A thermoplastic molding composition of the ABS type is disclosed. The composition that contains an elastic-thermoplastic graft polymer and a copolymer comprising styrene and acrylonitrile, is characterized in that the graft polymer is a product of radical emulsion polymerization process that is initiated by a combination of a persulfate compound and at least one azo compound and in that a first mixture that contains said azo compound and a first amount of monomers is fed in to a rubber in latex form and in a subsequent reaction step a second mixture is introduced that contains the persulfate compound and a second amount of monomers.

The present invention provides thermoplastic moulding compositions of the ABS type containing specific highly effective graft polymer components which are obtained by emulsion polymerization using specific initiator systems and observing defined reaction conditions.
Moulding compositions of the ABS type are two-phase plastics comprising
I) a thermoplastic copolymer comprising styrene and acrylonitrile, in which the styrene may be wholly or partially replaced by xcex1-methylstyrene or methyl methacrylate; this copolymer, also known as SAN resin or matrix resin, forms the external phase;
II) at least one graft polymer which has been produced by grafting reaction of one or more of the monomers mentioned under I) on butadiene-, homo- or -copolymer (xe2x80x9cgraft basexe2x80x9d). This graft polymer (xe2x80x9celastomer phasexe2x80x9d or xe2x80x9cgraft rubberxe2x80x9d) forms the disperse phase in the matrix resin.
With identical matrix the strength of an ABS moulding composition is substantially determined by the graft rubber. For highly stressed moulded parts, however, the strength achievable with conventional ABS moulding compositions is not always sufficient with the necessary reliability, particularly when very high strengths at low temperature are also required or these requirements are only met at the expense of other equally desirable properties such as hardness or processing behaviour.
There is therefore a need for graft polymers on the basis of which ABS moulding compositions with very high strength values at room temperature and at low temperature can be produced without deterioration of the remaining properties, particularly hardness and processability.
Furthermore, it should also be possible to produce these graft rubbers on the basis of finer-particle rubber bases so that moulded parts with a high surface gloss may also be obtained if required.
It has now been found that moulding compositions of the ABS type with excellent strengths at room temperature and low temperature are obtained without serious losses as regards the other properties if the graft polymer used is produced using specific combinations of initiator systems and observing defined reaction conditions.
The production of graft rubbers using various initiator systems is known. Numerous documents including EP-A 154 244, for example, describe the use of potassium persulfate as initiator.
Documents such as EP-A 745 623 (see also the literature cited therein) describe the use of specific redox systems or azo initiators.
Although such initiator systems do indeed lead to graft polymers which lead to good properties for specific requirements in thermoplastic moulding compositions, good strength values at high and low temperatures while retaining the other properties are not, however, achieved to a sufficient extent.
The invention provides thermoplastic moulding compositions of the ABS type containing
A) at least one elastic-thermoplastic graft polymer obtained by radical emulsion polymerization of resin-forming vinyl monomers, preferably of styrene or acrylonitrile, wherein styrene and/or acrylonitrile may be wholly or partially replaced by xcex1-methylstyrene, methyl methacrylate or N-phenylmaleinimide, in the presence of rubber present in latex form with a glass transition temperaturexe2x89xa60xc2x0 C. using an initiator combination comprising a specific azo compound and a persulfate compound and
B) at least one copolymer comprising styrene and acrylonitrile, wherein styrene and/or acrylonitrile may be wholly or partially replaced by xcex1-methylstyrene or methyl methacrylate or N-phenylmaleinimide,
characterized in that the graft polymer A) is produced by feed of the monomers to the rubber latex, at the start of the graft polymerization reaction the specific azo compound is added in quantities of 0.2 to 3 wt. %, preferably 0.3 to 2.5 wt. % and particularly preferably 0.5 to 2 wt. % (related to the monomers metered in up to the time of the persulfate compound addition in each case), after a monomer addition of 10 to 95 wt. %, preferably 20 to 85 wt. %, particularly preferably 20 to 80 wt. %, in particular 30 to 75 wt. % and most particularly preferably 35 to 70 wt. % (related to total monomer quantity in each case) a persulfate compound is added in quantities of 0.05 to 1.5 wt. %, preferably 0.08 to 1.2 wt. % and particularly preferably 0.1 to 1.0 wt. % (related to the monomers metered in from the time of the persulfate compound addition in each case) and the polymerization is brought to an end, wherein a compound of formula (IIl)
where R=CH3, C2H5, C3H7, C4H9,
wherein the isomer groups n-C3H7, i-C3H7, n-C4H9, i-C4H9, t-C4H9 are included,
or a mixture thereof is used as azo compound.
In principle all rubber-like polymers present in emulsion form, with a glass transition temperature below 0xc2x0 C. are suitable as rubbers for the production of the elastic-thermoplastic graft polymers according to the invention.
Examples of those which may be used are:
diene rubbers, i.e. homopolymers of conjugated dienes with 4 to 8 C atoms such as butadiene, isoprene, chloroprene or their copolymers with up to 60 wt. %, preferably up to 30 wt. %, of a vinyl monomer, e.g. acrylonitrile, methacrylonitrile, styrene, xcex1-methylstyrene, halogen styrenes, C1-C4 alkyl styrenes, C1-C8 alkyl acrylates, C1-C8 alkyl methacrylates, alkylene glycol diacrylates, alkylene glycol dimethacrylates, divinyl benzene;
acrylate rubbers, i.e. homo and copolymers of C1-C10 alkyl acrylates, e.g. homopolymers of ethyl acrylate, butyl acrylate or copolymers with up to 40 wt. %, preferably not more than 10 wt. %, of monovinyl monomers, e.g. styrene, acrylonitrile, vinyl butyl ether, acrylic acid (ester), methacrylic acid (ester), vinyl sulfonic acid. Those acrylate rubber homo and/or copolymers are preferably used which contain 0.01 to 8 wt. % of divinyl or polyvinyl compounds and/or N-methylolacrylamide and/or N-methylolmethacrylamide or other compounds which act as crosslinking agents, e.g. divinyl benzene, triallyl cyanurate.
Polybutadiene rubbers, SBR rubbers with up to 30 wt. % of styrene incorporated by polymerization and acrylate rubbers, particularly those which have a core/shell structure, such as are described in DE-OS 3 006 804 for example, are preferred.
Latices with average particle diameters d50 of 0.05 to 2.0 xcexcm, preferably 0.08 to 1.0 xcexcm and particularly preferably 0.1 to 0.5 xcexcm, are considered for producing the graft polymers according to the invention. The gel contents of the rubbers used may be varied in wide limits, preferably they are between 30 and 95 wt % (determined by the wire cage method in toluene, (cf. Houben-Weyl, Methoden der Organischen Chemie, Makromolekulare Stoffe, Part 1, p. 307 (1961), Thieme Verlag publishers, Stuttgart)).
Most particularly preferred are mixtures of rubber latices with
a) average particle diameters d50xe2x89xa6320 nm, preferably 260 to 310 nm, and gel contentsxe2x89xa670 wt. %, preferably 40 to 65 wt. % and
b) average particle diameters d50xe2x89xa7370 nm, preferably 380 to 450 nm, and gel contentsxe2x89xa770 wt. %, preferably 75 to 90 wt. %.
The rubber latex (a) preferably has a spread of the particle size distribution of 30 to 100 nm, particularly preferably 40 to 80 nm, the rubber latex (b) one of 50 to 500 nm, particularly preferably 100 to 400 nm (measured in each case as the d90xe2x88x92d10 value from the integral particle size distribution).
The mixtures contain the rubber latices (a) and (b) preferably in the weight ratio 90:10 to 10:90, particularly preferably 60:40 to 30:70 (related in each case to the particular solids content of the latices).
The average particle diameter is determined by ultracentrifuge (cf. W. Scholtan, H. Lange: Kolloid-Z. u Z. Polymere 250, p. 782-796 (1972)).
The values quoted for the gel content relate to the determination by the wire cage method in toluene (cf. Houben-Weyl, Methoden der Organischen Chemie, Makromolekulare Stoffe, Part 1, p. 307 (1961), Thieme Verlag publishers, Stuttgart).
The rubber latices used may be produced by emulsion polymerization, the requisite reaction conditions, auxiliary substances and techniques are known in principle.
It is also possible initially to produce a fine-particle rubber polymer by known methods and then agglomerate it in known manner to set the required particle size. Relevant techniques are described (cf EP-PS 0 029 613; EP-PS 0 007 810; DD-PS 144 415; DE-AS 12 33 131; DE-AS 12 58 076; DE-OS 21 01 650; U.S. Pat. No. 1,379,391).
