Compounds of the formula I

The invention relates to alkylphenylbisacylphosphine oxides and to specific mixtures of bisacylphosphine oxide compounds with other photoinitiators.
Bisacylphosphine oxide compounds are known as photoinitiators from EP-A-184095, for example. Alkylbisacylphosphine oxides and also mixtures of these compounds with xcex1-hydroxy ketones or benzophenone compounds are disclosed in GB-A-2259704. EP-A-446175 describes mixtures of three components, namely mono- or bisacylphosphine oxide, xcex1-hydroxyketone and benzophenone.
In industry there is a need for effective photoinitiators and photoinitiator mixtures which are capable of curing photopolymerizable compositions efficiently and without extreme yellowing phenomena.
It has now been found that compounds of the formula I
in which
R1 is C1-C4alkyl,
R2 is hydrogen, C1-C4alkyl or C1-C4alkoxy and
R3, R4, R5, R6 and R7 independently of one another are hydrogen, halogen, C1-C20alkyl, cyclopentyl, cyclohexyl, C2-C12alkenyl, C2-C18alkyl which is interrupted by one or more oxygen atoms, or are phenyl-substituted C1-C4alkyl, or are phenyl which is unsubstituted or is mono- or disubstituted by C1-C4alkyl and/or C1-C4alkoxy, with the provisos that at least one of the radicals R3, R4, R5, R6 and R7 is other than hydrogen and that, if R1 and R2 are methyl, R3 and R6 are not methyl, are suitable as very good photoinitiators.
It has also been found that the photoinitiators of the formula 1a can be combined with compounds of the formula II, III and/or IV to give initiator mixtures (blends) having good curing properties, especially in respect of the required surface curing and through-curing of polymerizable compositions. The cured compositions, moreover, exhibit highly advantageous properties in the context of yellowing.
This application therefore provides a photoinitiator mixture comprising at least one compound of the formula (1a)
in which
R1 is C1-C4alkyl;
R2 is hydrogen, C1-C4alkyl or C1-C4alkoxy, and
R3, R4, R5, R6 and R7 independently of one another are hydrogen, halogen, C1-C20alkyl, cyclopentyl, cyclohexyl, C2-C12alkenyl, C2-C18alkyl which is interrupted by one or more oxygen atoms, or are phenyl-substituted C1-C4alkyl, or are phenyl which is unsubstituted or is mono- or disubstituted by C1-C4alkyl and/or C1-C4alkoxy;
and at least one compound of the formula (II)
in which
R8 is hydrogen, C1-C18alkyl, C1-C18alkoxy, xe2x80x94OCH2CH2xe2x80x94OR12, a group
xe2x80x83or a group
In which I is a number from 2 to 10 and A is a radical
R9 and R10 independently of one another are hydrogen, C1-C6alkyl, phenyl, C1-C16-alkoxy, OSiR13R14R14 or xe2x80x94O(CH2CH2O)qxe2x80x94C1-C16alkyl, in which q is a number from 1 to 20, or R9 and R10, together with the carbon atom to which they are attached, form a cyclohexyl ring;
R11 is hydroxyl, C1-C16alkoxy or xe2x80x94O(CH2CH2O)qxe2x80x94C1-C16alkyl;
where R9, R10 and R11 are not all simultaneously C1-C16alkoxy or xe2x80x94O(CH2CH2O)qxe2x80x94C1-C16alkyl,
R12 is hydrogen, C1-C8alkyl,
xe2x80x83and
R13, R14a and R14 independently of one another are C1-C4alkyl or phenyl; and/or at least one compound of the formula (III)
in which
R15, R15a, R16 and R17 independently of one another are hydrogen, methyl, phenyl, methoxy, xe2x80x94COOH, unsubstituted or C1-C4alkyl-substituted phenyl, or a group xe2x80x94OCH2CH2OR12 or xe2x80x94SCH2CH2R12 in which R12 is as defined for formula II; and/or at least one compound of the formula (IV)
in which
R18 is hydrogen, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, halogen or a group N(R22)2;
R19 is as defined for R18 or is the group
xe2x80x83in which case the radical R18 from the formula IV and the radical R18 of this group (IVa) together are a direct bond, and the other radicals are as defined below;
R20 is C1-C8alkyl;
R21 is hydrogen, xe2x80x94CHxe2x95x90CHR24, or phenyl which is unsubstituted or is substituted one to three times by C1-C12alkyl, C1-C4alkoxy or halogen;
or R20 and R21, together with the carbon atom to which they are attached, form a cyclohexyl ring;
R22 and R23 independently of one another are C1-C4alkyl, or
R22 and R23, together with the nitrogen atom to which they are attached, form a five- or six-membered saturated or unsaturated ring which can be interrupted by xe2x80x94Oxe2x80x94, xe2x80x94NHxe2x80x94 or xe2x80x94N(CH3)xe2x80x94,
R24 is hydrogen or C1-C4alkyl; and
R25 is hydrogen or C1-C12alkyl.
C1-C20alkyl can be linear or branched and is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl or eicosyl. Preference is given to C1-C18alkyl, e.g. C1-C12- or C1-C8alkyl, especially C1-C4alkyl.
C1-C18alkyl, C1-C6alkyl and C1-C4alkyl can have the same meanings as given above up to the corresponding number of carbon atoms.
C2-C18alkyl interrupted by one or more oxygen atoms is, for example, interrupted by 1-5, e.g. 1-3 or 1 or 2 times by xe2x80x94Oxe2x80x94. This produces structural units such as xe2x80x94O(CH2)2OH, xe2x80x94O(CH2)2OCH3, xe2x80x94O(CH2CH2O)2CH2CH3, xe2x80x94CH2xe2x80x94Oxe2x80x94CH3, xe2x80x94CH2CH2xe2x80x94Oxe2x80x94CH3, xe2x80x94[CH2CH2O]yxe2x80x94CH3, where y=1-5, xe2x80x94(CH2CH2O)5CH2CH3, xe2x80x94CH2xe2x80x94CH(CH3)xe2x80x94Oxe2x80x94CH2xe2x80x94CH2CH3 or xe2x80x94CH2xe2x80x94CH(CH3)xe2x80x94Oxe2x80x94CH2xe2x80x94CH3.
The radical xe2x80x94O(CH2CH2O)qxe2x80x94C1-C16alkyl represents 1 to 20 successive ethylene oxide units whose chain ends in a C1-C16alkyl. q is preferably q 1 to 10, e.g. 1 to 8, especially 1 to 6. The chain of ethylene oxide units ends in a C1-C12alkyl, e.g. C1-C8alkyl, in particular in a C1-C4alkyl. Here C1-C16alkyl can have the meanings given above up to the corresponding number of carbon atoms.
C2-C12alkenyl can be linear or branched and there may be more than one unsaturated bond in the molecule. Examples are vinyl, allyl, methylvinyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl.
C1-C18alkoxy can be linear or branched and is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, isopentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy or octadecyloxy. Further examples are C1-C12alkoxy or C1-C8alkoxy, especially C1-C4alkoxy.
C1-C6alkoxy and C1-C4alkoxy can have the same meanings as given above up to the corresponding number of carbon atoms.
C1-C4alkylthio can be linear or branched and is, for example, methylthio, ethylthio, propylthio, isopropylthio, butylthio or tert-butylthio, especially methylthio.
Phenyl-substituted C1-C4alkyl is, for example, benzyl, 2-phenylethyl, 3-phenylpropyl, xcex1-methylbenzyl or xcex1,xcex1-dimethylbenzyl, especially benzyl.
Substituted phenyl is substituted from one to five times, for example once, twice or three times, especially once or twice, on the phenyl ring. The pattern of substitution on the phenyl ring is, for example, 2-, 3-, 4-, 5-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-, 2,4,6- or 3,4,5-, C1-C4alkyl and C1-C4alkoxy substituents can have the meanings given above. Examples of substituted phenyl are tolyl, xylyl, 4-methoxyphenyl, 2,4- and 2,5-dimethoxyphenyl, ethylphenyl, and 4-alkoxy-2-methylphenyl.
Halogen is, for example, chlorine, bromine or iodine, especially chlorine.
If R1 is the group
where the radical R18 from the formula IV and the radical R18 of this group together are a direct bond, then the result is structures of the formula IVb
If R22 and R23, together with the nitrogen atom to which they are attached, form a ring which can additionally be interrupted by xe2x80x94Oxe2x80x94, xe2x80x94NHxe2x80x94 or xe2x80x94N(CH3)xe2x80x94, then the ring formed is, for example, a morpholino, piperidino or methylpiperidino ring.
The novel compounds of the formula I (and 1a) can be prepared, for example, by double acylation of a primary phosphine (V) with at least 2 equivalents of an acid chloride (VI) in the presence of at least two equivalents of a base and subsequent oxidation of the resulting diacylphosphine (VII) in accordance with the equations:
R1, R2, R3, R4, R5, R6 and R7 are as defined in claim 8.
Examples of suitable bases are tertiary amines, pyridine, alkali metals, lithium diisopropylamide, butyllithium, alkaline earth metal carbonates, alkali metal alcoholates and alkali metal hydrides. The first reaction stage takes place preferably in solution. Particularly suitable solvents are hydrocarbons, such as alkanes and alkane mixtures, cyclohexane, benzene, toluene and xylene. The reaction is carried out at various temperatures depending on the solvent and starting materials used. In the case of the use of bases such as lithium diisopropylamide or butyllithium, it is expedient to work, for example, at from xe2x88x9240 to 0xc2x0 C.
Reactions using tertiary amines, alkali metals or alkali metal hydrides as bases are expediently carried out, for example, at from 10 to 120xc2x0 C., preferably from 20 to 80xc2x0 C. After the base chloride formed has been separated off, the phosphine (VII) can be isolated by evaporative concentration. The crude reaction product can be used further without purification or else can be purified by means, for example, of crystallization. However, the second reaction stage can also be carried out without isolating (VII), using the solution of the crude product.
