenone, dibenzosuberone, xanthone, 2,5-bis(4-diethylaminobenzylidene)cyclopentanone, xcex1-(para-dimethylaminobenzylidene)ketones such as 2-(4-dimethylamino-benzylidene)-indan-1-one or 3-(4-dimethylamino-phenyl)-1-indan-5-yl-propenone, 3-phenylthiophthalimide, N-methyl-3,5-di(ethylthio)-phthalimide, N-methyl-3,5-di(ethylthio)-phthalimide;
Component (E) is suitably used in an amount from 0.015 to 60 parts by weight, preferably 0.03 to 30 parts by weight, based on 100 parts by weight of component (A).
In addition to the photoinitiator and/or the sensitizer compound the photopolymerizable mixtures may include various additives (F).
Examples of these are thermal inhibitors, which are intended to prevent premature polymerization, examples being hydroquinone, hydroquinone derivatives, p-methoxyphenol, xcex2-naphthol or sterically hindered phenols, such as 2,6-di-tert-butyl-p-cresol. In order to increase the stability on storage in the dark it is possible, for example, to use copper compounds, such as copper naphthenate, stearate or octoate, phosphorus compounds, for example triphenylphosphine, tributylphosphine, triethyl phosphite, triphenyl phosphite or tribenzyl phosphite, quaternary ammonium compounds, for example tetramethylammonium chloride or trimethylbenzylammonium chloride, or hydroxylamine derivatives, for example N-diethylhydroxylamine. To exclude atmospheric oxygen during the polymerization it is possible to add paraffin or similar wax-like substances which, being of inadequate solubility in the polymer, migrate to the surface in the beginning of polymerization and form a transparent surface layer which prevents the ingress of air. It is also possible to apply an oxygen-impermeable layer. Light stabilizers which can be added in a small quantity are UV absorbers, for example those of the hydroxyphenylbenzotriazole, hydroxyphenyl-benzophenone, oxalamide or hydroxyphenyl-s-triazine type. These compounds can be used individually or in mixtures, with or without sterically hindered amines (HALS).
Examples of such UV absorbers and light stabilizers are
1. 2-(2xe2x80x2-hydroxyyhenyl)benzotriazoles for example 2-(2xe2x80x2-hydroxy-5xe2x80x2-methylphenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-tert-butyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(5xe2x80x2-tert-butyl-2xe2x80x2-hydro-xyphe-nyl)benzotriazole, 2-(2xe2x80x2-hydroxy-5xe2x80x2-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-tert-butyl-2xe2x80x2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-methyl-phenyl)-5-chlorobenzotriazole, 2-(3xe2x80x2-sec-butyl-5xe2x80x2-tert-butyl-2xe2x80x2-hydroxyphenyl)benzotrizole, 2-(2xe2x80x2-hydroxy-4xe2x80x2-octoxyphenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-tert-amyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-bis-(xcex1,xcex1-dimethylbenzyl)-2xe2x80x2-hydroxyphenyl)-benzotriazole, mixture of 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3xe2x80x2-tert-butyl-5xe2x80x2-[2-(2-ethyl-hexyl-oxy)carbonylethyl]-2xe2x80x2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-methoxycarbonylethyl)phenyl)-benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3xe2x80x2-tert-butyl-5xe2x80x2-[2-(2-ethylhexyloxy)carbonylethyl]-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(3xe2x80x2-dodecyl-2xe2x80x2-hydroxy-5xe2x80x2-methylphenyl)-benzotriazole, and 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2xe2x80x2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-yl-phenol]; trans-esterification product of 2-[3xe2x80x2-tert-butyl-5xe2x80x2-(2-methoxycarbonylethyl)-2xe2x80x2-hydroxy-phenyl]-benzotriazole with polyethylene glycol 300; [Rxe2x80x94CH2CH2xe2x80x94COO(CH2)3]2- where R=3xe2x80x2-tert-butyl-4xe2x80x2-hydroxy-5xe2x80x2-2H-benzotriazol-2-yl-phenyl.
2. 2-Hydroxybenzophenones, for example the 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2xe2x80x2,4xe2x80x2-trihydroxy- and 2xe2x80x2-hydroxy-4,4xe2x80x2-dimethoxy derivative.
3. Esters of substituted or unsubstituted benzoicacids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl saiicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, and 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
4. Acrylates, for example isooctyl or ethyl xcex1-cyano-xcex2,xcex2-diphenyl acrylate, methyl xcex1-carbo-methoxycinnamate, butyl or methyl xcex1-cyano-xcex2-methyl-p-methoxycinnamate, methyl xcex1-carboxymethoxy-p-methoxycinnamate and N-(xcex2-carbomethoxy-xcex2-cyanovinyl)-2-methylindoline.
5. Sterically hindered amines, for example bis-(2,2,6,6-tetramethylpiperidyl) sebacate, bis-(2,2,6,6-tetramethylpiperidyl) succinate, bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate, bis-(1,2,2,6,6-pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N,Nxe2x80x2-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexa-methylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris-(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetraoate, 1,1xe2x80x2-(1,2-ethandiyl)bis(3,3,5,5-tetramethyl-piperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis-(1,2,2,6,6-pentamethylpiperidyl) 2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro-[4.5]decane-2,4-dione, bis-(1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis-(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, condensation product of N,Nxe2x80x2-bis-(2,2,6,6-tetra-methyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, condensation product of 2-chloro-4,6-di-(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis-(3-aminopropyl-amino)ethane, condensation product of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis-(3-amino propylamino)-ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione and 3-dodecyl-1-(1,2,2,6,6-penta-methyl-4-piperidyi)-pyrrolidine-2,5-dione.
6. Oxalamides, for example 4,4xe2x80x2-dioctyloxyoxanilide, 2,2xe2x80x2-diethoxyoxanilide, 2,2xe2x80x2-dioctyloxy-5,5xe2x80x2-di-tert-butyloxanilide, 2,2xe2x80x2-didodecyloxy-5,5xe2x80x2di-tert-butyloxanilide, 2-ethoxy-2xe2x80x2-ethyl-oxanilide, N,Nxe2x80x2-bis-(3-dimethylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2xe2x80x2-ethyloxanilide and its mixture with 2-ethoxy-2xe2x80x2-ethyl-5,4xe2x80x2-di-tert-butyloxanilide, mixtures of o- and p-methoxy- and of o- and p-ethoxy-disubstituted oxanalides.
7. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyl-oxy-phenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-dodecyl/tridecyl-oxy-(2-hydroxypropyl)oxy-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
8. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythrityl diphosphite, tris-(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythrityl diphosphite, bis-(2,4-di-tert-butylphenyl) pentaerythrityl diphosphite, bis-(2,6-di-tert-butyl-4-methylphenyl)pentaerythrityl diphosphite, bis-isodecyloxy pentaerythrityl diphosphite, bis-(2,4-di-tert-butyl-6-methylphenyl) pentaerythrityl diphosphite, bis-(2,4,6-tri-tert-butylphenyl)pentaerythrityl diphosphite, tristearyl sorbityl triphosphite, tetrakis-(2,4-di-tert-butylphenyl)-4,4xe2x80x2-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo [d,g]-1,3,2-dioxaphosphocine, bis-(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite and bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite.
Further additives known in the art may be added as component (F), as for example antistatics, flow improvers, adhesion promoters, thickeners, antifoaming agents, flow control agents and leveling agents.
In the photosensitive thermosetting resin composition of the present invention, for improving charasteristics such as adhesion property, hardness, etc., if necessary, there may be used an inorganic filler such as for example barium sulfate, barium titanate, silicon oxide powder, particulate silicone oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminium oxide, aluminium hydroxide, mica powder, etc. The ration of the filler in the formulation is 0 to 60% by weight, preferably 5 to 40% by weight of the photosensitive thermosetting resin composition.
Further, if, necessary, there may be used known additives such as a known coloring agents, e.g. Phthalocynine Blue, Phthalocyanine Green, Diazo Yellow, Crystal Violet, titanium oxide, carbone black, naphthalene black, etc.
The composition optionally additionally comprises as component (F) epoxy curing promoters such as, for example, an amine compound, an imidazole compound, a carboxylic acid, a phenol, a quaternary ammonium salt, or a methylol group-containing compound. The amount of said curing agent to be used is in the range of 0 to 10% by weight, preferably 0.05 to 5% by weight, of the photosensitive thermosetting resin composition.
Accordingly, subject of the invention are compositions as described above, comprising further additives (F), which are selected from the group consisting of inorganic fillers, colourants, epoxy curing agents, thermal polymerization inhibitors, thickeners, antifoaming agents and leveling agents, in particular inorganic fillers.
To accelerate the photopolymerization it is possible to add amines, for example triethanolamine, N-methyldiethanolamine, p-dimethylaminobenzoate or Michler""s ketone. The action of the amines can be intensified by the addition of aromatic ketones of the benzophenone type. Examples of amines which can be used as oxygen scavengers are substituted N,N-dialkylanilines, as are described in EP 339841. Other accelerators, coinitiators and autoxidizers are thiols, thioethers, disulfides, phosphonium salts, phosphine oxides or phosphines, as described, for example, in EP 438123, in GB 2180358 and in JP Kokai Hei 6-68309.
It is further possible to add chain transfer agents which are customary in the art to the compositions according to the invention. Examples are mercaptans, amines and benzothiazol.
The curing process can be assisted by, in particular, compositions which are pigmented (for example with titanium dioxide), and also by adding a component which under thermal conditions forms free radicals, for example an azo compound such as 2,2xe2x80x2-azobis(4-methoxy-2,4-dimethylvaleronitrile), a triazene, diazo sulfide, pentazadiene or a peroxy compound, for instance a hydroperoxide or peroxycarbonate, for example t-butyl hydroperoxide, as described for example in EP 245639.
The compositions according to the invention may comprise as further additive (F) a photoreducable dye, e.g., xanthene-, benzoxanthene-, benzothioxanthene, thiazine-, pyronine-, porphyrine- or acridine dyes, and/or trihalogenmethyl compounds which can be cleaved by irradiation. Similar compositions are for example described in EP 445624.
Further customary additives (F), depending on the intended use, are optical brighteners, wetting agents or levelling assistants.
In order to cure thick and pigmented coatings it is appropriate to add glass microspheres or pulverized glass fibres, as described for example in U.S. Pat. No. 5,013,768.
The choice of additive(s) (F) is made depending on the field of application and on properties required for this field. The additives described above are customary in the art and accordingly are added in amounts which are usual in the respective application.
In certain cases it may be of advantage to use mixtures of two or more of the o-acyloxim photoinitiators. It is of course also possible to use mixtures with known photoinitiators (B1), for example mixtures with camphor quinone, benzophenone, benzophenone derivatives, acetophenone, acetophenone derivatives, for example xcex1-hydroxycycloalkyl phenyl ketones or 2-hydroxy-2-methyl-1-phenyl-propanone, dialkoxyacetophenones, xcex1-hydroxy- or xcex1-amino-acetophenones, e.g. (4-methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane, 4-aroyl-1,3-dioxolanes, benzoin alkyl ethers and benzil ketals, e.g. dimethyl benzil ketal, phenylglyoxalic esters and derivatives thereof, dimeric phenylglyoxalic esters, monoacyl phosphine oxides, e.g. (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, bisacylphosphine oxides, bis(2,6-dimethoxy-benzoyl)-(2,4,4-trimethyl-pentyl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-dipentoxyphenylphosphine oxide, trisacylphosphine oxides, ferrocenium compounds, or titanocenes, e.g. bis(cyclopentadienyl)-bis(2,6-difluoro-3-pyrrylphenyl)titanium.
Where the o-acyloxime photoinitiators are employed in hybrid systems, use may be made, in addition to the free-radical hardeners, of cationic photoinitiators, for example peroxide compounds, such as benzoyl peroxide (other suitable peroxides are described in U.S. Pat. No. 4,950,581 column 19, lines 17-25), aromatic sulfonium-, phosphonium- or iodonium salts as described for example in U.S. Pat. No. 4,950,581, column 18, line 60 to column 19, line 10 or cyclopentadienyl-arene-iron(II) complex salts, for example (xcex76-iso-propylbenzene)(xcex75-cyclopentadienyl)iron(II) hexafluorophosphate, as well as oxime sulfonic acid esters, as are, for example described in EP 780729.
Subject of the invention therefore also is a composition comprising additionally at least one photoinitiator (B1).
The photoinitiator (B) usually is added in an amount of 0.015 to 60 parts by weight, preferably 0.03 to 30 parts by weight, based on 100 parts by weight of component (A).
The amount refers to the sum of all photoinitiators added, if mixtures of initiators are employed. Accordingly, the amount either refers to the photoinitiator (B) or the photoinitiators (B)+(B1).
The invention also pertains to compositions comprising 100 parts by weight of component (A), 0.015 to 60 parts by weight of component (B), 5 to 300 parts by weight of component (C), 10 to 150 parts by weight of component (D) and 0.015 to 60 parts by weight of component (E).