The so-called seed polymerization method may also be used, in which a fine-particle butadiene polymer is initially produced, for example, and then further polymerized to larger particles by further conversion with monomers containing butadiene.
The conventional anionic emulsifiers such as alkyl sulfates, alkyl sulfonates, aralkyl sulfonates, soaps of saturated or unsaturated fatty acids (e.g. oleic acid, stearic acid) and alkaline disproportionated or hydrogenated abietic or tall oil acid may be used as emulsifiers, preferably emulsifiers with carboxyl group (e.g. salts of C10-C18 fatty acids, disproportionated abietic acid) are used.
In principle rubber polymer latices may also be produced by emulsifying finished rubber polymers in aqueous media (cf. Japanese patent application 55 125 102).
Virtually all compounds which may be polymerized in emulsion to produce thermoplastic resins, e.g. aromatic vinyl compounds of formula (I) or compounds of formula (II) and/or mixtures thereof,
in which
R1 is hydrogen or methyl,
R2 is hydrogen, halogen or alkyl with 1 to 4 carbon atoms in ortho, meta or para position,
R3 is hydrogen or methyl and
X is CN, R4OOC or R5R6NOCxe2x80x94,
wherein
R4 stands for hydrogen or alkyl with 1 to 4 carbon atoms and
R5 and R6 independently of each other stand for hydrogen, phenyl or alkyl with 1 to 4 carbon atoms,
are suitable as graft monomers which are polymerized in the presence of the rubber-like polymers present in emulsion form.
Examples of compounds of formula (I) arc styrene, xcex1-methylstyrene, p-methylstyrene and vinyl toluene. Examples of compounds of formula (II) are acrylonitrile and methyl methacrylate. Further suitable monomers are vinyl acetate and N-phenylmaleinimide for example.
Preferred monomers are mixtures of styrene and acrylonitrile, xcex1-methylstyrene and acrylonitrile, of styrene, acrylonitrile and methyl methacrylate and combinations of these monomer mixtures with N-phenylmaleinimide.
Preferred graft polymers A) according to the invention are those which are obtained by graft polymerization of styrene and acrylonitrile in the weight ratio 90:10 to 50:50, preferably 80:20 to 65:35 (wherein styrene may be wholly or partially replaced by xcex1-methylstyrene or methyl methacrylate) in the presence of such quantities of rubber, preferably polybutadiene, that graft polymers with rubber contents of 20 to 80 wt. %, preferably 30 to 75 wt. % and particularly preferably 35 to 70 wt. % result.
The graft polymers A) are produced according to the invention in such a way that a specific azo compound is added to the rubber latex and/or to the rubber latex mixture at the start of the graft reaction.
Suitable specific azo compounds which are preferred are those of general formula (III)
where R=CH3, C2H5, C3H7, C4H9,
wherein the isomer groups n-C3H7, i-C3H7, n-C4H9, i-C4H9, t-C4H9 are included.
The compound of formula (III) where R=C2H5 is particularly preferred.
The quantities of azo compound used are 0.2 to 3 wt. %, preferably 0.3 to 2.5 wt. % and particularly preferably 0.5 to 2 wt. % (related in each case to the monomers metered in up to the time of the persulfate compound addition).
The graft monomers are then metered in and after an added quantity of 10 to 95 wt. %, preferably 20 to 85 wt. %, particularly preferably 20 to 80 wt. %, in particular 30 to 75 wt. % and most particularly preferably 35 to 70 wt. % (related to total monomer quantity in each case) is achieved, at least one persulfate compound is added in quantities of 0.05 to 1.5 wt. %, preferably 0.08 to 1.2 wt. % and particularly preferably 0.1 to 1.0 wt. % (related in each case to the monomers metered in from the start of the persulfate compound addition).
Examples of suitable persulfate compounds are sodium peroxodisulfate, potassium peroxodisulfate, ammonium peroxodisulfate, the preferred persulfate compound is potassium peroxodisulfate.
Both the azo compound and the persulfate compound are conventionally used in the form of aqueous solutions, aqueous emulsions, aqueous suspensions or other aqueous dispersions.
The remaining monomers are then metered in and polymerization is brought to an end.
The invention further provides the process for producing graft rubbers, wherein
i) the graft monomers are metered into the rubber latex,
ii) the azo compound is added at the start of the graft polymerization reaction in quantities of 0.2 to 3 wt. % (related to the monomers metered in up to the time of the persulfate compound addition)
iii) after a monomer addition of 10 to 95 wt. % (related to the total monomer quantity) a persulfate compound is added in quantities of 0.05 to 1.5 wt. % (related to the monomers metered in from the time of the persulfate compound addition) and
iv) the polymerization reaction is brought to an end,
wherein a compound of formula (III)
where R=CH3, C2H5, C3H7, C4H9,
wherein the isomer groups n-C3H7, i-C3H7, n-C4H9, i-C4H9, t-C4H9 are include,
is used as azo compound.
The reaction temperature in the production according to the invention of the graft rubbers A) may be varied in wide limits. It is 25xc2x0 C. to 160xc2x0 C., preferably 40xc2x0 C. to 90xc2x0 C.; most particularly preferably the temperature at the start of monomer metering differs from the temperature at the end of monomer metering by 20xc2x0 C. maximum, preferably 10xc2x0 C. maximum and particularly preferably 5xc2x0 C. maximum.
In addition, molecular weight regulators may be used in the graft polymerization, preferably in quantities of 0.05 to 2 wt. %, particularly preferably in quantities of 0.1 to 1 wt. % (related in each case to the total monomer quantity).
A procedure preferred according to the invention is to add molecular weight regulators only in the reaction stage after addition of the persulfate compound and to avoid any regulator addition in the reaction stage before the addition of the persulfate compound.
Examples of suitable molecular weight regulators are n-dodecylmercaptan, t-dodecylmercaptan, dimeric xcex1-methylstyrene, terpinolene and mixture combinations comprising these compounds.
The above-mentioned compounds may be used as emulsifier in the graft polymerization reaction, emulsifiers with carboxyl groups are preferred.
The graft rubber latex A) is prepared by known methods, such as by spray-drying or by addition of salts and/or acids, washing of the precipitation products and drying of the powder.
Copolymers of styrene and acrylonitrile in the weight ratio 90:10 to 50:50 are preferably used as vinyl resins B), wherein styrene and/or acrylonitrile may be wholly or partially replaced by xcex1-methylstyrene and/or methyl methacrylate; in quantitative terms up to 30 wt. % (related to vinyl resin) of a further monomer from the series maleic anhydride, maleic imide, N-(cyclo)-alkylmaleinimide, N-(alkyl)-phenylmaleinimide may be optionally co-used.
The weight average molecular weights ({overscore (M)}w) of these resins may vary within wide limits, preferably they are between approx. 40,000 and 200,000, particularly preferably between 50,000 and 150,000.
Particulars of the production of these resins are described in DE-AS 2 420 358 and DE-AS 2 724 360 for example. Resins produced by bulk and/or solution polymerization and by suspension polymerization have proved particularly successful.
The content of the elastic-thermoplastic graft polymer (A) in the moulding compositions according to the invention may vary within wide limits; preferably it is 10 to 80 wt. %, particularly preferably 20 to 75 wt. %.
The required and/or appropriate additives such as anti-oxidants, UV stabilizers, peroxide decomposers, anti-static agents, lubricants, mould release agents, flameproofing agents, filling or reinforcing material (glass fibres, carbon fibres etc.) and colorants may be added to the moulding compositions according to the invention on production, preparation, further processing and final moulding.
Final moulding may be undertaken on conventional commercial processing equipment and comprises, for example, processing by injection moulding, sheet extrusion with optionally subsequent thermoforming, cold forming, extrusion of pipes and profiles or calender processing.
The moulding compositions of the ABS type according to the invention may be mixed with other polymers. Suitable blend partners are selected, for example, from at least one polymer, chosen from the polycarbonates, polyesters, polyester carbonates and polyamides group.
Suitable thermoplastic polycarbonates and polyester carbonates are known (cf., for example, DE-AS 1 495 626, DE-OS 2 232 877, DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610, DE-OS 3 832 396, DE-OS 3 077 934), and may be produced, for example, by reaction of diphenols of formulae (IV) and (V)
in which
A is a single bond, C1-C5-alkylene, C2-C5-alkylidene, C5-C6-cycloalkylidene, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94 or xe2x80x94COxe2x80x94,
R7 and R8 independently of each other stand for hydrogen, methyl or halogen, particularly for hydrogen, methyl, chlorine or bromine,
R9 and R10 independently of each other stand for hydrogen, halogen preferably chlorine or bromine, C1-C8-alkyl, preferably methyl, ethyl, C5-C6-cycloalkyl, preferably cyclohexyl, C6-C10-aryl, preferably phenyl, or C2-C12-aralkyl, preferably phenyl-C1-C4-alkyl, particularly benzyl,