Particularly suitable oxidizing agents for the second stage in the preparation of the oxides are hydrogen peroxide and organic peroxy compounds, examples being peracetic acid, air and pure oxygen.
The reaction products can be purified by conventional methods, for example by crystallization or chromatography.
The phosphines of the formula (V) can be prepared, for example, by reducing the corresponding dichlorides (VII), phosphonic esters (IX) or phosphonous esters (X):
Rxe2x80x2 is, for example, methyl or ethyl.
Reductions are usually carried out with LiAlH4; SiHCl3; Ph2SiH2; a) LiH b) H2O; a) Li/tetrahydrofuran b) H2O or a) Naltoluene b) H2O.
Hydrogenation using LiAlH4, for example, can also be found in Helv. Chim. Acta 1966, No. 96, page 842.
The dichlorophosphine compounds of the formula VII can be obtained, for example, by reacting a corresponding aromatic compound with phosphorus trichloride and aluminium chloride.
The dichlorides (VII) can also be obtained, for example, by Grignard reaction of the corresponding brominated aromatic compounds (XI) with PCl3 (cf. e.g. Helv.Chim. Acta 1952, No 35, page 1412):
R1, R2 R3, R4, R5, R6 and R7 are as defined in claim 8.
The diesters of formula (IX) can be prepared, for example, by reacting the brominated aromatic compounds (XI) with a trisphosphorous ester (XII). Reactions of this kind are described, for example in DE-C-1810431.
The phosphonous esters (X) can be obtained, for example by reacting a phosphorus dichloride (VII) with an alcohol:
The brominated aromatic compounds (XI) are obtained by prior-art bromination reactions, for example by reacting alkoxylated aromatic compounds with N-bromosuccinimide or bromine/acetic acid.
The acid chlorides of the formula (VI) are prepared by generally known methods from the prior art.
The preparation of the compounds of the formulae II and III is generally known, and some of the compounds are commercially available. The preparation of oligomeric compounds of the formula II, for example, is described in EP-A-161 463. A description of the preparation of the compounds of the formula III can be found for example in EP-A-209 831. The preparation of compounds of the formula IV is given, for example, in EP-A-3002 or EP-A-284 561. Furthermore, some compounds of the formula IV are available commercially.
Examples of novel compounds are:
Bis(2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide;
bis(2,4,6-trimethylbenzoyl)-2-methylphenylphosphine oxide;
bis(2,4,6-trimethylbenzoyl)-4-methylphenylphosphine oxide;
bis(2,4,6-trimethylbenzoyl)-2,5-diethylphenylphosphine oxide;
bis(2,4,6-trimethylbenzoyl)-2,3,5,6-tetramethylphenylphosphine oxide.
The novel photoinitiator mixtures are prepared, for example, by mixing, milling, melting or dissolving the individual components, it being possible to use liquid components as solvents for the respective combination partners. It is also possible, however, to combine the components in an inert solvent.
The photoinitiator mixtures comprise, for example, 2-90%, e.g. 5-50%, 5-40%, especially 5-25%, of compounds of formula Ia and 98-50%, e.g. 95-60%, especially 95-75%, of compounds of the formula II, III and/or IV. Other mixtures which are of interest are those in which the proportion of compounds of the formula Ia in the mixture with compounds of the formula II and III and/or IV is from 30 to 70%.
Preferred examples of compounds of the formula II and III are 1-benzoylcyclohexanol, 2,2-dimethoxy-1,2-diphenylethan-1-one and 1-benzoyl-1-hydroxy-1-methylethane.
Examples of novel photoinitiator mixtures (blends) are
5% bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 95% 1-benzoyl-1-hydroxy-1-methylethane;
5% bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 95% 1-benzoylcyclohexanol;
25% bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 75% 1-benzoylcyclohexanol;
25% bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 75% 1-benzoyl-1-hydroxy-1-methylethane;
25% bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 75% 2,2-dimethoxy-1,2-diphenylethan-1-one;
5% bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 95% 2,2-dimethoxy-1,2-diphenylethan-1-one;
25% bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 75% 4-(2-hydroxyethoxy)benzoyl-1-hydroxy-1-methylethane;
5% bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 95% 4-(2-hydroxyethoxy)benzoyl-1-hydroxy-1-methylethane;
5% bis(2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide and 95% 1-benzoylcyclohexanol;
5% bis(2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide and 95% 1-benzoyl-1-hydroxy-1-methylethane;
25% bis(2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide and 75% 1-benzoylcyclohexanol;
25% bis(2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide and 75% 1-benzoyl-hydroxy-1-methylethane;
5% bis(2,4,6-trimethylbenzoyl)-4-tert-butyl-2,6-dimethylphenylphosphine oxide and 95% 1-benzoylcyclohexanol;
5% bis(2,4,6-trimethylbenzoyl)-4-tert-butyl-2,6-dimethylphenylphosphine oxide and 95% 1-benzoyl-1-hydroxy-1-methylethane;
25% bis(2,4,6-trimethylbenzoyl)-4-tert-butyl-2,6-dimethylphenylphosphine oxide and 75% 1-benzoylcyclohexanol;
25% bis(2,4,6-trimethylbenzoyl)-4-tert-butyl-2,6-dimethylphenylphosphine oxide and 75% 1-benzoyl-1-hydroxy-1-methylethane;
5% bis(2,6-dimethylbenzoyl)phenylphosphine oxide and 95% 1-benzoyl-1-hydroxy-1-methylethane;
5% bis(2,6-dimethylbenzoyl)phenylphosphine oxide and 95% 1-benzoylcyclohexanol;
25% bis(2,6-dimethylbenzoyl)phenylphosphine oxide and 75% 1-benzoyl-1-hydroxy-1-methylethane;
25% bis(2,6-dimethylbenzoyl)phenylphosphine oxide and 75% 1-benzoylcyclohexanol;
5% bis(2,4,6-trimethylbenzoyl)-2,5-dimethylphenylphosphine oxide and 95% 1-benzoylcyclohexanol;
5% bis(2,4,6-trimethylbenzoyl)-2,5-dimethylphenyl-phosphine oxide and 95% 1-benzoyl-1-hydroxy-1-methylethane;
25% bis(2,4,6-trimethylbenzoyl)-2,5-dimethylphenylphosphine oxide and 75% 1-benzoylcyclohexanol;
25% bis(2,4,6-trimethylbenzoyl)-2,5-dimethylphenylphosphine oxide and 75% 1-benzoyl-1-hydroxy-1-methylethane;
25% bis(2,4,6-trimethylbenzoyl)-2,5-dimethylphenylphosphine oxide and 75% 2,2-dimethoxy-1,2-diphenylethan-1-one;
25% bis(2,4,6-trimethylbenzoyl)-2,5-dimethylphenylphosphinoxide and 75% 4-(2-hydroxyethoxy)benzoyl-1-hydroxy-1-methylethane.
Photoinitiator mixtures of particular interest are those obtained by dissolving bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide in a liquid hydroxy ketone compound. More than 2 components, especially 3, are preferably used in the mixture. The three-component mixtures are expediently prepared by mixing the respective constituents and heating the mixture gently, for example at 50-60xc2x0 C.
The invention additionally provides photoinitiator mixtures comprising at least one compound of the formula Ia and two compounds of the formula II.
Preference is given, for example, to 3-component mixtures comprising
25% bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide,
70% 1-benzoylcyclohexanol and
5% 1-benzoyl-1-hydroxy-1-methylethane; or
25% bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide,
60% 1-benzoylcyclohexanol and
15% 1-benzoyl-1-hydroxy-1-methylethane; or
25% bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide,
50% 1-benzoylcyclohexanol and
25% 1-benzoyl-1-hydroxy-1-methylethane.
Preference is given to compounds of the formula I in which R3, R4, R5, R6 and R7 are hydrogen, C1-C8alkyl, phenyl, allyl, benzyl, cyclohexyl or chlorine.
Further advantageous compounds of the formula I and Ia are those in which 3, R4 and R5 are hydrogen, C1-C4alkyl, especially methyl, or phenyl.
Attention is drawn to compounds of the formula I and Ia in which R6 and R7 are hydrogen or C1-C4alkyl, especially methyl.
Particular preference is given to those compounds of the formula I and Ia in which R2 is hydrogen or C1-C4alkyl.
Preference extends to the compounds of the formula I and Ia in which R1 is methyl.
Preference is likewise given to compounds of the formula I and Ia in which R1 and R2 are the same.
Also of interest are compounds of the formula I and Ia in which R1 and R2 are C1-C4alkyl, especially methyl.
In the novel photoinitiator mixtures, preference is given to the use of compounds of the formula Ia, in which R3, R4, R5, R6 and R7 are hydrogen.
Further compounds of the formula Ia used with preference are those in which R3 and R6 are methyl.
Other photoinitiator mixtures of interest are those in which, in the compounds of the formula Ia, R3, R4, R5, R6 and R7 are hydrogen.
Further preferred photoinitiator mixtures are those comprising compounds of the formula Ia and compounds of the formula II in which R8 is hydrogen, C1-C4alkyl, C1-C4alkoxy, xe2x80x94OCH2CH2OR12, a group
or a group
R9 and R10independently of one another are hydrogen, C1-C3alkyl, phenyl, C1-C12alkoxy or xe2x80x94O(CH2CH2O)qxe2x80x94C1-C8alkyl in which q is a number from 1 to 10, or R9 and R10, together with the carbon atom to which they are attached, form a cyclohexyl ring; R11 is hydroxyl, C1-C4alkoxy or xe2x80x94O(CH2CH2O)qxe2x80x94C1-C8alkyl; and/or compounds of the formula III, and/or compounds of the formula IV in which R8 is hydrogen or methoxy; R19 is methoxy, methylthio, morpholino or a group of the formula IVa; R20 is methyl or ethyl; R22 and R23 are the same and are methyl or, together with the nitrogen atom to which they are attached, form a five- or six-membered saturated ring which can be interrupted by xe2x80x94Oxe2x80x94; and R25 is hydrogen or C1-C8alkyl.