The novel radiation-sensitive compositions find application as negative resists, having a very high sensitivity to light and being able to be developed in an aqueous alkaline medium without swelling. They are suitable as photoresists for electronics (electroless plating resist, electroplating resist, etch resist, solder resist).
The composition is applied uniformly to a substrate by means of known coating techniques, for example by spin coating, dip coating, knife coating, curtain coating, screen coating, brushing, spraying, especially by electrostatic spraying, and reverse-roll coating, and also by means of electrophoretic deposition. It is also possible to apply the photosensitive layer to a temporary, flexible support and then to coat the final substrate, for example a copper-clad circuit board, by transferring the layer via lamination.
The quantity applied (coat thickness) and the nature of the substrate (layer support) are dependent on the desired field of application. The range of coat thicknesses generally comprises values from about 0.1 xcexcm to more than 100 xcexcm, for example 0.1 xcexcm to 1 cm, preferably 1 xcexcm to 1000 xcexcm.
Following the coating of the substrates, the solvent is removed, generally by drying, to leave a coat of the photoresist on the substrate.
Subject of the invention also is a solder resist comprising a composition as described above.
The term xe2x80x9cimagewisexe2x80x9d exposure includes both, exposure through a photomask comprising a predetermined pattern, for example a slide, as well as exposure by means of a laser or light beam, which for example is moved under computer control over the surface of the coated substrate and in this way produces an image, and irradiation with computer-controlled electron beams. It is also possible to use masks made of liquid crystals that can be adressed pixel by pixel to generate digital images, as is, for example, described by A. Bertsch, J. Y. Jezequel, J. C. Andre in Journal of Photochemistry and Photobiology A: Chemistry 1997, 107, p. 275-281 and by K.-P. Nicolay in Offset Printing 1997, 6, p. 34-37.
As already mentioned, the compositions can be developed by aqueous alkalis. Particularly suitable aqueous-alkaline developer solutions are aqueous solutions of tetraalkylammonium hydroxides or of alkali metal silicates, phosphates, hydroxides and carbonates. Minor quantities of wetting agents and/or organic solvents may also be added, if desired, to these solutions. Examples of typical organic solvents, which may be added to the developer liquids in small quantities, are cyclohexanone, 2-ethoxyethanol, toluene, acetone and mixtures of such solvents.
The photosensitivity of the novel compositions can extend in general from about 200 nm to 600 nm (UV-vis region). Suitable radiation is present, for example, in sunlight or light from artificial light sources. Consequently, a large number of very different types of light sources are employed. Both point sources and arrays (xe2x80x9clamp carpetsxe2x80x9d) are suitable. Examples are carbon arc lamps, xenon arc lamps, medium-, high- and low-pressure mercury lamps, possibly with metal halide dopes (metal-halogen lamps), microwave-stimulated metal vapour lamps, excimer lamps, superactinic fluorescent tubes, fluorescent lamps, argon incandescent lamps, electronic flashlights, photographic flood lamps, light emitting diodes (LED), electron beams and X-rays. The distance between the lamp and the substrate to be exposed in accordance with the invention may vary depending on the intended application and the type and output of lamp, and may be, for example, from 2 cm to 150 cm. Laser light sources, for example excimer lasers, such as krypton F lasers for exposure at 248 nm are also suitable. Lasers in the visible region can also be employed. By this method it is possible to produce printed circuits in the electronics industry, lithographic offset printing plates or relief printing plates, and also photographic image recording materials.
The invention therefore also provides a process for the photopolymerization of compounds containing at least one ethylenically unsaturated double bond, which comprises adding to the abovementioned compounds at least one photoinitiator of formula I, II, III, IV, V or VI as described above and irradiating the resulting composition with electromagnetic radiation, in particular light of the wavelenghth 190 to 600 nm, namely a process for the photopolymerization of compounds containing ethylenically unsaturated double bonds, which comprises irradiating a composition as described above with electromagnetic radiation in the range from 190 to 600 nm, electron beam or X-rays.
The invention also pertains to a coated substrate which is coated on at least one surface with a composition as described above, as well as to a process for the photographic production of relief images, in which said coated substrate is subjected to imagewise exposure and then the unexposed portions are removed with a solvent.
Especially preferred is the use of the compositions according to the invention in an image-forming process, e.g. a process for the preparation of solder masks, wherein
(1) the components of the composition as described above are mixed
(2) the resulting composition is applied to the substrate (xe2x80x9ccoating of the substratexe2x80x9d)
(3) the solvent, if present, is evaporated, e.g. at a temperature between 80-90xc2x0 C.
(4) the coated substrate is exposed to irradiation through a negative mask (thereby initiating the reaction of the acrylate)
(5) the irradiated sample is developed, by washing with aqueous alkaline solution and thereby removing the uncured areas and
(6) the sample is thermally cured, e.g. at a temperature about 150xc2x0 C., thereby initiating the crosslinking between the carboxylic acid and the epoxy component.
This process is another object of the invention.
The compositions of the invention have a high sensitivity and resolution even at low concentration of the photoinitiator, with or without a sensitizer and are particularly suitable in aqueous developable photoresist applications. They have a good thermal stability and low volatility.
The examples which follow illustrate the invention in more detail. Parts and percentages are, as in the remainder of the description and in the claims, by weight, unless stated otherwise. Where alkyl radicals having more than three carbon atoms are referred to without any mention of specific isomers, the n-isomers are meant in each case.
The following oxime ester photoinitiators are used in the examples:
The following sensitzer compounds are used in the examples:

Photopolymerizable thermosetting resin compositions


A new and distinct cultivar of Anemone plant named ‘Pretty Lady Maria’, characterized by its upright and relatively compact plant habit; moderately vigorous growth habit; freely flowering habit; relatively large single type flowers that are white in color and positioned above the foliar plane; and good garden performance.

The present invention relates to a new and distinct cultivar of Anemone, botanically known as Anemone hupehensis and hereinafter referred to by the name 'Pretty Lady Maria'.
The new Anemone plant is a product of a planned breeding program conducted by the Inventor in Niigata, Japan. The objective of the breeding program is to create new uniform and freely-flowering Anemone plants with large flowers and attractive flower color.
The new Anemone plant originated from a cross-pollination in Niigata, Japan of Anemone hupehensis 'Alba', not patented, as the female, or seed, parent with an unnamed proprietary selection of Anemone hupehensis, not patented, as the male, or pollen, parent. The new Anemone plant was discovered and selected by the Inventor as a single flowering plant within the progeny of the stated cross-pollination in a controlled environment in Niigata, Japan in August, 2009.
Asexual reproduction of the new Anemone by root cuttings in a controlled environment in Niigata since October, 2009 has shown that the unique features of this new Anemone are stable and reproduced true to type in successive generations.


A first digital information signal, such as a digital video signal, is recorded in MPEG encoded form in the form of first packets in first track portions (TP.sub.1) on a record carrier. Program information contained packets (P.sub.0 ') are also recorded in the first track portions. In a subsequent editing step, an additional information signal, such as an audio signal, is MPEG encoded into second packets and recorded in second track portions (TP.sub.2) of the tracks. In order to enable a reproduction of the video signal and the additional audio signal in a later reproduction step, the program information contained packets (P.sub.0 ') recorded in the first track portions are such that the program information indicates that the first packets and at least the second packets belong together.

1. Field of the Invention
The invention relates to an apparatus for storing in a first recording step, a first digital information signal in a first storage region of a storage medium.
The invention also relates to a method for carrying out a recording and a subsequent edit step, and to a record carrier obtained with the apparatus or the method. More specifically, the invention relates to an apparatus of the helical scan type, for recording in a recording step, a digital video signal and a corresponding digital audio signal in first track portions on a record carrier.
2. Description of the Related Art
An apparatus for recording and/or reproducing a digital video signal is known from EP-A 492,704, corresponding to U.S. Pat. No. 5,245,483, document D1 in the list of related documents that can be found at the end of this description. The digital video signal is data compressed and subsequently channel encoded so as to obtain a signal that is suitable for recording in the first track portions in the tracks. The data compression technique carried out on the digital video signal may result in the digital video signal to be encoded into an MPEG encoded digital information signal.
The MPEG encoded information signal comprises transport packets that may occur irregularly in the serial datastream of the MPEG transport stream received. The ISO/IEC 13.818 international standard, part 1 `Systems`, dated Nov. 13, 1994, document D2 in the list of related documents, comprises a description of a transport system for transmitting an MPEG information signal, which may include a data compressed digital video signal and a corresponding data compressed digital audio signal, for broadcasting purposes or for transmission via a cable network. The MPEG information signal is in the form of transport packets comprises 188 bytes of information each.
Packets in the MPEG serial data stream comprise, apart from `system information`, one kind of information, that is: either a portion of a video signal, or a portion of an audio signal, or a portion of a data signal. A plurality of video signals and/or a plurality of audio signals and/or a plurality of data signals may be transmitted via the transport packets in the MPEG serial data stream. A packet also comprises information of only one of the video signals, or one of the audio signals or one of the data signals transmitted via the MPEG serial data stream. Further packets are present in the serial datastream which comprise information about which of packets belong to one and the same video or audio signal, and information indicating which of the video and audio signals belong together and form a so-called `program`.
A transmission of such MPEG information signal, in the form of a recording on and a reproduction from a record carrier, requires special measures to be taken in order to realize such kind of transmission.
Earlier filed applications U.S. Ser. No. 08/225,193, having a filing date of Aug. 4, 1994, now U.S. Pat. No. 5,579,183 (PHN 14.818), document (D3) in the list of related documents, and U.S. Ser. No. 08/253,535, having a filing date of Mar. 6, 1994, now U.S. Pat. No. 5,596,581 (PHA 21.886), document (D4) in the list of related documents, describe various of such measures to realize a recording and reproduction of an MPEG information signal.
It can generally be said that the recording of a complete MPEG information signal is not well possible, because of the too high data rate of the MPEG information signal.
One of the video signals and its corresponding audio signal(s) included in the MPEG serial datastream are now selected for recording. As a consequence, generally, transport packets will be selected on an irregular basis as a function of time. In order to preserve the timing relation between the subsequent packets selected, after having recorded and reproduced the packets, the earlier filed documents describe the measure to insert timing information (or a `time stamp`) in each of the packets recorded. Upon reproduction, the timing relation between the subsequent packets can be regained using the time stamps. The packets thus obtained are recorded in the first track portions after having been subjected to a channel encoding step.