m is a whole number from 4 to 7, preferably 4 or 5,
n is 0 or 1,
R11 and R12 can be individually selected for each X1 and independently of each other stand for hydrogen or C1-C6-alkyl and
X1 stands for carbon,
with carbonic acid halides, preferably phosgene, and/or with aromatic dicarboxylic acid dihalides, preferably benzene dicarboxylic acid dihalides, by phase boundary polycondensation or with phosgene by polycondensation in homogeneous phase (the so-called pyridine method), wherein the molecular weight may be set in known manner by means of a corresponding quantity of known chain terminators.
Examples of suitable diphenols of formulae (IV) and (V) are hydroquinone, resorcinol, 4,4xe2x80x2-dihydroxy diphenyl, 2,2-bis-(4-hydroxyphenyl)-propane, 2,4-bis-(4-hydroxyphenyl)-2-methyl butane, 2,2-bis-(4-hydroxy-3,5-dimethylphenyl)-propane, 2,2-bis-(4-hydroxy-3,5-dichlorophenyl)-propane, 2,2-bis-(4hydroxy-3,5-dibromophenyl)-propane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethyl cyclohexane, 1,1-bis-(4-hydroxyphenyl)-3,3-dimethyl cyclohexane, 1,1-bis-(4-hydroxyphenyl)-3,3,5,5,-tetramethyl cyclohexane or 1,1-bis-(4-hydroxyphenyl)-2,4,4,-trimethyl cyclopentane.
Preferred diphenols of formula (IV) are 2,2-bis-(4-hydroxyphenyl)-propane and 1,1-bis-(4-hydroxyphenyl)-cyclohexane, the preferred phenol of formula (V) is 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethyl cyclohexane.
Mixtures of diphenols may also be used.
Examples of suitable chain terminators are phenol, p-tert.-butyl phenol, long-chain alkyl phenols such as 4-(1,3-tetramethyl-butyl)phenol according to DE-OS 2 842 005, monoalkyl phenols, dialkyl phenols with a total of 8 to 20 C atoms in the alkyl substituents according to DE-OS 3 506 472, such as p-nonyl phenol, 2,5-di-tert.-butyl phenol, p-tert.-octyl phenol, p-dodecyl phenol, 2-(3,5-dimethylheptyl)-phenol and 4-(3,5-dimethylheptyl)-phenol. The required quantity of chain terminators is generally 0.5 to 10 mole %, related to the sum of the diphenols (IV) and (V).
The suitable polycarbonates and/or polyester carbonates may be linear or branched; branched products are preferably obtained by the incorporation of 0.05 to 2.0 mole %, related to the sum of the diphenols used, of tri- or more than tri-functional compounds such as those with three or more than three phenolic OH groups.
The suitable polycarbonates and/or polyester carbonates may contain aromatically bound halogen, preferably bromine and/or chlorine; preferably they are halogen-free.
They have average molecular weights ({overscore (M)}w, weight average), determined by ultracentrifuging or light-scattering measurement for example, of 10,000 to 200,000, preferably of 20,000 to 80,000.
Suitable thermoplastic polyesters are preferably polyalkylene terephthalates, i.e. reaction products of aromatic dicarboxylic acids or their reactive derivatives (e.g. dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or arylaliphatic diols and mixtures of such reaction products.
Preferred polyalkylene terephthalates may be produced by known methods (Kunststoff-Handbuch, Vol. VIII, p. 695 ff., Carl Hanser Verlag publishers, Munich 1973) from terephthalic acids (or their reactive derivatives) and aliphatic or cycloaliphatic diols with 2 to 10 C atoms.
In preferred polyalkylene terephthalates 80 to 100, preferably 90 to 100 mole % of the dicarboxylic acid groups, terephthalic acid groups and 80 to 100, preferably 90 to 100 mole % of the diol groups are ethylene glycol and/or butane-1,4-diol groups.
In addition to ethylene glycol and/or butane-1,4-diol groups the preferred polyalkylene terephthalates may contain 0 to 20 mole % of groups of other aliphatic diols with 3 to 12 C atoms or cycloaliphatic diols with 6 to 12 C atoms, e.g. groups of propane-1,3-diol, 2-ethylpropane-1,3-diol, neopentyl glycol, pentane-1,5-diol, hexane-1,6-diol, cyclohexanedi-1,4-methanol, 3-methylpentane-1,3- and 1,6-diol, 2-ethyl hexane-1,3-diol, 2,2-diethylpropane-1,3-diol, hexane-2,5-diol, 1,4-di(xcex2-hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy-1,1,3,3-tetramethyl cyclobutane, 2,2-bis-(3-xcex2-hydroxyethoxyphenyl)-propane and 2,2-bis-(4-hydroxypropoxypbenyl)-propane (DE-OS 2 407 647, 2 407 776, 2 715 932).
The polyalkylene terephthalates may be branched by incorporation of relatively small quantities of trihydric or tetrahydric alcohols or tribasic or tetrabasic carboxylic acids, as described in DE-OS 1 900 270 and U.S. Pat. No. 3 692 744. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylol ethane and propane and pentaerythritol. It is advisable to use no more than 1 mole % of the branching agent, related to the acid component.
Particularly preferred are polyalkylene terephthalates which have been produced solely from terephthalic acid and its reactive derivatives (e.g. its dialkyl esters) and ethylene glycol and/or butane-1,4-diol and mixtures of these polyalkylene terephthalates.
Preferred polyalkylene terephthalates are also copolyesters which are produced from at least two of the above-mentioned alcohol components; particularly preferred copolyesters are poly-(ethylene glycol butane-1,4-diol) terephthalates.
The polyalkylene terephthalates which are preferably suitable, generally have an intrinsic viscosity of 0.4 to 1.5 dl/g, preferably 0.5 to 1.3 dl/g, in particular 0.6 to 1.2 dl/g, measured in phenol/o-dichlorobenzene (1:1 parts by weight) at 25xc2x0 C. in each case.
Suitable polyamides are known homopolyamides, copolyamides and mixtures of these polyamides. They may be partly crystalline and/or amorphous polyamides.
Polyamide-6, polyamide-6,6, mixtures and corresponding copolymers comprising these components are suitable as partly crystalline polyamides. Partly crystalline polyamides which are also considered are ones whose acid component consists wholly or partially of terephthalic acid and/or isophthalic acid and/or suberic acid and/or sebacic acid and/or azelaic acid and/or adipic acid and/or cyclohexane dicarboxylic acid, whose diamine component consists wholly or partially of m-and/or p-xylylene diamine and/or hexamethylene diamine and/or 2,2,4-trimethylhexamethylene diamine and/or 2,2,4-trimethylhexamethylene diamine and/or isophoron diamine and whose composition is known in principle.
Furthermore, polyamides may be mentioned which are produced wholly or partially from lactams with 7-12 C atoms in the ring, optionally with the co-use of one or more of the above-mentioned starting components.
Particularly preferred partly crystalline polyamides are polyamides-6 and polyamide 6,6 and their mixtures. Known products may be used as amorphous polyamides. They are obtained by polycondensation of diamines such as ethylene diamine, hexamethylene diamine, decamethylene diamine, 2,2,4- and/or 2,4,4-trimethylhexamethylene diamine, m- and/or p-xylylene diamine, bis-(4-aminocyclohexyl)-methane, bis-(4-aminocyclohexyl)-propane, 3,3xe2x80x2-dimethyl-4,4xe2x80x2-diamino-dicyclohexylmethane, 3-aminomethyl,3,5,5,-trimethylcyclohexylamine, 2,5- and/or 2,6-bis-(aminomethyl)-norbornene and/or 1,4-diaminomethyl cyclohexane with dicarboxylic acids such as oxalic acid, adipic acid, azelaic acid, decane dicarboxylic acid, heptadecane dicarboxylic acid, 2,2,4- and/or 2,4,4-trimethyl adipic acid, isophthalic acid and terephthalic acid.
Copolymers which are obtained by polycondensation of several monomers are also suitable, further copolymers which are produced with addition of aminocarboxylic acids such as xcex5-aminocaproic acid, xcfx89-aminoundecanoic acid or xcfx89-aminolauric acid or their lactams.
Particularly suitable amorphous polyamides are the polyamides produced from isophtbalic acid, hexamethylene diamine and further diamines such as 4,4xe2x80x2-diaminodicyclohexylmethane, isophoron diamine, 2,2,4- and/or 2,4,4-trimethylhexamethylene diamine, 2,5- and/or 2,6-bis-(aminomethyl)-norbornene; or from isophthalic acid, 4,4xe2x80x2-diamino-dicyclohexylmethane and xcex5-caprolactam; or from isophthalic acid, 3,3xe2x80x2-dimethyl-4,4xe2x80x2-diamino-dicyclohexylmethane and laurinlactam; or from terephthalic acid and the isomer mixture comprising 2,2,4- and/or 2,4,4triethylhexamethylene diamine.
Instead of the pure 4,4xe2x80x2-diaminodicyclohexylmethane, mixtures of the positional isomer diaminodicyclohexylmethanes may be used, which are composed of 70 to 99 mole % of the 4,4xe2x80x2-diamino isomer 1 to 30 mole % of the 2,4xe2x80x2-diamino isomer 0 to 2 mole % of the 2,2xe2x80x2-diamino isomer and optionally correspondingly more highly condensed diamines which are obtained by hydrogenation of technical grade diaminodiphenylmethane. Up to 30% of the isophthalic acid may be replaced by terephthalic acid.
If at least one polymer, selected from the polycarbonates, polyesters, polyester carbonates and polyamides group, is used in addition, the quantity thereof is up to 500 parts by weight, preferably up to 400 parts by weight and particularly preferably up to 300 parts by weight (related to 100 parts by weight of A+B in each case).
In the examples which follow, the parts quoted are parts by weight at all times and the percentages quoted are percentages by weight, unless otherwise stated.