There is likewise interest in a photoinitiator mixture comprising compounds of the formula II in which R8 is hydrogen, C1-C4alkyl, C1-C4alkoxy or xe2x80x94OCH2CH2OR12; R9 and R10 independently of one another are hydrogen, phenyl, methyl, or methoxy or R9 and R10, together with the carbon atom to which they are attached, form a cyclohexyl ring; and R11 is hydroxyl or methoxy.
Other preferred photoinitiator mixtures are those in which the compound of the formula III is benzophenone, 2,4,6-trimethylphenyl phenyl ketone, 4-methylphenyl phenyl ketone, (3-methyl-4-methoxyphenyl 3-methylphenyl ketone, 4-(4-methylphenylthio)phenyl phenyl ketone, 2-carboxyphenyl phenyl ketone or 4-(2-hydroxyethoxy)phenyl phenyl ketone. Also preferred are photoinitiator mixtures in which the compound of the formula II is 1-benzoyl-1-hydroxy-1-methylethane, 1-benzoylcyclohexanol, 4-[(2-hydroxyethoxy)benzoyl]-1-hydroxy-1-methylethane, 1-(4-isopropylbenzoyl)-1-hydroxy-1-methylethane or 2,2-dimethoxy-1,2-diphenylethan-1-one.
Preference extends to photoinitiator mixtures in which the compound of the formula IV is 1-(3,4-dimethoxybenzoyl)-1-benzyl-1-morpholinopropane, 1-(4-methylthiobenzoyl)-1-methyl-1-morpholinoethane, 1-(4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane or 3,6-bis(2-methyl-2-morpholinopropan-1-one)-9-octylcarbazole.
Also of interest are photoinitiator mixtures in which the compound of the formula Ia is bis(2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide, bis[2,6-dimethyl-4-(2-methylpropyl)benzoyl]phenylphosphine oxide, bis(2,6-dimethylbenzoyl)phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or bis(2,4,6-trimethylbenzoyl)-2,5-dimethylphenylphosphine oxide.
The novel photoinitiator mixtures comprise, as compound of the formula Ia, preferably bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.
Preference is given to mixtures without benzophenone.
Preference is given to mixtures comprising compounds of the formula II.
Also of interest are photoinitiator mixtures comprising, as compound of the formula Ia, bis(2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide; bis(2,4,6-trimethylbenzoyl)-2-methylphenylphosphine oxide; bis(2,4,6-trimethylbenzoyl)-4-methylphenylphosphine oxide; bis(2,4,6-trimethylbenzoyl)-2,5-diethylphenylphosphine oxide and/or bis(2,4,6-trimethylbenzoyl)-2,3,5,6-tetramethylphenylphosphine oxide.
Particular preference is given to a photoinitiator mixture comprising 25% bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 75% 1-benzoylcyclohexanol. Likewise preferred is a photoinitiator mixture comprising 25% bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 75% 1-benzoyl-1-hydroxy-1-methylethane.
Also of interest are photoinitiator mixtures comprising two or more compounds of the formula Ia, or mixtures of compounds of the formula Ia with other bisacylphosphine oxides and/or monacylphosphine oxides and compounds of the formulae II and/or III, for example a combination of bis (2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)(1,4,4-trimethylpentyl)phosphine oxide, 1-benzoylcyclohexanol or, for example, of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)(1,4,4-trimethylpentyl)phosphinoxide and 1-benzoyl-1-hydroxy-1-methylethane or for example, of bis (2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-dimethylphenylphosphine oxide, 1-benzoyl-1-hydroxy-1-methylethane and/or 1-benzoyl-1-hydroxy-1-methylethane, of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1-benzoyl-1-hydroxyl-1-methylethane and/or 1-benzoyl-1-hydroxy-1-methylethane, or of bis(2,4,6-trimethylbenzoyl)-2,4-dipentoxyphenylphosphine oxide, 1-benzoyl-1-hydroxy-1-methylethane and/or 1-benzoyl-1-hydroxy-1-methylethane.
In accordance with the invention, the compounds of the formula I and the mixtures (blends) of compounds of the formula Ia with compounds of the formula II and/or III and/or IV can be used as photoinitiators for the photopolymerization of ethylenically unsaturated compounds and of mixtures which include such compounds. This use may also be practised in combination with other additives.
The invention therefore also provides photopolymerizable compositions comprising
(a) at least one ethylenically unsaturated photopolymerizable compound and
(b) as photoinitiator, at least one compound of the formula I or a photoinitiator mixture as described above,
it being possible for the composition to contain not only component (b) but also other additives.
The unsaturated compounds may contain one or more olefinic double bonds. They may be of low molecular mass (monomeric) or of relatively high molecular mass (oligomeric). Examples of monomers containing a double bond are alkyl or hydroxyalkyl acrylates or methacrylates, for example, methyl, ethyl, butyl, 2-ethylhexyl- or 2-hydroxyethyl acrylate, isobornyl acrylate, or methyl or ethyl methacrylate. Silicone acrylates are also of interest. Further examples are acrylonitrile, acrylamide, methacrylamide, N-substituted (meth)acrylamides, vinyl esters such as vinyl acetate, vinyl ethers such as isobutyl vinyl ether, styrene, alkyl- and halostyrenes, N-vinylpyrrolidone, vinyl chloride or vinylidene chloride.
Examples of monomers containing two or more double bonds are the diacrylates of ethylene glycol, propylene glycol, neopentyl glycol, hexamethylene glycol and of bisphenol-A,4,4xe2x80x2-bis(2-acryloyloxyethoxy)diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, vinyl acrylate, divinyl benzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate and tris(2-acryloylethyl) isocyanurate.
Examples of relatively high molecular mass (oligomeric) polyunsaturated compounds are acrylicized epoxy resins, and polyethers, polyurethanes and polyesters which are acrylicized or contain vinyl ether groups or epoxy groups. Further examples of unsaturated oligomers are unsaturated polyester resins which are mostly prepared from maleic acid, phthalic acid and one or more diols and have molecular weights of from about 500 to 3000. In addition it is also possible to employ vinyl ether monomers and vinyl ether oligomers, and also maleate-terminated oligomers having polyester, polyurethane, polyether, polyvinyl ether and epoxy main chains. Combinations of oligomers which carry vinyl ether groups and of polymers as described in WO 90/01512 are particularly suitable. However, copolymers of vinyl ether and maleic acid functionalized monomers are also appropriate. Such unsaturated oligomers can also be referred to as prepolymers.
Examples of particularly suitable compounds are esters of ethylenically unsaturated carboxylic acids and polyols of polyepoxides, and polymers containing ethylenically unsaturated groups in the chain or in side groups, for example unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers containing (meth)acrylic groups in side chains, and mixtures of one or more such polymers.
Examples of unsaturated carboxylic acids are acrylic, methacrylic, crotonic, itaconic and cinnamic acid, and unsaturated fatty acids such as linolenic acid and oleic acid. Acrylic acid and methacrylic acid are preferred.
Suitable polyols are aromatic polyols and, in particular, aliphatic and cycloaliphatic polyols. Examples of aromatic polyols are hydroquinone, 4,4xe2x80x2-dihydroxydiphenyl, 2,2-di(4-hydroxyphenyl)propane, and also novolaks and resols. Examples of polyepoxides are those based on the said polyols, especially on the aromatic polyols and epichlorohydrin. Other suitable polyols include polymers and copolymers which contain hydroxyl groups in the polymer chain or in side groups, for example polyvinyl alcohol and copolymers thereof, or hydroxyalkyl polymethacrylates or copolymers thereof. Further suitable polyols are oligoesters containing hydroxyl end groups.
Examples of aliphatic and cycloaliphatic polyols are alkylene diols, preferably with 2 to 12 carbon atoms, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols with molecular weights of preferably from 200 to 1500, 1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris(xcex2-hydroxyethyl)amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaaerythritol and sorbitol.
The polyols may be partially or completely esterified by means of one or more unsaturated carboxylic acids, where the free hydroxyl groups in partial esters may be modified, for example etherified or esterified with other carboxylic acids.
Examples of esters are:
Trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol octacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate, tripentaerythritol octamethacrylate, pentaerythritol diitaconate, dipentaerythritol trisitaconate, dipentaerythritol pentaitaconate, dipentaerythritol hexaitaconate, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diitaconate, sorbitol triacrylate, sorbitol tetraacrylate, pentaerythritol-modified triacrylate, sorbitol tetramethyacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, oligoester acrylates and methacrylates, glycerol di- and -triacrylate, 1,4-cyclohexane diacrylate, bisacrylates and bismethacrylates of polyethylene glycol of molecular weight from 200 to 1500, or mixtures thereof.
Further suitable components (a) are the amides of identical or different unsaturated carboxylic acids of aromatic, cycloaliphatic and aliphatic polyamines, preferably having 2 to 6, in particular 2 to 4, amino groups. Examples of such polyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine, phenylendiamine, bisphenylenediamine, di-xcex2-aminoethyl ether, diethylenetriamine, triethylenetetramine, di(xcex2-aminoethoxy)- or di(xcex2-aminopropoxy)ethane. Further suitable polyamines are polymers and copolymers which may contain additional amino groups in the side chain, and oligoamides containing amino end groups. Examples of unsaturated amides of this kind are: methylenebisacrylamide, 1,6-hexamethylenebisacrylamide, diethylenetriaminetrismethacrylamide, bis(methacrylamidopropoxy)ethane, xcex2-methacrylamidoethyl methacrylate, and N-[(xcex2-hydroxyethoxy)ethyl]acrylamide.