Recording/reproducing apparatus for storing a digital information signal in a storage medium using packet a method and a record carrier, which further allows for editing the stored digital information signal by including references to additional packets


Shampoos are disclosed which comprise a synthetic surfactant, an insoluble, non-volatile silicone, a suspending agent and water. Suitable suspending agents include long chain esters of ethylene glycol, esters of long chain fatty acids, long chain amine oxides among many others.

Human hair becomes soiled due to its contact with the surrounding atmosphere and, to a greater extent, from sebum secreted by the head. The build-up of the sebum causes the hair to have a dirty feel and an unattractive appearance. The soiling of the hair necessitates it being shampooed with frequent regularity.
Shampooing the hair cleans by removing excess soil and sebum. However, the shampooing process has disadvantages in that the hair is left in a wet, tangled and generally unmanageable state. A variety of approaches have been developed to alleviate the after-shampoo problems. These range from the inclusion of hair conditioning aids in shampoos to post-shampoo application of hair conditioners, i.e., hair rinses. Hair rinses typically work by depositing a polymeric film or other material onto the hair. However, such solutions to a very prevalent problem have not been fully satisfactory. For one thing, hair rinses are generally liquid in nature and must be applied in a separate step following the shampooing, left on the hair for a length of time, and rinsed with fresh water. This, of course, is time consuming and is not convenient.
While shampoos have been disclosed which contain conditioning aids, they have not been totally satisfactory for a variety of reasons. One problem relates to compatibility problems between good cleaning anionic surfactants and the fatty cationic agents which are good conditioning agents. This caused other surfactants such as nonionics, amphoterics and zwitterionics to be examined by workers in the field. Many of these efforts are reflected in patients issued in the conditioning shampoo are. See for example U.S. Pat. No. 3,849,348, Nov. 19, 1974 to Hewitt; U.S. Pat. No. 3,990,991, Nov. 9, 1961 to Gerstein; and U.S. Pat. No. 3,822,312, July 2, 1974 to Sato.
The use of these other surfactants solved many of the compatibility problems but still did not provide complete answers in all areas. For instance cationic conditioners may not deliver the desired level of softness desired by users. Materials which can provide increased softness are silicones, both those which are soluble as well as insoluble in the shampoo matrix.
Silicones in shampoo compositions have been disclosed in a number of different publications. Such publications include U.S. Pat. No. 2,826,551, Mar. 11, 1958 to Geen; U.S. Pat. No. 3,964,500, June 22, 1976 to Drakoff; U.S. Pat. No. 4,364,837, Dec. 21, 1982 to Pader; and British Pat. No. 849,433, Sept. 28, 1960 to Woolston. While these patents disclose silicone containing compositions, they also do not provide answers to all of the problems encountered in making a totally satisfactory product. One problem is that of keeping a dispersed, insoluble silicone material suspended and the total product stable. A variety of materials have been included in silicone containing shampoos for purposes of thickening and stabilization but totally satisfactory solutions are lacking. It has been surprisingly found that certain long chain acyl derivatives and certain other long chain derivatives can provide stabilization without interfering unduly with deposit of the silicone material onto the hair and other shampoo functions.
It is an object of the present invention to provide a stable silicone containing conditioning shampoo.
It is a further object of the present invention to provide silicone shampoo compositions containing certain long chain derivatives.
These and other objects will become readily apparent from the detailed description which follows.
Unless otherwise indicated, all percentages and ratios herein are by weight.


A quick release connector includes a connector body, a positioning ring, a mounting sleeve, and an elastic member. The connector body has a peripheral wall formed with two opposite receiving holes and two opposite guide slots. The positioning ring is provided with a plurality of flexible locking blocks. Thus, the locking blocks are combined together by the positioning ring, so that the locking blocks of the positioning ring are placed into the receiving holes and the guide slots of the connector body easily and quickly, thereby simplifying the construction of the quick release connector, and thereby facilitating assembly and fabrication of the quick release connector.