Thermoplastic moulding materials based on special highly effective grafted polymer components


A bowtie monopole antenna is fabricated of a sheet metal radiating body 102 that is triangular shaped, and having a longitudinal dimension and axis (106) and a width (108). One corner of the radiating body is tapered to form a feed point (104). The length dimension determines the antenna's lowest resonance frequency while the taper created by the width determines the highest point of resonance. For using the bowtie monopole antenna in a communication device, the radiating body (102) is folded or wrapped around towards itself To facilitate the folding or wrapping a mounting substrate (202) is used. The substrate may be provided with retaining features (206) to capture the antenna assembly within the communication device.

Mobile communication devices are in widespread use and have become extremely popular and proven useful for business and personal activities. In addition to conventional cellular calling, these devices are being designed to access other types of communication resources, such as wireless local area networks for both data and voice calling, for example. Often these different communication resources are accessed at substantially different frequency bands. Communicating in different frequency bands present a challenge to designers. A designer may chose to use multiple antennas, one for each frequency band, but that approach is impractical and not likely to be received well in the market. A second approach is to design a wideband antenna system using multiple antenna elements. Typically a whip antenna element is paired with a helical antenna element. However, as the size of mobile communication devices continues to decrease, whip antenna elements are not favored, and instead users prefer smaller stub antennas. Therefore there exists a need for a short, stub antenna that provides a broadband response for use with multiple transceivers in a mobile communication device.

Bowtie monopole antenna and communication device using same


The invention describes novel crosslinking compounds that include photoactivatable moieties. Several families of compounds are disclosed that can include one or more hydrophilic moieties that help to solubilize the compounds in aqueous environments.

There exist many ways to coat, adhere, adsorb, modify, etc. a surface with a material, such that the material changes the characteristics of the surface. For example, suitable coatings can be prepared that when applied to a given surface render the surface hydrophobic. In other instances, the coating may provide enhanced ability to bind with a target molecule, such as a protein.
In particular, there are known crosslinking materials that include a latent reactive group, such as a photoactivatable group. The crosslinking material has, in general, at least two photoactivatable groups, such that one group can be activated and attached to the surface of the substrate. The remaining latent group, can then later be, or simultaneously with the surface attachment, activated to react with a target molecule such as a polymer or a biomolecule.
There are generally three types of crosslinking materials with photoactivatable groups. One type is hydrophobic in nature, making it difficult to dissolve in an aqueous systems. The second type is hydrophilic, but includes quaternary charged moieties. Quaternary compounds tend to promote non-specific binding of non-target molecules, which is often not a desired result. A third type of crosslinking material with photoactivatable groups includes negatively "charged" groups, such as carboxylic acids, sulfonic acids, phosphoric acids and the like. Although these materials are considered to be hydrophilic, they also increase non-specific binding interactions with non-targeted molecules by the crosslinking material.
Therefore, a need exists for a crosslinking material that includes photoactivatable groups that is hydrophilic in nature and does not promote non-specific binding interactions with non-target molecules.

This patent is subject to a terminal disclaimer.

Photochemical crosslinkers for polymer coatings and substrate tie-layer


The present invention provides systems and methods for maintaining the stability of a network. The present invention includes systems and methods that identify an open circuit condition and reconfigure the network bus to continue communications without slowing the communication rate or removing the network bus from service. The system includes a termination device associated with each network device. Each termination device includes a network termination element that can be switchably connected to the network bus in response to a command issued by a bus controller when an open circuit condition downstream of the network device has been detected. In another embodiment, the present invention provides systems and methods for controlling input current to a remote device located on a network. A sensing element is associated with the device that is capable of sensing the input current and through switches, altering the input current to the remote device.