Suitable unsaturated polyesters and polyamides are derived, for example, from maleic acid and diols or diamines. Some of the maleic acid may be replaced by other dicarboxylic acids. They can be employed together with ethylenically unsaturated comonomers, for example styrene. The polyesters and polyamides may also be derived from dicarboxylic acids and ethylenically unsaturated diols or diamines, especially from relatively long-chain compounds containing, for example, from 6 to 20 carbon atoms. Examples of polyurethanes are those built up from saturated or unsaturated diisocyanates and from unsaturated and/or saturated diols.
Polybutadiene and polyisoprene and copolymers thereof are known. Examples of suitable comonomers are: olefins such as ethylene, propene, butene, hexene, (meth)acrylates, acrylonitrile, styrene and vinyl chloride. Polymers containing (meth)acrylate groups in the side chain are also known. These may be, for example, products of the reaction of novolak-based epoxy resins with (meth)acrylic acid, homopolymers or copolymers of vinyl alcohol or hydroxyalkyl derivatives thereof which have been esterified using (meth)acrylic acid, or homopolymers and copolymers of (meth)acrylates which have been esterified using hydroxyalkyl (meth)acrylates.
The photopolymerizable compounds can be employed alone or in any desired mixtures. Preference is given to mixtures of polyol (meth)acrylates.
It is also possible to add binders to the novel compositions, which is particularly expedient if the photopolymerizable compounds are liquid or viscous substances. The amount of binder may be, for example, 5-95% by weight, preferably 10-90% by weight and, in particular, 40-90% by weight, based on the overall solids content. The binder is chosen depending on the field of use and on the properties required therefor, such as the facility for development in aqueous and organic solvent systems, adhesion to substrates, and sensitivity to oxygen.
Examples of suitable binders are polymers having a molecular weight of about 5,000-2,000,000, preferably 10,000-1,000,000. Examples are homo- and copolymeric acrylates and methacrylates, for example copolymers of methyl methacrylate/ethyl acrylate/methacrylic acid, poly(alkyl methacrylate), poly(alkyl acrylates); cellulose esters and cellulose ethers, such as cellulose acetate, cellulose acetate butyrate, methylcellulose, ethylcellulose; polyvinylbutyral, polyvinylformal, cyclized rubber, polyether such as polyethylene oxide, polypropylene oxide, polytetrahydrofuran; polystyrene, polycarbonate, polyurethane, chlorinated polyolefins, polyvinyl chloride, copolymers of vinyl chloride/vinylidene chloride, copolymers of vinylidene chloride with acrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate, copoly(ethylene/vinyl acetate), polymers such as polycaprolactam and poly(hexamethyleneadipamide), and polyesters such as poly(ethylene glycol terephthalate) and poly(hexamethylene glycol succinate).
The unsaturated compounds can also be used in mixtures with non-photopolymerizable film-forming components. These may, for example, be physically drying polymers or solutions thereof in organic solvents, for example nitrocellulose or cellulose acetobutyrate. However, they can also be chemically curable or heat-curable resins, for example polyisocyanates, polyepoxides or melamine resins. The additional use of heat-curable resins is important for use in so-called hybrid systems, which are photopolymerized in a first step and are crosslinked by thermal after treatment in a second step.
The photopolymerizable mixtures may contain various additives in addition to the photoinitiator. 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. The shelf life in the dark can be increased, for example, by using copper compounds, such as copper naphthenate, copper stearate or copper octoate, phosphorus compounds, for example triphenylphosphine, tributylphosphine, triethyl phosphite, triphenyl phosphite or tribenzyl phosphite, quaternary ammonium compounds, such as tetramethylammonium chloride or trimethylbenzylammonium chloride, or hydroxylamine derivatives, such as N-diethylhydroxylamine. In order to keep out atmospheric oxygen during the polymerization, paraffin or similar waxlike substances can be added; these migrate to the surface on commencement of the polymerization because of their low solubility in the polymer, and form a transparent surface layer which prevents the ingress of air. It is likewise possible to apply an oxygen barrier layer. Light stabilizers which can be added are UV absorbers, for example those of the hydroxyphenylbenzotriazole, hydroxyphenylbenzophenone, oxalamide or hydroxyphenyl-s-triazine type. It is possible to use individual such compounds or mixtures thereof, with or without the use of sterically hindered amines (HALS).
Examples of such UV absorbers and light stabilizers are
1. 2-(2xe2x80x2-Hydroxyphenyl)benzotriazoles, for example 2-(2xe2x80x2-hydroxy-5xe2x80x2-methylphenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-tert-butyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(5xe2x80x2-tert-butyl-2xe2x80x2-hydroxyphenyl)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-methylphenyl)-5-chlorobenzotriazole, 2-(3xe2x80x2-sec-butyl-5xe2x80x2-tert-butyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 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, a mixture of 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3xe2x80x2-tert-butyl-5xe2x80x2-[2-(2-ethylhexyloxy)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-ylphenol]; the transesterification product of 2-[3xe2x80x2-tert-butyl-5xe2x80x2-(2-methoxy-carbonylethyl)-2xe2x80x2-hydroxyphenyl]benzotriazole with polyethylene glycol 300; [Rxe2x80x94CH2CH2xe2x80x94COO(CH2)3]2 where R=3xe2x80x2-tert-butyl-4xe2x80x2-hydroxy-5xe2x80x2-2H-benzotriazol-2-ylphenyl.
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 benzoic acids, for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, 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, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
4. Acrylates, for example ethyl xcex1-cyano-xcex2,xcex2-diphenylacrylate or isooctyl xcex1-cyano-xcex2,xcex2-diphenylacrylate, methyl xcex1-carbomethoxycinnamate, methyl xcex1-cyano-xcex2-methyl-p-methoxy-cinnamate or butyl xcex1-cyano-xcex2-methyl-p-methoxycinnamate, methyl xcex1-carbomethoxy-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, the condensate of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensate of N,Nxe2x80x2-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine 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-butanetetraoate, 1,1xe2x80x2-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpipemaznone), 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, the condensate of N,Nxe2x80x2-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6-di(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, the condensate of 2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)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, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)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-5,5xe2x80x2-di-tert-butyloxanilide, 2-ethoxy-2xe2x80x2-ethyloxanilide, 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 and mixtures of o- and p-methoxy and of o- and p-ethoxy-disubstituted oxanilides.
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-propyloxyphenyl)-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-butyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-dodecyl/tridecyloxy-(2-hydroxypropyl)oxy-2-hydroxyphenyl]-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 pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bisisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4di-tert-butylphenyl) 4,4xe2x80x2-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite.
Consequently, the invention also provides photopolymerizable compositions comprising as photoinitiator at least one compound of the formula I, or a photoinitiator mixture as described above, and a UV absorber from the class of the hydroxyphenyl-s-triazines and/or hydroxyphenylbenzotriazoles and/or sterically hindered amines based on 2,2,6,6-tetramethylpiperidines.
Preference is given to a composition comprising a photoinitiator mixture of compounds of the formulae la, especially bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and compounds of the formula II, especially 1-benzoylcyclohexanol and 1-benzoyl-1-hydroxy-1-methylethane, and a mixture of 85% 4,6-di(2,4-dimethylphenyl)-2-[2-hydroxy-4-(mixture of dodecyloxy and tridecyloxy)(2-hydroxy)propyl-3-oxyphenyl]-1,3,5-triazine and 15% 1-methoxy-2-propanol as UV absorber.
To accelerate the photopolymerization it is possible to add amines, for example triethanolamine, N-methyldiethanolamine, ethyl p-dimethylaminobenzoate or Michler""s ketone. The action of the amines can be intensified by the addition of aromatic ketones of the benzophenone type. If use is made of novel mixtures comprising compounds of the formula III, an improvement in the reactivity can be obtained through the addition of amines. Examples of amines which can be used as oxygen scavengers are substituted N,N-dialkylanilines as described in EP-A-339 841. Further accelerators, coinitiators and autoxidizers are thiols, thioethers, disulfides and phosphines, as are described, for example, in EP-A-438 123 and GB-A-2 180 358.
The photopolymerization can also be accelerated by the addition of photosensitizers, which shift or broaden the spectral sensitivity. These are, in particular, aromatic carbonyl compounds, such as benzophenone derivatives, thioxanthone derivatives, anthraquinone derivatives and 3-acylcoumarin derivatives, and also 3-(aroylmethylene)thiazolines, and also eosine, rhodamine and erythrosine dyes.
The curing procedure can be assisted, in particular, by compositions which are pigmented (for example with titanium dioxide), and also by adding a component which forms free radicals under thermal conditions, for example an azo compound such as 2,2xe2x80x2-azobis(4-methoxy-2,4-dimethylvaleronitrile), a triazene, a diazo sulfide, a pentazadiene or a peroxy compound, such as a hydroperoxide or peroxycarbonate, for example t-butyl hydroperoxide, as described in EP-A 245 639.
The novel compositions can also include a photoreducible dye, for example xanthene, benzoxanthene, benzothioxanthene, thiazine, pyronine, porphyrin or acridine dyes, and/or a trihalomethyl compound which can be cleaved by radiation. Similar compositions are described, for example, in EP-A-445 624.
Other conventional additives arexe2x80x94depending on the intended applicationxe2x80x94fluorescent whiteners, fillers, pigments, dyes, wetting agents or levelling assistants.
Thick and pigmented coatings can suitably be cured by the addition of glass microbeads or powdered glass fibres, as described in U.S. Pat. No. 5,013,768, for example.
The invention also provides compositions comprising as component (a) at least one ethylenically unsaturated, photopolymerizable compound which is emulsified or dissolved in water.