1. Field of the Invention
The present invention relates to a connector and, more particularly, to a quick release connector.
2. Description of the Related Art
A conventional quick release connector in accordance with the prior art shown in FIGS. 6-8 comprises a connector body 50 having an inside formed with a mounting chamber 58 and having a peripheral wall formed with four receiving holes 51 connected to the mounting chamber 58, four locking blocks 60 movably mounted in the receiving holes 51 of the connector body 50 and extendable into the mounting chamber 58 of the connector body 50, a mounting sleeve 70 movably mounted on the connector body 50 and having an inner wall provided with a plurality of push blocks 72 that are movable to push the locking blocks 60 into the mounting chamber 58 of the connector body 50, and an elastic member 61 mounted on the connector body 50 and biased between the connector body 50 and the mounting sleeve 70 to push the mounting sleeve 70 outwardly relative to the connector body 50 and to push the push blocks 72 to press the locking blocks 60. The connector body 50 has an end portion provided with a protruding limit flange 53. Each of the receiving holes 51 of the connector body 50 is provided with two catch walls 52. The inner wall of the mounting sleeve 70 is provided with a plurality of limit plates 71 that are movable to rest on the limit flange 53 of the connector body 50 to prevent the mounting sleeve 70 from being detached from the connector body 50.
In operation, when the mounting sleeve 70 is pressed toward the connector body 50, the elastic member 61 is compressed, and the push blocks 72 of the mounting sleeve 70 is movable to detach from the locking blocks 60, so that the locking blocks 60 are movable in the receiving holes 51 of the connector body 50. Thus, when an insert is inserted into the mounting chamber 58 of the connector body 50, the locking blocks 60 are extendable into an annular retaining groove of the insert. After the mounting sleeve 70 is released, the mounting sleeve 70 is pushed outwardly relative to the connector body 50 by the restoring force of the elastic member 61 so that the push blocks 72 of the mounting sleeve 70 are movable to press the locking blocks 60 into the retaining groove of the insert, so that the insert is locked onto the connector body 50 by the locking blocks 60.
However, it is necessary to place all of the locking blocks 60 into the receiving holes 51 of the connector body 50, so that the quick release connector cannot be assembled easily and quickly, thereby wasting time and increasing costs of assembly and fabrication of the quick release connector In addition, the catch walls 52 of each of the receiving holes 51 of the connector body 50 are formed by four slides "A" in a die during the molding process as shown in FIG. 8, so that the number of the slides "A" is increased, thereby increasing the costs of fabrication. Further, the connector body 50 is provided with four pairs of catch walls 52 so that the connector body 50 needs a relatively larger die removal space in the die, and the die only forms a few connector bodies 50 at a time, thereby decreasing the working efficiency, and thereby increasing the costs of fabrication.

Quick release connector that is assembled easily and quickly


The disclosure relates to the establishment of a cell line having immune tolerance property using an optimal temperature profiling technique under a human body-like environment, and use thereof.

Cell therapeutic agents can be used as a fundamental therapeutic method for recovering the function and tissue of a damaged cell by manipulating and culturing the cells collected from a patient or other people in vitro and injecting them into the patient. Therefore, development of cell therapeutic agents for the diseases which are impossible or difficult to treat by existing treatment methods, such as neurological diseases, pulmonary diseases, liver diseases, and cancers, is actively carried out. In particular, there has been a great interest worldwide in clinical trials using stem cells having self-renewal capability and differentiation capability into other cells, as more than thousands of cases are under progress.
However, since stem cells are acquired through long-term in vitro culture and then injected into patients, there is a risk of mutation of stem cells into cancer cells and tumor formation during these processes and a risk caused by heterologous proteins such as FBS used for cell storage and culture, and there are problems associated with immunogenicity caused by major histocompatibility complex (MHC) mismatches, and immune rejection that requires short-term or long-term follow-up due to the immunogenicity. Accordingly, these risks and problems bring about the biggest technical difficulty in the commercialization of stem cell therapeutics agents. In addition, with respect to cell transplantation and transplantation of extracellular vesicles such as exosomes and microvesicles secreted from the cells, various immunomodulatory and inhibitory drugs have been developed in order to solve immune rejections caused by immunogenicity such as cell therapeutic agents, but they can only be a partial solution for the problems.
Meanwhile, it has been known that a culture medium of stem cells contains various growth factors and cytokines produced from stem cells, and therefore, its commercial use as pharmaceuticals and cosmetics is rapidly increasing. As related prior arts, there have been developed a cosmetic composition for improving scalp comprising a stem cell culture medium (Korean Patent Application Publication No. 10-2017-0132460) and a method for producing a culture supernatant of mesenchymal stem cells having exceptional tissue regeneration capacity, exceptional disease healing action, or high physiological activity (Korean Patent Application Publication No. 10-2017-0121205).
However, stem cell culture media are currently produced by culturing stem cells isolated from human body fat, etc., using a general cell culture method, and substances that can be included in the culture media are limited, and accordingly, various effects cannot be achieved.

Cell line consecutively expressing HLA-G protein and method for preparing the same

Abstract: The stem cell line exhibits immune tolerance property as they consecutively secret and express HLA-G proteins, and the culture medium of the stem cells contains a large amount of proteins capable of recovering various physiological functions and extracellular vesicles, and thus, the novel cell line or a culture medium thereof can be effectively used in various industries such as medicines and cosmetics.