As systems, such as the multimedia entertainment, communications and diagnostic systems utilized by the automotive and aerospace industries, become more complex, a need arises for additional devices to communicate, either with each other or with a central controller or the like. Historically, these systems included dedicated wiring extending between the various devices in order to support communications therebetween. As systems have become more integrated and the communications requirements have been increased, the amount of dedicated wiring that would be required can quickly become excessively large, both in terms of the space required for the wiring and the cost of the wiring and the attendant installation. Moreover, as the amount of dedicated wiring increases, the overall complexity of the system also generally increased as well as the likelihood that some portion of the wiring might be damaged or broken during or following installation.
As such, network buses have been developed to provide a common communication path between a plurality of devices. In automotive and aerospace applications, for example, a network bus can be utilized to monitor various components and to collect diagnostic and status information. In this regard, diagnostic and status information relating to the strain, acceleration, pressure and/or temperature to which the various components are subjected may be collected and analyzed. By way of further example, a network bus architecture is currently being developed to support communications and the delivery of multimedia information to the occupants of a vehicle, such as an automobile, minivan, sports utility vehicle, aircraft, boat or the like. Advantageously, this network bus would transport the audio signals, including streaming audio signals, produced by one or more of a radio, a cassette tape player, a compact disc player or the like to selected speakers or headphone jacks throughout the vehicle. Similarly, the network bus may support voice and data communications with a cellular telephone carried by an occupant of the vehicle, as well as communications with a laptop computer, a handheld computing device or the like. Also, the network bus may transmit video signals, including streaming video signals, from a television receiver, a videocassette recorder or other video source to one or more video monitors. In addition, the network bus may transmit sensor and actuator signals to and from devices such as drivetrain devices, passive restraint devices, crash avoidance devices, drive-by-wire devices, or the like.
In addition to the variety of devices that are connected to a network bus, one or more controllers are also generally connected to the network bus for receiving data from the various devices and for sending commands to the devices. Among other things, these commands specify the manner in which the various devices are to function including the manner in which the various devices are to transmit information over the network bus. Additionally, the controller(s) can receive input from an operator, such as an occupant of the vehicle. This input can include, for example, an indication of the source(s) of the signals to be transmitted over the network bus as well as the destination of the signals.
Traditionally, networks of the type described above have transmitted data in analog format. Unfortunately, analog signals are susceptible to noise introduced into the signals during data transmission. Given that many of the transmitted signals have a low amplitude to start with, this noise can corrupt the signal and decrease the signal to noise ratio to levels that cause loss of resolution in the signal. Further, as many of these network devices are scattered some distance from the controller, the electrical lines connecting the network devices to the controller may be sufficiently long to cause signal degradation due to DC resistance in the wiring.
In light of these shortcomings, it would be advantageous to utilize digital networks. But, many conventional digital networks suffer from a variety of problems themselves. For example, many existing digital networks operate according to complicated protocols which require each network device to have a relatively high level processor, thereby increasing the cost of the network devices. Complicated protocols also introduce overhead into the messages on the bus that are not necessary for data acquisition and control. This overhead can severely limit the number of data samples that can be transmitted on the bus. These networks also have other problems. For example, some do not support both acquisition and control. Further, these networks typically have bulky network device interfaces, slow network communication rates and/or a low network device count. Additionally, many computer systems that include digital networks do not operate in a time-deterministic manner. As such, these computer systems generally lack the capability to schedule a trigger command to the network components that repeats or is interpreted and executed with any precision timing.
Regardless of the digital or analog nature of network, the network bus may be damaged during or following installation. In this regard, the network bus typically consists of a plurality of conductors or wires that may extend great lengths between the various controllers and network devices. Due to accidents or other unforeseen circumstances, one or more of the wires may be broken, thereby creating an open circuit. Thus, components on one side of the open circuit will be unable to communicate via the broken conductor with components on the other side of the open circuit. Additionally, signals transmitted over the broken conductor will be reflected by the broken end of the conductor due to the impedance mismatch. The reflected signals will then be returned along the conductor, thereby interfering, both constructively and destructively, with other signals being transmitted via the conductor. While the components on one side of the open circuit may be able to communicate at relatively low communication rates, such as ten kilobits per second, reflected signals will generally prevent effective communications between the components at higher communication rates such as ten megabits per second or the like. Moreover, the open circuit will render the broken conductor more susceptible to noise, thereby further limiting effective communications.
In instances in which one or more conductors of the network bus are broken, one of two different approaches has generally been taken. According to one approach, the network bus remains unrepaired for at least some period of time rendering the network bus useless until repairs are made. The network may utilize a redundant bus, which, after the damaged network bus is retired, carries the communications for the network until the damaged network bus is repaired. In addition, communications can continue over the network bus, albeit at a relatively slow communication rate that is selected so as not to be corrupted by the reflected signals. Since a number of applications require that communications be conducted via the network bus at relatively high communication rates, the intentional slowing of the data over the network bus to reduce, if not negate, the deleterious impact of reflected signals may be inappropriate. Alternatively, communications via the network bus can be halted and the technician can troubleshoot the network bus to identify the break in the network bus and can then physically repair the broken conductors. Once the repairs have been completed, the communications over the network bus can be recommenced. However, the physical repair of the network bus oftentimes requires that the network bus be removed from service for some period of time, which action may also be inappropriate for certain applications, such as time-sensitive applications, safety-critical applications, applications that result in some type of liability if inoperable, or other applications that demand continuous monitoring or feedback.
Accordingly, it would be advantageous to develop an improved network bus that could accommodate bus failure caused by an open circuit condition, such as the breaking of one or more conductors of the network bus. Moreover, it would be desirable for the improved network bus to support continued communications between the devices connected to the network bus after the open circuit condition, without having to remove the network bus from service in order to physically repair the network bus.
In addition to problems with open circuits in a network, there may also be problems associated with provision of excessive current to a device on the network. To protect the often complex and costly remote devices of many networks, a circuit breaker or fuse is connected at a distribution area to a power supply that supplies input current to the remote devices, such as via the network bus. Typically, circuit breakers and fuses interrupt the current in an electric circuit, sometimes referred to as tripping the circuit breaker or fuse, when the current through the circuit becomes higher than that allowed by the circuit breaker or fuse. Conventional circuit breakers and fuses are typically rated for a specific current level that generally depends upon the components in the circuit and their current tolerances. When the current through the circuit breaker exceeds the rated current level, the circuit breaker or fuse trips and interrupts the current in the circuit.
In one type of conventional circuit breaker, such as a mechanical circuit breaker, when enough current runs through the circuit to trip the circuit breaker, a pair of contacts that are normally in contact in order to conduct current through the circuit breaker and the rest of the circuit are separated, such as by preloaded springs, thus breaking the circuit. Generally, a conventional fuse includes a strip of a low-melting metal that is connected in series with the circuit. Because of its electrical resistance, the metal strip is heated by current through the circuit. And if the current exceeds the current rating of the fuse, the strip melts, thus breaking the circuit.
While conventional circuit breakers and fuses are used in many power systems, they pose some problems. Generally, conventional circuit breakers and fuses are positioned at the distribution point between the power source and the network bus to protect the network bus and all of the devices as a whole instead of the devices individually. But because different remote devices can have different current tolerances, a single conventional circuit breaker or fuse cannot optimally protect all of the remote devices of the network from excessive current.
Occasionally in networks employing a single conventional circuit breaker or fuse the remote devices can draw an excessive amount current that is over the current tolerance of the respective remote devices, such as during defective operation of one or more remote devices. In such an instance, it would be desirable for the circuit breaker or fuse to break the circuit to protect the remote devices drawing the excessive amount of current. But in some instances the excessive amount of current is below the current rating of the circuit breaker or fuse and, therefore, the circuit breaker or fuse provides no protection for the remote devices drawing the excessive amount of current. In such an instance, the affected remote devices suffer from an unnecessary danger of damage caused by overheating and even fire due to the excessive amount of current. Conversely, if the current rating of the circuit breaker or fuse is set according to the remote device with the lowest current tolerance, the circuit breaker or fuse will trip if remote devices having higher current tolerances attempt to draw current levels within their tolerance but below the lowest current tolerance. As shown, a single circuit breaker or fuse connected to the network bus at a distribution point is undesirable because remote devices typically have different current tolerances. Because a single circuit breaker or fuse results in all-or-nothing power to the remote devices on the network since, if one remote device requires protection from excessive current, all of the devices on the network must receive the same protection, even if it is unnecessary.
In addition to the inability of a single conventional circuit breaker or fuse to optimally protect all of the remote devices of the network from excessive current, conventional mechanical circuit breakers and fuses suffer from limitations due to their material characteristics. Most conventional circuit breakers and fuses cannot be adjusted for different requirements without replacing the entire circuit breaker. For example, if a mechanical circuit breaker is rated for a ten amp trip and is attached to a circuit containing a remote device rated for five amps, the ten amp rated circuit breaker would need to be replaced with a five amp rated circuit breaker to provide over-current protection for the five amp rated remote device.
One method by which to protect all of the remote devices from individual excessive current situations is to provide an individually current rated circuit breaker or fuse to each remote device connected to the network bus, in addition to the circuit breaker or fuse connected at the distribution point to protect the network bus. But disadvantageously, such a method leads to an increase in the cost, size and weight of the network because it requires added components (i.e., circuit breakers). Additionally, because such a method merely employs multiple conventional circuit breakers, it suffers from the same material drawbacks as conventional circuit breakers and fuses in that it does not allow for adjustments to account for changes in the characteristics of the remote device, such as replacing the remote device with one current rating with a remote device with a different current rating.
Accordingly, it would be advantageous to develop an improved system to control the input current to the remote devices to protect remote devices on an individualized basis based upon the respective current tolerances of each remote device without adding additional circuit breakers to the network. Moreover, it would be desirable for the improved system to allow for adjustments in the current rating protection afforded to the remote devices to account for changes in the current tolerance of the remote device.

Systems and methods for maintaining network stability


This invention relates to photosensitive silicone resins and resin compositions containing the same. Silicone resins of this invention are characterized by that a triorganosilyl group represented by the following general formula (1)