Radiation-curable, aqueous prepolymer dispersions of this type are commercially available in numerous variations. This term is taken to mean a dispersion of water and at least one prepolymer dispersed therein. The concentration of water in these systems is, for example, from 5 to 80% by weight, in particular from 30 to 60% by weight. The radiation-curable prepolymer or prepolymer mixture is present, for example, in concentrations of from 95 to 20% by weight, in particular from 70 to 40% by weight. The total of the percentages indicated for water and prepolymers in these compositions is in each case 100, to which are added the auxiliaries and additives in various amounts depending on the intended application.
The radiation-curable, water-dispersed, film-forming prepolymers, which are frequently also dissolved, are, for aqueous prepolymer dispersions, monofunctional or polyfunctional ethylenically unsaturated prepolymers which are known per se, can be initiated by means of free radicals and contain, for example, from 0.01 to 1.0 mol of polymerizable double bonds per 100 g of prepolymer, and have a mean molecular weight of, for example, at least 400, in particular from 500 to 10,000. Depending on the intended application, however, prepolymers having higher molecular weights might also be suitable.
For example, use is made of polyesters containing polymerizable Cxe2x80x94C double bonds and having a maximum acid number of 10, polyethers containing polymerizable Cxe2x80x94C double bonds, hydroxyl-containing products of the reaction of a polyepoxide containing at least two epoxide groups per molecule with at least one xcex1,xcex2-ethylenically unsaturated carboxylic acid, polyurethane (meth)acrylates, and xcex1,xcex2-ethylenically unsaturated acrylic copolymers containing acrylic radicals, as are described in EP-A-12 339. Mixtures of these prepolymers may ,also be used. Also suitable are the polymerizable prepolymers described in EP-A-33 896, which are thioether adducts of polymerizable prepolymers having a mean molecular weight of at least 600, a carboxyl group content of from 0.2 to 15% and a content of from 0.01 to 0.8 mol of polymerizable Cxe2x80x94C double bonds per 100 g of prepolymer. Other suitable aqueous dispersions based on specific alkyl (meth)acrylate prepolymers are described in EP-A-41 125; suitable water-dispersible, radiation-curable prepolymers made from urethane acrylates are disclosed in DE-A-2 936 039.
These radiation-curable, aqueous prepolymer dispersions may include, as further additives, dispersion assistants, emulsifiers, antioxidants, light stabilizers, dyes, pigments, fillers, for example talc, gypsum, silica, rutile, carbon black, zinc oxide and iron oxides, reaction accelerators, levelling agents, lubricants, wetting agents, thickeners, matting agents, defoamers and other assistants which are customary in coatings technology. Suitable dispersion assistants are water-soluble organic compounds of high molecular mass which contain polar groups, examples being polyvinyl alcohols, polyvinylpyrrolidone and cellulose ethers Emulsifiers which can be used are nonionic emulsifiers and possibly also ionic emulsifiers.
The photopolymerizable compositions comprise the photoinitiator or the photoinitiator mixture (b) advantageously in an amount of from 0.05 to 15% by weight, preferably from 0.1 to 5% by weight, based on the composition.
Where the novel photoinitiators are employed in hybrid systems, use is madexe2x80x94in addition to the novel free-radical hardenersxe2x80x94of cationic photoinitiators, for example benzoyl peroxide, aromatic sulfonium or iodonium salts, or cyclopentadienylarene iron(II) complex salts.
In certain cases it may be an advantage to use further initiators in addition to the novel compounds or photoinitiator mixtures. For example, phosphines or phosphonium salts or, for example, compounds of the formula
(described in U.S. Pat. No. 5,436,280 or JP-A-Hei 6 263809) in which Q is S or O and R1xe2x80x2, R2xe2x80x2, R3xe2x80x2 and R4xe2x80x2 are, for example, alkyl, alkenyl or aryl, and phosphites can be used as additives.
The photopolymerizable compositions can be used for various purposes, for example as printing inks, as transparent coatings, as white paints, for example for wood or metal, as coating materials for substrates including paper, wood, metal and plastic, as daylight-curable coatings for marking buildings and roads, for photographic reproduction techniques, for holographic recording materials, for image recording processes or for the production of printing plates which can be developed using organic solvents or aqueous-alkaline media, for the production of masks for screen printing, as dental filling materials, as adhesives, as pressure-sensitive adhesives, as laminating resins, as etch resists or permanent resists, and as solder masks for electronic circuits, for the production of three-dimensional articles by bulk curing (UV curing in transparent moulds) or by the stereolithography process, as is described, for example in U.S. Pat. No. 4,575,330, for the preparation of composite materials (e.g. styrenic polyesters, which may, if appropriate, contain glass fibres and other auxiliaries) and other thick-layer compositions, for the coating or encapsulation of electronic components, or as coatings for optical fibres.
The novel compounds and photoinitiator mixtures can additionally be used as initiators for emulsion polymerizations, as initiators of a polymerization for the fixing of ordered states of liquid-crystalline monomers and oligomers, and as initiators for the fixing of dyes on organic materials.
In surface coatings, mixtures of a prepolymer with polyunsaturated monomers are often used which also include a monounsaturated monomer. The prepolymer here is primarily responsible for the properties of the coating film, and variation thereof allows the person skilled in the art to influence the properties of the cured film. The polyunsaturated monomer functions as a crosslinking agent which renders the coating film insoluble. The monounsaturated monomer acts as a reactive diluent by means of which the viscosity is reduced without the need to use a solvent.
Unsaturated polyester resins are usually used in two-component systems together with a monounsaturated monomer, preferably with styrene. For photoresists, specific single-component systems are often used, for example polymaleimides, polychalkones or polyimides, as are described in DE-A-2 308 830.
The novel compounds and mixtures may also be used, for example, in coating materials which are in organic solvents and/or water or are solvent-free.
The novel compounds and mixtures thereof can also be used as free-radical photoinitiators or photoinitiating systems for radiation-curable powder coatings. The powder coatings can be based on solid resins and monomers containing reactive double bonds, for example maleates, vinyl ethers, acrylates, acrylamides and mixtures thereof. A free-radically UV-curable powder coating can be formulated by mixing unsaturated polyester resins with solid acrylamides (for example methyl methylacrylamidoglycolate) and a novel free-radical photoinitiator, such formulations being as described, for example, in the paper xe2x80x9cRadiation Curing of Powder Coatingxe2x80x9d, Conference Proceedings, Radtech Europe 1993 by M. Wittig and Th. Gohmann. Free-radically UV-curable powder coatings can also be formulated by mixing unsaturated polyester resins with solid acrylates, methacrylates or vinyl ethers and with a novel photoinitiator (or photoinitiator mixture). The powder coatings may also comprise binders as are described, for example, in DE-A-42 28 514 and in EP-A-636 669. The UV-curable powder coatings may additionally comprise white or coloured pigments. For example, preferably rutiletitanium dioxide can be employed in concentrations of up to 50% by weight in order to give a cured powder coating of good hiding power. The procedure normally comprises electrostatic or tribostatic spraying of the powder onto the substrate, for example metal or wood, melting of the powder by heating, and, after a smooth film has formed, radiation-curing of the coating with ultraviolet and/or visible light, using, for example, medium-pressure mercury lamps, metal halide lamps or xenon lamps. A particular advantage of the radiation-curable powder coatings over their heat-curable counterparts is that the flow time after melting of the powder particles can be delayed if desired in order to ensure the formation of a smooth, high-gloss coating. In contrast to heat-curable systems, radiation-curable powder coatings can be formulated to melt at lower temperatures without the unwanted effect of shortening their lifetime. For this reason, they are also suitable as coatings for heat-sensitive substrates, for example wood or plastics.
In addition to the novel photoinitiators, the powder coating formulations may also include UV absorbers. Appropriate examples are listed above in sections 1.-8.
The novel photocurable compositions are suitable, for example, as coating materials for substrates of all kinds, for example wood, textiles, paper, ceramic, glass, plastics such as polyesters, polyethylene terephthalate, polyolefins or cellulose acetate, especially in the form of films, and also metals such as Al, Cu, Ni, Fe, Zn, Mg or Co and GaAs, Si or SiO2 to which it is intended to apply a protective layer or, by means of imagewise exposure, to generate a reproduced image.
Coating of the substrates can be carried out by applying to the substrate a liquid composition, a solution or a suspension. The choice of solvents and the concentration depend principally on the type of composition and on the coating technique. The solvent should be inert, i.e. it should not undergo a chemical reaction with the components and should be able to be removed again, after coating, in the course of drying. Examples of suitable solvents are ketones, ethers and esters, such as methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, N-methylpyrrolidone, dioxane, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 1,2-dimethoxyethane, ethyl acetate, n-butyl acetate and ethyl 3-ethoxypropionate. The solution is applied uniformly to a substrate by means of known coating techniques, for example by spin coating, dip coating, knife coating, curtain coating, brushing, spraying, especially by electrostatic spraying, and reverse-roll coating. 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 (layer thickness) and the nature of the substrate (layer support) are dependent on the desired field of application. The range of layer thicknesses generally comprises values from about 0.1 xcexcm to more than 100 xcexcm.
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 (electroplating resist, etch resist, solder resist), the production of printing plates, such as offset printing plates or screen printing formes and/or the production of dies, for use in chemical milling or as a microresist in the production of integrated circuits. The possible layer supports, and the processing conditions of the coated substrates, are just as varied.
Substrates used for photographic information recording include, for example, films of polyester, cellulose acetate or polymer-coated papers; substrates for offset printing formes are specially treated aluminium, substrates for producing printed circuits are copper-clad laminates, and substrates for producing integrated circuits are silicon wafers. The layer thicknesses for photographic materials and offset printing forms are generally from about 0.5 xcexcm to 10 xcexcm, while for printed circuits they are from 0.4 xcexcm to about 2 xcexcm.
Following the coating of the substrates, the solvent is removed, generally by drying, to leave a coat of the photoresist on the substrate.