A glitch protect valid cell and method for maintaining a desired logic state value. The glitch protect valid cell includes a memory element, a state machine, and a glitch protect circuit. The glitch protect circuit includes a propagation delay assembly coupled to a restore assembly. The propagation delay assembly includes a first pull down network coupled to a NOR gate. The restore assembly includes a second pull down network coupled to the propagation delay assembly. Responsive to a glitch signal and timing signal, the first pull down network resets the initial state value of a true valid bit to ultimately enable a pull up network in the NOR gate. Responsive to enablement of the NOR gate pull up network, the second pull down network resets the complement valid bit in the memory element to consequently restore the initial state of the true valid bit.

1. Field of the Invention
The present invention generally relates to a semiconductor memory device. More particularly, but not by way of limitation, the present invention relates to a glitch protect valid cell and method for maintaining a desired state value of a true valid bit in response to a glitch signal and a timing signal.
2. Description of the Related Art
Some common semiconductor memory devices, such as a content addressable memory (CAM) device, typically attach a valid cell at the beginning of a row of integrated data storage units. In effect, valid cells grant access for word data to be stored to and retrieved from a row of data storage units according to the logical state value of a true valid bit stored in a valid cell. Typically, access to entry data is granted if the state value of the true valid bit is "valid", often valued as a logical "1", and denied if the logic state value of the true valid bit is "invalid", often valued as a logical "0".
Illustratively, each word entry in a CAM device features a true valid bit stored in a valid cell. As opposed to other semiconductor devices that first require at least one specific memory address prior to retrieving entry data, CAM semiconductor devices provide high speed data access whereby contents in memory-are accessed through a relatively faster search and match operation scheme. Accordingly, because of their quick and effective search and match capabilities, CAM semiconductor devices with valid cells are often used in high speed switching systems ranging from communication and computer networks to voice and image recognition systems, such as routers, core switches, remote access servers, processor address translation, memory cache hierarchies, and digital-subscriber-line access multiplexers.
Problems may arise, accumulate, and potentially compound if one or many signals for invalidating a true valid bit arrive too late after a typical high speed compare and match operation between the valid cell and CAM array. Unfortunately, there exists no known device that adequately compensates for time delayed invalidate functions, hereinafter referred to as a "glitch signal(s)", with respect to a true valid bit within a valid cell. In this disclosure and appended claims the term "glitch signal" refers to a signal variance typically in the form of a brief pulse which could possibly trigger a logic state change of a true valid bit. Typically, a signal variance results from a time delay in a combinational logic circuit from the point in time that input signals are applied until their effect propagates through the various components of the combinational logic circuit and resulting outputs react to the inputs.
Therefore, a need exists for a device that is responsive to at least one glitch signal. In particular, there exists a need for a device that restores an initial valid state value of a true valid bit after being subjected to at least one glitch signal. Moreover, there exists a need for a device that maintains an initial invalidate state value of a true valid bit after being subjected to at least one glitch signal. Many other problems and disadvantages of the prior art will become apparent to one skilled in the art after comparing such prior art with the present invention as herein described.

Glitch protect valid cell and method for maintaining a desired state value


The present invention provides a pyrazole derivative of the general formula (1),

Conventionally, there are known a number of pyrazole derivatives having pesticidal activity such as herbicidal activity or insecticidal activity. However, nothing has been reported on any pyrazole derivative having a substituted oxy group at the 3-position of a pyrazole ring and a substituted carbamoyl group or a substituted thiocarbamoyl group on a nitrogen atom at the 1-position as shown in the following general formula (1) in the present invention, nor is there any report on biological activities thereof. As pyrazole derivatives structurally similar to the pyrazole derivative (1) of the present invention, there are known pyrazole derivatives described in WO97/24332 (EP876351, JP2000/502686, U.S. Pat. No. 6,075,149) and EP256667 (JP63/044571, U.S. Pat. No. 5,374,644). However, these pyrazole derivatives are completely different from the pyrazole derivative (1) of the present invention in that they have an alkyl group on a nitrogen atom of their pyrazole ring. Further, it is described that the pyrazole derivatives described in the above WO97/24332 and EP256667 have pesticidal activity against fungi and harmful insects, but these Publications describe nothing concerning any other biological activity.

Pyrazole derivative, intermediate therefor, processes for producing these, and herbicide containing these as active ingredient

Abstract: which has an excellent efficacy as an active component for a herbicide, an intermediate for the production thereof, processes for the production thereof, and a herbicide containing the derivative as an active ingredient.


Expandable reamer tools include an outer body, a fluid passageway extending through the outer body, and at least one blade configured to slide relative to the outer body between a retracted position and an expanded position. In some embodiments, the tools may include a formation-engaging surface comprising a gage area. In other embodiments, the tools may include a radially recessed area extending from a back edge of the formation-engaging surface. Methods for removing such expandable reamer tools from a borehole are also disclosed.