This invention relates to silicone resins and photosensitive resin compositions containing the same useful as resist materials.
In the fields of a variety of electronic devices including semiconductor devices that require microfabrication, there is a rising demand for higher density and higher degree of integration of devices and finer patterning has become essential to meet this demand. Moreover, in plasma display panels (PDP), barriers of a high aspect ratio, that is, a high ratio of height to width, are in demand in order to have light of high luminance emitted by enlarging the electric discharge space for display.
A method for obtaining higher resolution in patterning is to use light of shorter wavelength in patterning of photoresists. However, the use of shorter wavelength poses a problem of the depth of focus (DOF) becoming reduced with a drop in sensitivity and aspect ratio. Multi-level resist processes have been proposed to solve this problem. According to a process of this kind, a material such as novolac and polyimide that can be readily dry-etched by oxygen plasma is deposited by spin coating on a substrate and planarized, a resist resistant to dry etching by oxygen is applied to the surface of the planarized layer, a pattern is formed, and then the pattern is transferred to the bottom layer by anisotropic etching by oxygen plasma. As this process yields patterns of a high aspect ratio, developmental works are being conducted extensively on resist materials resistant to oxygen plasma etching.
Resist materials utilizing silicone resins are known to be highly resistant to oxygen plasma etching and, for example, compositions consisting of ladder type polysiloxane esters or polysiloxanes substituted with epoxy-containing alkyl groups and a photosensitive compound capable of generating acid upon exposure to light are proposed in JP 7-56354 (1995)A1 and JP 8-193167 (1996)A1. Moreover, resist compositions containing photosensitive silicone resins that are polysiloxanes to which a diazonaphthoquinonesulfonyloxy group and an azido group are linked are proposed in JP 6-27671 (1994)A1 and JP 6-95385 (1994)A1.
As for the barrier (rib) of a plasma display panel (PDP), a process for constructing a rib with the use of a paste formulated from photosensitive resins and inorganic powders to raise the aspect ratio is described in JP 10-62981 (1998)A1. The photosensitive resins in question are acrylic polymers and the like.
Polyorganosilsesquioxanes are occasionally abbreviated to polysiloxanes and they are known to occur in three types, that is, cage, ladder, and random. Their structures and methods of preparation are described in detail in the specifications of WO98/41566, JP 50-139900 (1975)A1, JP 6-329687 (1994)A1, JP 6-248082 (1994)A1 and elsewhere. A method for introducing functional groups to the ends of these polyorganosilsesquioxanes is also described in detail in the aforementioned WO98/41566.
An object of this invention is to provide photosensitive silicone resins which exhibit excellent performance as resist materials for multi-level resist processes and for forming PDP barriers. Another object of this invention is to provide resist materials which exhibit excellent plasma resistance (resistance to O2-RIE) and form patterns of a high aspect ratio.
This invention relates to silicone resins composed of polyorganosilsesquioxanes whose ends are partly or wholly linked to a triorganosilyl group represented by the following general formula (1)
(wherein R is a divalent organic group and Rxe2x80x2 is a divalent group or a direct bond).
This invention also relates to the aforementioned silicone resins wherein the polyorganosilsesquioxanes have a repeating unit represented by the following general formula (2)
(wherein R2 is an unsubstituted or substituted phenyl group) and the average number of repeating units is 2-5,000.
Furthermore, this invention relates to the aforementioned silicone resins wherein the polyorganosilsesquioxanes consist of one type or a mixture of two types or more selected from ladder type, cage type, and mixed cage-ladder type and the weight average molecular weight Mw is 800-100,000 as determined by gel permeation chromatography (GPC) and calibrated against polystyrene.
Still more, this invention relates to the aforementioned silicone resins wherein R is xe2x80x94R1COOX1xe2x80x94 or xe2x80x94R1COOX1xe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94 (wherein R1 is the divalent residue of a polycarboxylic acid or derivative thereof and X1 is a divalent group).
Still further, this invention relates to photosensitive resin compositions formulated from the aforementioned silicone resins and a photogenerator of acid.
Finally, this invention relates to a process for preparing the aforementioned silicone resins which comprises treating polyorganosilsesquioxanes with Xxe2x80x94Si(R3)2xe2x80x94Y or Xxe2x80x94Si(R3)2OSi(R3)2xe2x80x94Y [wherein X and Y are groups capable of linking with carboxyl groups or functional groups capable of reacting with terminal OH groups or terminal OM groups is an alkali metal) of the backbone of polyorganosilsesquioxanes and R3 is a monovalent organic group] to give modified polyorganosilsesquioxanes containing X or Y at all or a part of their terminal positions, and treating the terminal groups with txe2x80x94BuOOCxe2x80x94R1xe2x80x94COOH (wherein txe2x80x94Bu is t-butyl group and R1 is the divalent residue of a polycarboxylic acid or derivative thereof). The group R3 here is a monovalent organic group such as alkyl and aryl, preferably methyl, and R3 in a given molecule may be of the same kind or of two or more kinds.
Photosensitive silicone resins of this invention are structurally polyorganosilsesquioxanes to which a triorganosilyl group represented by the aforementioned general formula (1) is linked to all or a part of the ends of the backbone chain. The backbone chain may be represented by the general formula (R2Si2O3)n and n designates the number of repetition and is 2 or more. Preferable polyorganosilsesquioxanes have a repeating unit represented by the aforementioned general formula (2) and the average number of repeating units is 2-5,000, more preferably 5-500. The group R2 is a monovalent organic group and may be a hydrocarbon group such as aryl and alkyl and an alkoxy group, but R2 is preferably an alkyl group with 1-6 carbon atoms or an unsubstituted or substituted phenyl group, more preferably a phenyl group.
In the triorganosilyl group represented by the general formula (1), R is a divalent organic group and, as indicated by the aforementioned general formula (1), R may be said to contain the residue of a carboxylic acid. The group Rxe2x80x2 designates a divalent group or a direct bond and, in the case of a divalent group, it is linked on the other side to the terminal Sixe2x80x94Oxe2x80x94 group of polyorganosilsesquioxanes. The t-butyl group at the end of of the triorganosilyl group comes off to leave a free carboxyl group behind when it contacts the acid generated from a photogenerator of acid thereby enhancing the the alkali solubility of silicone resins and it is this property that is utilized in patterning.
Carboxylic acids which give the divalent group R include monocarboxylic acids such as benzoic acid and acetic acid and polycarboxylic acids and they are preferably polycarboxylic acids. Such polycarboxylic acids include pyromellitic acid, trimellitic acid, phthalic acid, biphenyldicarboxylic acid, biphenyltetracarboxylic acid, biphenylhexacarboxylic acid, benzophenonedicarboxylic acid, benzophenonetetracarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl sulfone tetracarboxylic acid, diphenyl sulfide dicarboxylic acid, diphenyl sulfide tetracarboxylic acid, benzanilidedicarboxylic acid, benzanilidetricarboxylic acid, benzanilidetetracarboxylic acid, benzanilidepentacarboxylic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, succinic acid, adipic acid, maleic acid, and fumaric acid.
In the case of polycarboxylic acids, the carboxyl group not linked to t-butyl group may be present as free carboxyl (xe2x80x94COOH) or in the form of ester or salt. In particular, it is preferable that one of the carboxyl groups forms an ester linkage with Si either directly or through a divalent group X as illustrated by txe2x80x94Buxe2x80x94OOCxe2x80x94R1xe2x80x94COOxe2x80x94Xxe2x80x94Si(Me)2xe2x80x94. Here, the group R in the general formula (1) corresponds to R1xe2x80x94COOX and X is a divalent group such as alkylene or arylene or a direct bond.
In case polycarboxylic acids is tricarboxylic or higher acids, at least one of the carboxyl groups remains intact and it may remain so or it may be converted to the neutral form such as ester and salt. Alkali solubility becomes poorer if the carboxyl group in question exists in the neutral form such as ester. The acid from a photogenerator of acid contributes to enhance alkali solubility by dissociating the t-butyl group and generating a carboxylic acid. In the cases in which patterning is effected by utilizing this phenomenon, there should desirably be a large difference in alkali solubility between the exposed and unexposed regions and, for this reason, the free carboxyl groups are converted to esters, preferably to t-butyl esters by treating with t-butyl alcohol or derivative thereof.
The group R may contain not only the residue of a carboxylic acid but also a part of the residue of a terminal modifier which modifies the ends of polyorganosilsesquioxanes as described above. A suitable terminal modifier can be represented by Xxe2x80x94Si(CH3)2xe2x80x94Y in which Y is a functional group capable of linking to the backbone polyorganosilsesquioxanes and X is a functional group capable of linking to a group such as carboxyl. For example, a terminal modifier represented by Xxe2x80x94Si(CH3)2xe2x80x94Oxe2x80x94Si(CH3)2xe2x80x94Y [wherein Y is a functional group such as epoxy capable of reacting with the terminal OH or OM group (M is an alkali metal)] reacts with polyorganosilsesquioxanes at one end through Y to give polyorganosilsesquioxanes containing X at the other end. The X-terminated polyorganosilsesquioxanes then react with the aforementioned polycarboxylic acid or derivative thereof to give a product whose R contains xe2x80x94CH2xe2x80x94CH(OH)xe2x80x94 in case X is an epoxy group. A variety of groups such as ester and amide can be formed by changing X. In the aforementioned terminal modifier, X and Y may naturally be identical with or different from each other, but one of them needs to be reactive with the terminal group (or terminal group being generated during the reaction) of polyorganosilsesquioxanes and the other needs to be reactive with a group such as carboxyl or derivative thereof. As is apparent from the above description, the backbone polyorganosilsesquioxanes and the triorganosilyl group represented by the general formula (1) are linked not necessarily through a siloxane linkage but through an appropriate group.
Photosensitive silicone resins of this invention can be prepared by utilizing a known reaction. In the case of polyorganosilsesquioxanes containing terminal silanol, for example, the terminal modification is effected by treating the polymers with a monohalide such as Xxe2x80x94Si(CH3)2xe2x80x94Cl. One of preferable procedures for terminal modification is to treat polyorganosilsesquioxanes such as silanol-free cage type and/or ladder type octaphenylsesquioxane with a terminal modifier such as the aforementioned Xxe2x80x94Si(R3)2xe2x80x94Oxe2x80x94Si(R3)2xe2x80x94X in the presence of an alkali metal catalyst to give X-terminated polyorganosilsesquioxanes.
A silicon atom in polyorganosilsesquioxanes and the silicon atom in a terminal modifier such as Xxe2x80x94Si(CH3)2xe2x80x94Y tend to undergo exchange reaction and a procedure utilizing this property is also effective for terminal modification. In this case, at least one of X and Y needs to be reactive with a carboxyl group. Moreover, it is possible to effect the aforementioned reaction and the exchange reaction simultaneously by using Y as a group capable of reacting with the end of polyorganosilsesquioxanes.
A preferable procedure for preparing silicone resins of this invention from terminally modified polyorganosilsesquioxanes is, for example, to treat the terminally modified polyorganosilsesquioxanes with an acidic ester prepared by the reaction of t-butyl alcohol with a polycarboxylic acid or derivative thereof such as acid anhydride in the presence of a quaternary ammonium salt as a catalyst.
Silicone resins of this invention have a weight average molecular weight of 800-100,000, preferably 5,000-50,000, as determined by GPC and calibrated against polystyrene. The silicone resins in question are solid at normal temperature and soluble in many organic solvents such as esters and ethers. Furthermore, silicone resins of this invention are preferably polyorganosiloxanes represented by the general formula (C6H5S3/2)n having a triorganosilyl group represented by the general formula (1) at all or 10% or more of their replaceable ends, for example, one triorganosilyl group for n=4-20, preferably one for n=2-8.
Silicone resins of this invention are best suited for use as positive resist materials. In such end uses, it is possible to incorporate generators of acid or a variety of additives in order to enhance sensitivity or improve heat or a plasma resistance.
Additives indispensable to photosensitive resin compositions of this invention are photogenerators of acid. Such photogenerators of acid include, but are not limited to, sulfonium salts such as triphenylsulfonium trifluorosulfonate, triphenylsulfonium trifluoromethaneantimonate, triphenylsulfonium benzenesulfonate, and cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, iodonium compounds such as diphenyliodonium trifluoromethanesulfonate, and N-hydroxysuccinimide trifluoromethanesulfonate. A detailed description of the chemical formulas and actions of these photogenerators of acid is found in the aforementioned JP 8-193167 (1996)A1 and xe2x80x9cNew Development of Practical Polymer Resist Materialsxe2x80x9d, p. 57 (in Japanese) published by CMC. A photogenerator of acid is normally added at a rate of 0.2-25% by weight of total solids.
An organic solvent is used to adjust the viscosity. Preferable solvents include, but are not limited to, Methyl Cellosolve acetate, propylene glycol monoethyl ether acetate, methyl lactate, ethoxyethyl acetate, methyl pyruvate, methyl methoxypropionate, N-methylpyrrolidinone, cyclohexanone, methyl ethyl ketone, dioxane, ethylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether.
Photosensitive resin compositions of this invention contain the aforementioned photosensitive silicone resins and photogenerators of acid as indispensable components and often contain solvents. In addition, it is permissible to incorporate surfactants, colorants, stabilizers, coating improvers, and inorganic powders as needed.
Photosensitive silicone resins of this invention and their compositions can be used as resist materials and barrier materials of PDP. Although there is no restriction on the mode of their use as resist material, they are best suited for multi-level resist processes.
According to a multi-level resist process, a material such as novolac which can be readily dry-etched by oxygen plasma is applied by spin coating to the surfaceof a substrate, a material of this invention is applied thereto, the layers are exposed to a laser such as excimer to generate acid from a photogenerator of acid and let the acid dissociate silicone resins, patterning is effected by developing with an aqueous alkaline solution, and the bottom layer resist is etched by oxygen plasma to give a pattern of a high aspect ratio.
As for the preparation of barrier materials of PDP, methods such as sandblasting, embedding, and photopaste are known. Since any of the methods uses photosensitive resist materials, materials of this inventin can be used as such. In particular, when applied to the photopaste method or the like in which the resist remains unremoved, materials of this invention can fully produce the effect of excellent plasma resistance.