The term xe2x80x9cimagewisexe2x80x9d exposure includes both exposure through a photomask comprising a predetermined pattern, for example a slide, exposure by means of a laser 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.
Following the imagewise exposure of the material and prior to development, it may be advantageous to carry out thermal treatment for a short time. In this case only the exposed sections are thermally cured. The temperatures employed are generally 50-150xc2x0 C., preferably 8-130xc2x0 C.; the period of thermal treatment is in general between 0.25 and 10 minutes.
The photocurable composition may additionally be used in a process for producing printing plates or photoresists as is described, for example, in DE-A-40 13 358. In such a process the composition is exposed for a short time to visible light with a wavelength of at least 400 nm, without a mask, prior to, simultaneously with or following imagewise irradiation.
After the exposure and, if implemented, thermal treatment, the unexposed areas of the photosensitive coating are removed with a developer in a manner known per se.
As already mentioned, the novel 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.
Photocuring is of great importance for printing inks, since the drying time of the binder is a critical factor for the production rate of graphic products, and should be in the order of fractions of seconds. UV-curable inks are particularly important for screen printing.
As already mentioned above, the novel mixtures are also highly suitable for producing printing plates. This application uses, for example, mixtures of soluble linear polyamides or styrene/butadiene and/or styrenefisoprene rubber, polyacrylates or polymethyl methacrylates containing carboxyl groups, polyvinyl alcohols or urethane acrylates with photopolymerizable monomers, for example acrylamides and/or methacrylamides, or acrylates and/or methacrylates, and a photoinitiator. Films and plates of these systems (wet or dry) are exposed over the negative (or positive) of the printed original, and the uncured parts are subsequently washed out using an appropriate solvent.
Another field where photocuring is employed is the coating of metals, in the case, for example, of the coating of metal plates and tubes, cans or bottle caps, and photocuring of polymer coatings, for example of floor or wall coverings based on PVC.
Examples of the photocuring of paper coatings are the colourless varnishing of labels, record sleeves and book covers.
Also of interest is the use of the novel compounds for curing shaped articles made from composite compositions. The composite composition consists of a self-supporting matrix material, for example a glass fibre fabric, or alternatively, for example, plant fibres [cf.K. -P. Mieck, T. Reussmann in Kunststoffe 85 (1995), 366-370], which is impregnated with the photocuring formulation. Shaped parts comprising composite compositions, when produced using the novel compounds, attain a high level of mechanical stability and resistance. The novel compounds can also be employed as photocuring agents in moulding, impregnating and coating compositions as are described, for example, in EP-A-7086. Examples of such compositions are gel coat resins, which are subject to stringent requirements regarding curing activity and yellowing resistance, and fibre-reinforced mouldings, for example light-diffusing panels which are planar or have lengthwise or crosswise corrugation. Techniques for producing such mouldings, such as hand lay-up, spray lay-up, centrifugal casting or filament winding, are described, for example, by P. H. Selden in xe2x80x9cGlasfaserverstxc3xa4rkte Kunststoffexe2x80x9d, page 610, Springer Verlag Berlin-Heidelberg-New York 1967. Examples of articles which can be produced by these techniques are boats, fibre board or chipboard panels with a double-sided coating of glass fibre-reinforced plastic, pipes, containers, etc. Further examples of moulding, impregnating and coating compositions are UP resin gel coats for mouldings containing glass fibres (GRP), such as corrugated sheets and paper laminates. Paper laminates may be based on urea resins or melamine resins. Prior to production of the laminate, the gel coat is produced on a support (for example a film). The novel photocurable compositions can also be used for casting resins or for embedding articles, for example electronic components, etc. Curing is carried out using medium-pressure mercury lamps as are conventional in UV curing. However, there is also particular interest in less intense lamps, for example of the type TL 40W/03 or TL40W/05. The intensity of these lamps corresponds approximately to that of sunlight. It is also possible to use direct sunlight for curing. A further advantage is that the composite composition can be removed from the light source in a partly cured, plastic state and can be shaped, With full curing taking place subsequently.
The use of photocurable compositions for imaging techniques and for the optical production of information carriers is also important. In such applications, as already described above, the layer (wet or dry) applied to the support is irradiated through a photomask with UV or visible light, and the unexposed areas of the layer are removed by treatment with a solvent (=developer). Application of the photocurable layer to metal can also be carried out by electrodeposition. The exposed areas are polymeric through crosslinking and are therefore insoluble and remain on the support. Appropriate colourafion produces visible images. Where the support is a metallized layer, the metal can, following exposure and development, be etched away at the unexposed areas or reinforced by electroplating. In this way it is possible to produce printed electronic circuits and photoresists.
The photosensitivity of the novel compositions extends in general from the UV (about 200 nm) region about 600 nm and therefore spans a very broad range. Suitable radiation is present, for example, in sunlight or light from artificial light sources. Consequently, a large number of very different types of light source 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 doped with metal halide (metal-halogen lamps), microwave-stimulated metal vapour lamps, excimer lamps, superactinic fluorescent tubes, fluorescent lamps, argon incandescent lamps, electronic flashlamps, photographic floodlamps, electron beams and X-rays, produced by means of synchrotrons or laser plasma. 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 the lamp, and may be, for example, from 2 cm to 150 cm. Laser light sources, for example excimer lasers, are especially suitable, such as krypton F lasers for exposure at 248 nm. Lasers in the visible region can also be employed. In this case, the high sensitivity of the novel materials are very advantageous. 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 additionally provides for the use of the above-described composition for preparing coating materials, printing inks, printing plates, dental compositions, resist materials, and as image recording material, especially for holographic recordings.
The invention additionally provides a coated substrate which is coated on at least one surface with a composition as described above, and provides a process for the photographic production of relief images, in which a coated substrate is subjected to imagewise exposure and then the unexposed portions are removed with a solvent. Imagewise exposure in this case can take place through a mask or else using a controlled laser (without a mask).
The invention thus also provides a process for the photopolymerization of compounds containing ethylenically unsaturated double bonds, which comprises irradiating a composition as described above, with light in the range from 200 to 600 nm.
The compounds of the formulae I and Ia are photosensitive solids, which are generally yellow, and which are soluble, for example, in esters, aromatic compounds, alcohols and chlorinated hydrocarbons.
The novel photoinitiator mixtures (blends) are of good solubility in the substrate that is to be cured. In this context, the solubility of the blends in the substrate to be cured is generally better than the solubility of the individual components. In the blend, one component acts as a solubilizer for the others.
When carrying out curing with the novel blends, an optimum ratio can be obtained between the curing of the surface of the substrate and its through-curing.
The photoinitiator mixtures are reactive, and low yellowing values can be achieved in the course of curing.

Photoinitiator mixtures and compositions with alkylphenylbisacylphosphine oxides

Abstract: Compounds of the formula I

Abstract: in which R1 is C1-C4alkyl, R2 is hydrogen, C1-C4alkyl or C1-C4alkoxy and R3, R4, R5, R6 and R7 independently of one another are hydrogen, halogen, C1-C20alkyl, cyclopentyl, cyclohexyl, C2-C12alkenyl, C2-C18alkyl which is interrupted by one or more oxygen atoms, or are phenyl-substituted C1-C4alkyl, or are phenyl which is unsubstituted or is mono- or disubstituted by C1-C4alkyl and/or C1-C4alkoxy, with the provisos that at least one of the radicals R3, R4, R5, R6 and R7 is other than hydrogen and that, if R1 and R2 are methyl, R3 and R6 are not methyl, and mixtures of such compounds with xcex1-hydroxy ketones, benzophenones and xcex1-amino ketones, are suitable as photoinitiators.


Seamless guest access to spaces and meetings may be provided. A trusted user device may send an identity object and may receive an identifier and an authorization token in response to sending the identity object. Then the trusted user device may send a request to add a guest user associated with the identifier to a collaboration event and may receive, in response to sending the request to add the guest user, location data associated with the collaboration event. The trusted user device may then send collaboration space data to a guest user device associated with the guest user. The collaboration space data may comprise the authorization token, the location data, and an application indicator associated with the collaboration event.

A collaboration tool helps people to collaborate. The purpose of a collaboration tool is to support a group of two or more individuals to accomplish a common goal or objective. Collaboration tools may be either of a non-technological nature such as paper, flipcharts, post-it notes, or whiteboards. They can also include software tools and applications such as collaborative software applications.


Endoscopic bipolar scissor blades are formed in a laminate assembly of an electrically conductive electrode, an electrically insulating material, and a metal shearing surface which is electrically insulated and physically spaced from the electrode by the insulating material which is disposed therebetween. In one embodiment, the electrode is a metal blade, while the insulating material is a ceramic which is fixed to the metal blade, and the metal shearing surface which also provides the cutting edge is of a metal material which is fixed to the ceramic. In a second embodiment, the insulating material is a molded ceramic blade, with the electrode and the metal shearing surface layer metalized or otherwise fixed to the ceramic blade. In a third embodiment, the electrode is metalized on a thin layer insulating material which is fixed onto a metallic blade. In a fourth embodiment, metallic shearing and electrode layers are laminated to opposite sides of a fiberglass material. In all embodiments, the metal cutting edges and surfaces are insulated from the electrodes, and no short circuit can form between the electrodes even though the cutting edges and shearing surfaces are metal.

1. Field of the Invention
The present invention relates generally to endoscopic surgical instruments. More particularly, the invention relates to an endoscopic surgical instrument having end effectors made out of a combination of conductive and non-conductive materials. The invention has particular use with respect to bipolar endoscopic cautery. For purposes herein, the term xe2x80x9cendoscopic instrumentsxe2x80x9d is to be understood in its broadest sense to include laparoscopic, arthroscopic, and neurological instruments, as well as instruments which are inserted through an endoscope.