In drilling oil, gas, and geothermal wells, casing is conventionally installed and cemented to prevent the well walls from caving into the subterranean borehole. Casing is also conventionally installed to isolate different formations, to prevent crossflow of formation fluids, and to enable control of formation fluids and pressure as the borehole is drilled. To increase the depth of a previously drilled borehole, new casing is laid within the previous casing. While adding additional casing allows a borehole to reach greater depths, it has the disadvantage of narrowing the borehole. Narrowing the borehole restricts the diameter of any subsequent sections of the well because the drill bit and any further casing must pass through the existing casing. As reductions in the borehole diameter are undesirable because they limit the production flow rate of oil and gas through the borehole, it is often desirable to enlarge a subterranean borehole to provide a larger borehole diameter for installing additional casing beyond previously installed casing or to enable better production flow rates of hydrocarbons through the borehole.
A variety of approaches have been employed for enlarging a borehole diameter. One conventional approach used to enlarge a subterranean borehole includes using eccentric and bi-center bits. For example, an eccentric bit with an extended or enlarged cutting portion is rotated about its axis thereby producing an enlarged borehole diameter. An example of an eccentric bit is disclosed in U.S. Pat. No. 4,635,738, assigned to the assignee of the present invention. A bi-center bit assembly employs two longitudinally superimposed bit sections with laterally offset axes, which when rotated produce an enlarged borehole diameter. An example of a bi-center bit is disclosed in U.S. Pat. No. 5,957,223, which is also assigned to the assignee of the present invention.
Another conventional approach used to enlarge a subterranean borehole includes employing an extended bottom-hole assembly with a pilot drill bit at the distal end thereof and a reamer assembly some distance above. This arrangement permits the use of any standard rotary drill bit type, be it a rock bit or a drag bit, as the pilot bit, and the extended nature of the assembly permits greater flexibility when passing through tight spots in the borehole as well as the opportunity to effectively stabilize the pilot drill bit so that the pilot hole and the following reamer will traverse the path intended for the borehole. This aspect of an extended bottom-hole assembly is particularly significant in directional drilling. The assignee of the present invention has, to this end, designed as reaming structures so-called "reamer wings," which generally comprise a tubular body having a fishing neck with a threaded connection at the top thereof and a tong die surface at the bottom thereof, also with a threaded connection. U.S. Pat. Nos. 5,497,842 and 5,495,899, both assigned to the assignee of the present invention, disclose reaming structures including reamer wings. The upper midportion of the reamer wing tool includes one or more longitudinally extending blades projecting generally radially outwardly from the tubular body, the outer edges of the blades carrying PDC cutting elements.
Conventional expandable reamers may include blades pivotably or hingedly affixed to a tubular body and actuated by way of a piston disposed therein as disclosed by U.S. Pat. No. 5,402,856 to Warren. In addition, U.S. Pat. No. 6,360,831 to Akesson et al., discloses a conventional borehole opener comprising a body equipped with at least two hole-opening aims having cutting means that may be moved from a position of rest in the body to an active position by exposure to pressure of the drilling fluid flowing through the body. The blades in these reamers are initially retracted to permit the tool to be run through the borehole on a drill string and once the tool has passed beyond the end of the casing, the blades are extended so the bore diameter may be increased below the casing.
The blades of conventional expandable reamers have been sized to minimize a clearance between themselves and the tubular body in order to prevent any drilling mud and earth fragments from becoming lodged in the clearance and binding the blade against the tubular body.
Notwithstanding the various prior approaches to drill and/or ream a larger-diameter borehole below a smaller-diameter borehole, the need exists for improved apparatus and methods for doing so. For instance, bi-center and reamer wing assemblies are limited in the sense that the pass-through diameter is nonadjustable and limited by the reaming diameter. Furthermore, conventional bi-center and eccentric bits may have the tendency to wobble and deviate from the path intended for the borehole. Conventional expandable reaming assemblies, while more stable than bi-center and eccentric bits, may be subject to damage when passing through a smaller diameter borehole or casing section, may be prematurely actuated, and may present difficulties in removal from the borehole after actuation.


An electronic product includes an electronic enclosure having a housing pocket fabricated as a seamless single unitary molded structure. The single unitary molded structure defines a cavity therein and has at least one molded undercut feature extending over a portion of the cavity. The housing pocket includes a side opening that is sufficiently large to allow lateral insertion of the electronic assembly into position in the cavity with at least a portion of the electronic assembly extending underneath the at least one molded undercut feature.

Hollow enclosures ("electronic enclosures") are commonly used to house electrical or electronic components and circuits ("electronic assemblies") of a variety of electronic products and instruments. The electronic enclosures serve to provide structural support to hold the electronic assemblies in place and also to protect or isolate the electronic assemblies from external environmental hazards (e.g., dust). The variety of electronic products and instruments using such electronic enclosures is diverse (e.g., consumer electronics, game consoles, handheld and desktop computers, industrial PC's, keyboards, computer input devices, pushbuttons, cell phones, smartphones, and charging stations, etc.).
An enclosure for an electronic instrument or product is an integral part of its design, playing a key role in its looks, presentation, value and quality perception. Electronic enclosures are generally rectangular in shape and are designed to house a specific electronic product or instrument (e.g., remote controls, cash register or calculator, etc.). The electronic enclosures are often made by fitting or joining together, for example, several shaped parts or sub-parts. For example, an electronic enclosure for a common computer keyboard includes a shaped top panel fitted on to a shaped semi-hollowed bottom panel. The two panels, which may be glued, screwed or fastened together, are shaped to form a hollow space or cavity to hold keyboard switches and circuits. The top panel may include cutouts for securely mounting and surrounding "keys" or pushbuttons. In the case of an electronic enclosure made of plastic, the shaped parts or sub-parts of the enclosure are commonly made by plastic injection processes using mold core/cavity splits.
A requirement of the plastic injection processes used to make the shaped parts is that the mold cores should eject freely from the injected plastic parts. This requirement prevents ledges, overhangs, or undercuts from being designed on the shaped parts or sub-parts that are used to assemble an electronic enclosure (e.g., a box-like enclosure). Thus, several parts (e.g., at least a top panel and a bottom panel) have to be used to assemble an electronic enclosure whose overall structure includes an undercut cavity. As a result of using several parts, unavoidable parting lines are formed where different parts are fitted or joined together in the enclosure assembly. Further, assembling electronic enclosures from several parts can be an expensive proposition.
Consideration is now being given to ways of making electronic enclosures.