Silicone resin and photosensitive resin composition containing the same

Abstract: wherein R is a divalent organic group and Rxe2x80x2 is a divalent group or a direct bond is linked to all or a part of the ends of the backbone of polyorganosilsesquioxanes. Photosensitive resin compositions of this invention are formulated from the aforementioned silicone resins and a photogenerator of acid. The aforementioned silicone resins and photosensitive resin compositions show excellent performance as resist materials for multi-level resist processes and for forming barriers of PDP and, on account of their excellent plasma resistance (resistance to O2-RIE), yield patterns of a high aspect ratio.


A liquid crystal display device includes a liquid crystal display panel on a mold, and a backlight placed in the mold. The backlight includes a light guide panel, an LED provided on a side surface of the liquid guide panel, and other components. A main flexible wiring substrate is attached to the liquid crystal display panel, and extends to a back surface of the mold. The LED is mounted on an LED flexible wiring substrate. At least one electronic component mounted on the main flexible wiring substrate is arranged on an end surface of the mold. Then, an insulating sheet is provided between the at least one electronic component and the LED to prevent short circuit between them, instead of using a partition wall for electrical insulation.

For a liquid crystal display device used in mobile phone and personal digital assistant (PDA), a reduction in thickness is demanded. In addition, there is also a strong demand for making the screen larger while keeping the overall size smaller, namely, making it in the so-called narrow frame form. The small liquid crystal display device uses a light emitting diode (LED) as a light source of a backlight. However, the method of arranging the LED, the method of supplying electric current to the LED, and the use efficiency of the light from the LED are problems when trying to reduce the thickness and overall size of the liquid crystal display device.
In the configuration disclosed in JP-A No. 128820/2007, an LED is provided on a side surface of a light guide panel. A reflective sheet is provided on the back side of the light guide panel. The thickness of a portion of the reflective sheet is reduced, in which an LED flexible wiring sheet is provided to supply power to the LED.
In the configuration disclosed in JP-A No. 344851/2003, an LED is mounted on a main flexible wiring substrate attached to a liquid display panel. The main flexible wiring substrate is folded toward the back side so that the LED is provided on a side surface of the light guide panel. In JP-A No. 344851/2003, at this time, a light shielding pattern is formed in a portion of the back side of the main flexible wiring substrate to prevent the light of the LED from leaking to the outside through the main flexible wiring substrate.
In the method described above, the LED mounted on the main flexible wiring substrate is placed on a side surface of the light guide panel by folding the main flexible wiring substrate toward the back side of the light guide panel. However, this method has a problem in that it is difficult to obtain sufficient accuracy of the LED arrangement. In order to solve this problem, the following method has been proposed. There are separately formed two substrates, one is a main flexible wiring substrate attached to a liquid crystal display panel, and the other is an LED flexible wiring substrate for supplying power to the LED. Then, the main flexible wiring substrate and the LED flexible wiring substrate are attached to each other. This method can facilitate the LED to be placed at appropriate place in the light guide panel, without being constrained by the position of the main flexible wiring substrate.
In this case, the LED flexible wiring substrate is fixed to a portion of the light guide panel. The main flexible wiring substrate is fixed to a mold on which the liquid crystal display panel is mounted. Because the setting of the LED flexible wiring substrate and the main flexible wiring substrate at appropriate locations is prioritized, interference may occur between the electronic component mounted on the main flexible wiring substrate, and the LED mounted on the LED flexible wiring substrate.
The electronic component, solder around the connection, wiring, and the like, are formed to be exposed in the main flexible wiring substrate. Also the LED, solder around the connection, and the like, are formed to be exposed in the FED flexible wiring substrate. The main flexible wiring substrate and the LED flexible wiring substrate are arranged to overlap each other, and are finally attached to each other. In such a configuration, there may be a risk of short circuit between the electronic component, the solder around the connection, the wiring, and the like, in the main flexible wiring substrate, and the LED and the solder around the connection in the LED flexible wiring substrate.
This risk has been reduced by forming a partition wall between the portion of the electronic component mounted on the main flexible wiring substrate, and the portion of the LED, in order to prevent the electronic component from coming into contact with the LED, or with the solder around the connection and the like.
However, in this configuration, it is necessary to form the partition wall within the mold, thereby increasing the overall size of the mold. As a result, the overall size of the liquid crystal display device is increased. In addition, the space on both sides of the partition wall should be large enough to prevent the destruction of the LED or the electronic component due to the contact between the partition wall and the LED or the electronic component. This space requirement has caused a further increase in the overall size of the mold or in the overall size of the liquid crystal display device.

Panasonic Liquid Crystal Display Co., Ltd.


Systems and methods for operating a wireless communication system are provided. A network node can determine a first frequency band criteria and a second frequency band criteria based on information from an access node. The network node can determine a first timer duration of a first timer. The first timer duration can be based on the first frequency band criteria. The network node can determine a second timer duration of a second timer. The second timer can be based on the second frequency band criteria. The first timer duration can be different from the second timer duration. The access node can transmit the first timer duration and the second timer duration to the wireless device after the wireless device establishes communication with the access node.

Wireless network operators can provide access to wireless devices to allow communications over a wireless communication network. Wireless devices can select to establish communications with an access node of the network from a plurality of different frequency bands. The different frequency bands can include frequency bands within the same radio access technology, frequency bands within differing radio access technologies, frequency bands provided by the same network provider, and/or frequency bands provided by different network providers.
While a wireless device has the ability to communicate over various frequency bands, generally a wireless device can only establish communications over the network with one frequency band at a time. When the wireless device connects to the network over a less-preferred frequency band, a wireless device can scan for a more preferred frequency band. Typically, a wireless device initiates a single timer and scan for all available frequency bands during a single scan duration.
A timer duration (e.g. time between scans) and/or a scanning duration (e.g. the total time the wireless device scans for more preferred frequency bands) can undesirably affect a user experience. For example, when the timer duration is too short, the wireless device can use a significant amount of time and battery power by frequently scanning for other frequency bands. When the timer duration is too long, the wireless device can establish a communication session over a less preferred frequency band for extended periods, which can potentially result in a dropped call. When the scanning duration is too short, preferred frequency bands can be overlooked when the list of available frequency bands is longer than the scan duration allows. When the scanning duration is too long, the wireless device can be delayed in receiving a paging messages over the current frequency band because the wireless device cannot scan for other frequency bands while monitoring a paging channel for pages sent form the network.