2. State of the Art
Endoscopic surgery is widely practiced throughout the world today and its acceptance is growing rapidly. In general, endoscopic/laparoscopic surgery involves one or more incisions made by trocars where trocar tubes are left in place so that endoscopic surgical tools may be inserted through the tubes. A camera, magnifying lens, or other optical instrument is often inserted through one trocar tube, while a cutter, dissector, or other surgical instrument is inserted through the same or another trocar tube for purposes of manipulating and/or cutting the internal organ. Sometimes it is desirable to have several trocar tubes in place at once in order to receive several surgical instruments. In this manner, organ or tissue may be grasped with one surgical instrument, and simultaneously may be cut with another surgical instrument; all under view of the surgeon via the optical instrument in place in the trocar tube.
Various types of endoscopic surgical instruments are known in the art. These instruments generally comprise a slender tube containing a push rod which is axially movable within the tube by means of a handle or trigger-like actuating means. An end effector is provided at the distal end of the tube and is coupled to the push rod by means of a clevis so that axial movement of the push rod is translated to rotational or pivotal movement of the end effector. End effectors may take the form of scissors, grippers, cutting jaws, forceps, and the like. Because of their very small size and the requirements of strength and/or sharpness, end effectors are difficult to manufacture and are typically formed of forged stainless steel. As such, they form an expensive portion of the endoscopic instrument.
Modern endoscopic procedures often involve the use of electrocautery, as the control of bleeding by coagulation during surgery is critical both in terms of limiting loss of blood and in permitting a clear viewing of the surgical site. As used herein, cautery, electrocautery, and coagulation are used interchangeably. Several types of electrocautery devices for use in endoscopic surgery are described in the prior art. Monopolar electrosurgical instruments employ the instrument as an electrode, with a large electrode plate beneath end in contact with the patient serving as the second electrode. High frequency voltage spikes are passed through the instrument to the electrode (i.e., end effector) of the endoscopic instrument to cause an arcing between the instrument and the proximate tissue of the patient. The current thereby generated continues through the patient to the large electrode plate beneath the patient. Monopolar cautery has the disadvantage that the current flows completely through the patient. Because control of the current path through the body is not possible, damage can occur to tissue both near and at some distance from the surgical site. In addition, it is has been observed that monopolar cautery can result in excessive tissue damage due to the arcing between the end effector and the tissue.
In order to overcome the problems associated with monopolar cautery instruments, bipolar instruments have been introduced. In bipolar electrosurgical instruments, two electrodes which are closely spaced together are utilized to contact the tissue. Typically, one end effector acts as the first electrode, and the other end effector acts as the second electrode, with the end effectors being electrically isolated from each other and each having a separate current path back through to the handle of the instrument. Thus, in a bipolar instrument, the current flow is from one end effector electrode, through the tissue to be cauterized, to the other end effector electrode.
Various endoscopic instruments with cautery capability are known in the art. U.S. Pat. No. 4,418,692 to Guay, for example, discloses a device for use in laparoscopic tubal cauterization for blocking the Fallopian tubes of a patient. The device comprises a substantially tubular body member having a spring-biased piston slidably mounted therein. A pair of electrodes (either monopolar or bipolar) are disposed to grasp living tissue when the piston is in a first position biased by the spring and to release the tissue when a button is pressed which moves the piston into a second position. The device includes a circuit breaker which interrupts current flowing to the electrodes when the piston is in the second position. When the electrodes grasp the tissue, however, current is supplied to the entire surface of the electrode, that is, both the grasping surface and the outer non-grasping surface.
Another electrosurgical instrument for use in combination with an endoscope is disclosed in U.S. Pat. No. 5,007,908 to Rydell for xe2x80x9cElectrosurgical Instrument Having Needle Cutting Electrode and Spot-Coag Electrodexe2x80x9d. Rydell""s device includes an elongated flexible tubular member with a plurality of lumens. The distal end of the tubular member is provided with a bullet shaped ceramic tip covered with a conductive layer and having an opening coupled to a first one of the lumens. The conductive layer is coupled to a conductor which extends through a second one of the lumens to an electrical source. A second conductor, also coupled to the electrical source is slidable through the first lumen by a plunger. The two electrodes form a bipolar pair. In a second embodiment, the conductive layer on the ceramic tip is split by an insulating gap and both halves of the tip form a bipolar pair of electrodes. As with the Guay device, above, substantially the entire distal surface of Rydell""s device serves as an electrode when energized.
Several hemostatic bipolar electrosurgical scissors have also been described. U.S. Pat. No. 3,651,811 to Hildebrandt describes a bipolar electrosurgical scissors having opposing cutting blades forming active electrodes. The described scissors enables a surgeon to sequentially coagulate the blood vessels contained in the tissue and then to mechanically sever the tissue with the scissor blades. In particular, with the described bipolar electrosurgical scissors, the surgeon must first grasp the tissue with the scissor blades, energize the electrodes to cause hemostasis, de-energize the electrodes, and then close the scissor blades to sever the tissue mechanically. The scissors are then repositioned for another cut accomplished in the same manner. With the bipolar electrosurgical scissors of Hildebrandt, the surgeon cannot maintain the electrodes in a continuously energized state because the power supply would be shorted out and/or the blades damaged if the blades are permitted to contact each other while energized.
The disadvantages of the bipolar scissors of Hildebrandt are overcome by the disclosure in U.S. Pat. Nos. 5,324,289 and 5,330,471 to Eggers. In its preferred embodiment, the bipolar electrosurgical scissors of Eggers comprise a pair of metal scissor blades which are provided with an electrically insulating material interposed between the shearing surfaces of the blades so that when the scissor blades are closed, the metal of one blade never touches the metal of the other blade, i.e., the insulating material provides the cutting edge and the shearing surface. With the arrangement provided by Eggers, a cautery current will pass from the top back edge of the bottom metal blade through the tissue which is to be cut and to the bottom back edge of the top metal blade directly in advance of the cutting action. As the scissors are gradually closed, the hemostasis preferentially occurs at a location just in advance of the cutting point which itself moves distally along the insulated cutting edges of the blades in order to sever the hemostatically heated tissue. With this arrangement, the scissors may be maintained in a continuously energized state while performing the cutting. The Eggers patent describes various alternative embodiments of the bipolar scissors, including the use of metal blades with only one blade being insulated on its shearing surface, and the use of insulating blades with back surfaces coated with metal.
It is therefore an object of the invention to provide a pair of scissor blades for a bipolar cauterizing surgical scissors which provide a metal on metal cutting/shearing action.
It is another object of the invention to provide a pair of scissors blades for a bipolar cauterizing surgical scissors which have shearing surfaces that are insulated from cautery surfaces.
It is also an object of the invention to provide an endoscopic bipolar cauterizing scissors which provides a metal on metal cutting action and which may be either curved or flat.
In accord with the objects of the invention, the scissor blades of the present invention are comprised of an electrically conductive electrode, an electrically insulating material, and a metal shearing surface which is electrically insulated and physically spaced from the electrode by the insulating material which is disposed therebetween. The scissor blades, for example, may comprise but are not limited to a composite assembly of an electrode layer, an insulating layer, and a metal shearing surface layer. In the presently preferred embodiment, the electrode layer is a metal blade which is typically constructed from stainless steel, while the insulating layer is a ceramic which is deposited, bonded, or otherwise fixed on the metal blade, and the metal shearing surface layer which also provides the cutting edge is a metal (e.g., copper, gold, stainless steel etc.) which is metalized, deposited, sputtered, plated, bonded, or otherwise fixed onto the ceramic. In a second embodiment, the insulating layer is a ceramic support, with the electrode layer and the metal shearing surface layer being metalized, deposited, sputtered, plated, bonded, or otherwise fixed to the ceramic support. In a third embodiment, the insulating layer is deposited, bonded, or otherwise fixed onto a metal blade which includes the cutting edge and shearing surface, while the electrode metal layer is metalized, deposited, sputtered, plated, bonded, or otherwise fixed onto the insulating layer. In a fourth embodiment, the insulating layer is a composite material such as fiberglass which is provided with metal electrode and metal shearing surface layers which are metalized, deposited, sputtered, plated, bonded, or otherwise fixed onto opposite sides of the fiberglass layer. In all embodiments, since the metal cutting edges and shearing surfaces are insulated from the electrodes, no short circuit can form between the electrodes even though the cutting edges and shearing surfaces are metal.
As the scissor blades are intended for use as part of an endoscopic instrument, each blade is preferably provided with a first hole which receives an axle or clevis pin around which the blades rotate. In addition, each blade is preferably provided with a pin or protrusion extending from a proximal or base portion of the blade. The pins are provided to receive links which couple the blades to an actuator mechanism.
The endoscopic bipolar cautery scissors instrument which utilizes the blades of the invention is substantially as is described in copending application U.S. Ser. No. 08/284,793, the complete disclosure of which is hereby incorporated by reference herein, and utilizes a push rod assembly with two conductive push rods which are stabilized and insulated relative to each other. The distal ends of the push rods are coupled to the end effectors by the links. The proximal ends of the push rods extend through the handle and lever of the scissors instrument and present electrical cautery pins onto which a standard bipolar cautery plug can be mated.
Additional objects and advantages of the invention will become apparent to those skilled in the art upon reference to the detailed description taken in conjunction with the provided figures.

Bipolar endoscopic surgical scissor blades and instrument incorporating the same


The invention is directed to reusable, clip-type oximetry sensors that comprise opposing top and bottom members. In one aspect, the sensor includes a resilient spring member interposed between the top and bottom members to provide a closing force, wherein the resilient spring member comprises tensile and compressive portions. That is, upon positioning a patient appendage in the sensor different portions of the resilient spring member are in tension and in compression so as to combinatively provide an enhanced closing force utilized to secure the patient appendage between the top and bottom members. The resilient spring member may be of a molded, monolithic construction, comprising an elastomeric material. In another aspect, the inventive sensor includes cushions interconnected to the top and bottom members via snap-fit engagement. The snap-fit engagement may be provided by a plurality of interconnecting member pairs (e.g., projections and mating recesses), wherein the connection axes of the members comprising each pair are transversely disposed to yield enhanced interconnection via two-dimensional restraint between the cushions assemblies and top and bottom members.

The present invention is generally directed to photoplethysmographic measurement instruments, and more specifically to clip-type pulse oximetry sensors which attach to patient appendages.
A common technique used to monitor blood oxygen levels is pulse oximetry. In this regard, it is known that the light transmissivity and color of blood is a function of the oxygen saturation of the heme in the blood""s hemoglobin. For example, heme that is saturated with oxygen appears bright red because saturated heme is relatively permeable to red light. In contrast, heme that is deoxygenated appears dark and bluish as it is less permeable to red light. A pulse oximeter system measures the oxygen content of arterial blood by first illuminating the blood with red and infrared radiation and determining the corresponding amounts of red and infrared radiation that are absorbed by the heme in the blood. In turn, such light absorption amounts may be employed in conjunction with known calibration information to determine blood oxygen levels.
Pulse oximetry sensors generally include one or more light emitters, a detector, and a means for holding the emitter(s) and detector in contact with a patient""s tissue so that an optical path is established through the tissue. There are various means for holding the emitter(s)/detector in contact to a patient""s tissue; however, two common types are flexible and clip-type sensors. Flexible sensors may simply comprise an adhesive strip onto which the emitter(s)/detector are mounted for placement about a patient appendage. Clip-type sensors typically include two hingedly connected housings onto which the emitter(s) and detector are mounted. Generally, clip-type sensors are releasably attached to a patient""s appendage (e.g., finger, ear lobe or the nasal septum) so that the appendage is isolated between the two housings.
Both mentioned sensor types present advantages and disadvantages. In particular, clip-type sensors may be advantageously reused on different patients and are relatively easy to attach to and remove from a patient tissue site. Further, the present inventor has recognized the desirability of providing a reusable sensor which securely attaches to a patient""s appendage while reducing any interference with blood circulation, which is resistant to contamination, which yields reduced relative appendage movement, which is durable and which is configured for ease of assembly.
In view of the foregoing, a primary object of the present invention is to provide a reusable oximeter sensor which securely and reliably attaches to a patient""s appendage while reducing any arterial blood flow interference.
Another objective of the present invention is to provide a reusable oximeter sensor that inhibits contaminant infiltration.
A further object of the present invention is to provide a reusable oximeter sensor which reduces relative movement of an inserted appendage.
An additional object of the present invention is to provide a reusable oximeter sensor having enhanced durability.
Yet another objective of the present invention is to provide a reusable pulse oximetry sensor which is relatively easy to assemble.
One or more of the above objectives and additional advantages are realized by the present invention. In one aspect, a clip-type pulse oximetry sensor is provided which comprises top and bottom members disposed in opposing and hinged relation, and a spring member interposed therebetween. More particularly, a resilient spring member may be located between the sensor""s top and bottom members near a rearward end of the members (e.g., an end opposite to that which securably receives a patient appendage). The resilient spring member acts to provide the force required to close and thereby hold the forward ends of the top and bottom members on a patient""s inserted appendage. Of note, the closing force may be provided by a combination of tensile and compressive portions integrated into the spring member. That is, when the sensor is secured upon a patient appendage a portion of the resilient hinge member is actuated to be tensioned and another portion is actuated to be compressed. Attempting to return to their non-deformed static condition, the tensile and compressive portions combinatively exert an enhanced closing force to reliably hold the sensor to the inserted appendage.
Preferably, contact surfaces of the spring member directly engage both the top and bottom members when the sensor is assembled, thereby facilitating force transfer therebetween. The contact surfaces may comprise wings which extend rearwardly at the top and bottom of the spring member. Relatedly, rearward ends of the top and bottom members may be rimmed and/or otherwise configured to provide conformal seats for flushly receiving the spring member wings. When compressive forces are applied to the rearward ends of the top and bottom members (e.g., via hand manipulation) the spring member wings are forced towards one another, compressing a rearward-facing portion of the spring member while tensioning a forward-facing portion of the spring member. Correspondingly, the forward ends of the top and bottom members will open to accommodate patient appendage insertion/positioning therebetween. When the compressive forces are released, the tensile and compressive portions of the spring member co-act to provide the above-noted closing force.
A rearward-facing side of the spring member (e.g., extending between the above-noted wings) is preferably defined by a continuous surface. For example, in a winged embodiment having a U-shaped profile, the rearward side of the spring member may comprise a concave, semi-cylindrical surface that extends between the top and bottom members across the width of the sensor to completely close the rear-end of the sensor. As may be appreciated, the provision of a continuous rearward surface on the spring member reduces contaminate infiltration into the sensor.
Of note, the spring member may be advantageously defined as a one-piece unit. More particularly, the resilient spring member may have an integral, monolithic structure. To provide such a structure, the spring member may advantageously comprise a molded polymeric material.
In the latter regard, and more generally, the resilient spring member preferably comprises an elastomeric material. By way of example only, the spring member may a material selected from a group consisting of thermoplastic elastomers, liquid silicone rubbers, polyolefin elastomers, thermoplastic rubbers urethanes and natural rubbers. The utilization of an elastomeric spring member facilitates the realization of a range of spring constants for different applications of the inventive sensor. As such, the same basic design/componentry of the inventive sensor may be employed for a number of different patient applications entailing different desired clamping forces for patient appendage securement. That is, only the specific elastomer utilized in the spring members needs to vary from sensor to sensor. For example, a large-finger patient sensor may comprise a spring member having a different modulus of elasticity than that of another spring member utilized in a small finger patient sensor.
Preferably, the spring member may comprise one or more openings to accommodate hinged interconnection of the top and bottom members and/or to allow for the routing of electrical wiring between the top and bottom members. More particularly, the spring member may comprise an opening extending laterally therethrough from side to side to accommodate a hinge pin that hingedly interconnects the top and bottom members. In this embodiment, the hinge pin acts as a fulcrum or hinge axis for the top and bottom members. Additionally, the hinge pin functionally separates the above-noted tensile and compressive portions of the hinge member. For example, when the sensor is opened (e.g. to accommodate insertion or after insertion of a patient appendage), the portion of the spring member in front of the hinge pin is pulled in tension while the portion rearward the pin is compressed.
The spring member may also include a slot that extends from the top of the spring member to the bottom thereof to provide a passageway to route electrical wiring for emitter and/or detector componentry carried by the top and bottom members. Preferably, the slot is located on a forward-facing side of the spring member. In one embodiment, the slot is located on the spring member""s vertical centerline and extends from the front of the spring member and in to the lateral opening of the spring member. This arrangement effectively divides the above-noted tensile portion into two separated sides. During assembly electrical wiring for emitter and/or detector componentry may be routed through the slot and retained behind the hinge pin, thereby isolating and protecting the wires.
The lateral opening through the resilient spring member may also advantageously include a keyway slot. Correspondingly, the hinge pin may include an outwardly projecting key member slidably positionable in the keyway slot. Such an arrangement orients the hinge pin about a symmetry plane of the spring member. During actuation of the spring member, the slot allows the hinge pin to float with the symmetry plane, thereby equalizing the stress within the spring member. In turn, the actuation life of the spring member may be enhanced.
According to another aspect of the present invention, a clip-type pulse oximeter sensor is disclosed that comprises opposing and hingedly connected top and bottom members, and a cushion interconnected to one of the top and bottom members. Preferably, cushions are interconnected to each of the top and bottom members.
Each cushion may comprise a frame and a pliable member supported about a polygonal area by the frame. In turn, an optical window (e.g., a plastic lens) may be supported about its periphery within said polygonal area by the pliable member. Generally, each cushion may be interconnected to a top or bottom member, wherein the pliable member is free to flexibly conform to a patient""s appendage and thereby locate the optical window in intimate relation to the patient appendage. Relatedly, one or more light emitter(s) or light detector(s) may be located adjacent to, and preferably connected to, each optical window.
Of note, the pliable member may comprise an elastomeric material (e.g., a synthetic rubber) that is over-molded onto the frame. In turn, the frame may comprise a molded polymeric material (e.g., a glass-filled polymer that bonds well with an elastomeric pliable member). Such an arrangement enhances the pliable member/frame interconnection and facilitates effective load transfer therebetween.
Of note, the cushions may be advantageously attached to the top and bottom members using snap-fit means. The snap-fit means may include a plurality of interconnecting member sets to attach each given cushion to a top or bottom member. Each of the interconnecting member sets may comprise a projection and a mating recess. In turn, each of the cushions and top and bottom members may comprise at least one projection and at least one mating recess to facilitate secured interconnection therebetween. Further, the recesses may be configured so as to restrict movement of a corresponding projection in at least two dimensions.
As may be appreciated, the projections and recesses may be integrated into the above-noted cushion frames and interfacing top and bottom members. In such arrangements, the frames and each of the top and bottom members may advantageously comprise at least one projection and at least one mating recess. Preferably, different ones of a plurality of interconnecting member sets may be located on the opposing sides of the sensor and on the forward side of the sensor.
As noted, a plurality interconnecting member sets may be advantageously utilized. Preferably, these interconnecting member sets are oriented so that their respective interconnection axes are transverse to one another. By transversely orienting the connection axes, a given cushion may be securely locked into a top/bottom member to restrict relative movement in three dimensions. For example, use of interconnecting members sets on at least two sides of a polygonal (e.g. rectangular) cushion frame and interfacing bottom/top member facilitates a secure interconnection both laterally and longitudinally, as well as in the depth profile. Such arrangements effectively restrict relative movement between sensor componentry upon patient movements during use.
Additional aspects advantages of the present invention will become apparent upon consideration of the further description that follows.

Pulse oximetry sensor with improved appendage cushion