Variable scanning timers in a multi band/multi-operator network


A portable apparatus includes a position detection unit, an azimuth detection unit, a map image a display control unit acquisition unit, and an orientation detection unit. The position detection unit detects a position of the portable apparatus. The azimuth detection unit detects an azimuth of the portable apparatus. The map image acquisition unit acquires a map image within a range based on the position and the azimuth. The display control unit displays the acquired map image on a display unit. The orientation detection unit detects an orientation of the portable apparatus. The display control unit displays the map image on the display unit according to the detected orientation.

1. Field of the Invention
The present invention relates to a portable apparatus which can display a captured image and map image.
2. Description of the Related Art
In recent years, portable apparatuses such as digital cameras, which can display a map image, have been proposed. For example, a portable apparatus proposed by Japanese Patent No. 4264099 has mounted on it a position detection unit such as a Global Positioning System (GPS) module, and is configured to display a map image of the region in the vicinity of the current position as detected by the position detection unit. Also, the portable apparatus proposed by Japanese Patent No. 4264099 can display an electronic viewfinder image (also called a through-image or the like). The portable apparatus of this literature is configured to switch an electronic viewfinder image and map image to be displayed according to an orientation change of the portable apparatus so as to smoothly switch the electronic viewfinder image and map image to be displayed.


A pulling rope fixing structure includes a handle, a grip rope, a fixing device, an elastic element and a pulling rope. The handle is a hollow tubular body with the grip rope passed through the handle; the grip rope has first and second ends with first and second openings respectively; the fixing device includes a retaining ring and a fastening element, and the fastening element has a hollow sleeve passed into the first and second openings and operated with the retaining ring to fix the grip rope. The elastic element is installed in the hollow sleeve and has a penetrating hole for passing the pulling rope and separating the pulling rope from the fixing device. The pulling rope not in a direct contact with the metal fixing device will not be worn directly during exercises, and the service life of the pulling rope can be extended effectively.

1. Field of the Invention
The present invention relates to an elastic fitness pulling rope structure, in particular to the pulling rope fixing structure capable of preventing damages caused by long-term contact and friction between a pulling rope and a fixing device installed onto the pulling rope.
2. Description of the Related Art
As our life becomes busier day after day, the time we spend on exercises becomes less and less. Since we live in an environment crowded with tall buildings, there is very little space left for exercises. To let people enjoy the fun of exercises in such environment, portable fitness equipments capable of maximizing the utility of space and time such as treadmills, steppers and elastic fitness devices are introduced.
With reference to FIG. 1 for a schematic view of a conventional elastic fitness device 1, the elastic fitness device 1 comprises a pulling rope 10, two handles 11, two strips 12 and two fixing elements 13, wherein each strip 12 is passed through the respective handle 11 and extended out from both ends of the handle 11; the fixing element 13 is provided for fixing and connecting both ends of the strip 12; and the pulling rope 10 is installed to the fixing element 13 and has an abutting portion 101 abutting the fixing element 13 to prevent the pulling rope 10 from being separated from the fixing element 13. When use, a user holds the two handles 11 and applies a force to the pulling rope 10, while overcoming the elastic force of the pulling rope 10 to achieve an in-situ exercise effect.
However, the aforementioned method of fixing the pulling rope 10 may break the pulling rope 10 at its contact point with the fixing element 13 by a fatigue wear, and users may be injured by the damaged pulling rope 10 during exercise.
In view of the foregoing problem, the inventor of the present invention developed a pulling rope fixing structure with the effects of preventing the pulling rope and the fixing device from rubbing with each other, preventing damages caused by frictions produced between the pulling rope and the fixing device, and extending the service life of the pulling rope, so as to overcome the foregoing problem of the prior art.

Plus ‘O’Minus Fitness Products (Suzhou) Co., Ltd.


A multi-zone screenless well fracturing method and apparatus which allows multiple zones in a well to be treated with one trip of the apparatus into the hole. The apparatus includes a tool string generally comprising a crossover, a packer below the crossover, and a concentric wash pipe extending below the packer. The crossover has a first portion in communication with a tubing string connected thereto and a second portion in communication with a well annulus above the packer. The first portion of the crossover is in communication with the inner wash pipe, and the second portion of the crossover is in communication with the outer wash pipe. The tool string is adapted to stab through a plurality of big bore casing packers which are positioned between adjacent zones. A method of fracturing multiple zones in a well while monitoring conditions at the zone is also disclosed.

1. Field of the Invention
This invention relates to fracturing zones in a well, and more particularly, to a method and apparatus which allows multiple zones to be treated with one trip of the apparatus into the hole and which does not require hydraulic fracturing to be removed from each zone separately.
2. Description of the Prior Art
Hydraulic fracturing is the parting of a desired section of a well formation or zone by an application of hydraulic pressure. A fracture made in this manner may be extended from the wellbore by continued pumping. Extended distance will depend on several factors such as injection rates, formation or zone characteristics, fracturing fluid properties and injected volume of fluid.
Selected particles, added to the fracturing fluid, are transported into the fracture. These act as propping agents to hold the fracture open when the applied pressure is dissipated, thus leaving a channel of high flow capacity connected to the wellbore.
Initially, fracturing was applied primarily to old wells, but now a majority of the treatments performed are on new ones. Many new fields and field extensions have resulted from the application of this production stimulation technique.
Research dealing with theory, methods and materials has resulted in a wide selection of fracturing fluids, additives and equipment to satisfy the many well conditions encountered.
Procedures have been developed to enhance the possibility of obtaining additional fractures during a single treatment of a well. These techniques are known as Multi-Frac. They are especially applicable on wells having multiple pay zones or long producing zones.
Any of a variety of known fracturing fluids may be employed to produce a fracture in the well. Then, that fracture is bridged or sealed. Additional fracturing fluid is then diverted to other parts of the zone, or to other zones, to produce another fracture. Repetition of this procedure has made varied numbers of fractures, as indicated by surveys conducted before and after the treatment. Granular type materials of specific size and characteristics have proven to be very effective for quick sealing and bridging fractures, thus diverting the fluid to other portions of the formation. These are called bridging agents.
The assignee of the present invention has developed a multiple-stage fracturing system which reduces elapsed times between stages, thus allowing operators to reduce rig time, completion time and expense. The system utilizes one or more tubing or casing baffles positioned in the completion string between the zones to be stimulated. Each zone may be perforated, fractured and then temporarily isolated with a bridging ball while a shallower zone is being completed in like manner. Thus, a two-, three-, four- or five-stage fracturing operation usually can be completed in a semi-continuous manner allowing for the short time delay required to perforate each zone before treatment.
Casing or tubing baffles installed between zones in the completion string have graduated internal openings. Sealing balls are selected and mated with the baffles so that the smaller diameter balls or plugs will pass through the larger ID baffles that are installed at the more shallow depths. Some of the balls are of such density that they usually are expelled from the tubing with the flow of fluids and gas when the well is opened to test or production.
Other, more conventional methods utilize setting a plug below a zone and positioning a fracturing tool thereabove which includes a packer. The tool is then removed from the wellbore and another bridge plug positioned below the next higher zone, and the tool utilized again to fracture the formation. This can be repeated as many times as necessary. This system has the disadvantage of having to remove the fracturing tool at each formation so that another plug can be set.
The apparatus of the present invention solves these problems by providing a tool which can be utilized to fracture multiple zones without requiring that the tool be removed from each zone separately. Rather, it can be used to fracture multiple zones in a single trip.

Multi-zone screenless well fracturing method and apparatus


A downsizable image generating apparatus capable of reducing the number of components is obtained. This thermal transfer printer (image generating apparatus) comprises a drive gear arranged on a first end of a support rod for rotating a head portion by transmitting driving force of a motor to a head portion pressing member. The head portion pressing member is provided with a gear portion meshing with the drive gear and a protrusion. The head portion is provided with a notch engaging with the protrusion of the head portion pressing member upon upward rotation of the head portion pressing member.

1. Field of the Invention
The present invention relates to an image generating apparatus, and more particularly, it relates to an image generating apparatus comprising a print head.
2. Description of the Background Art
A thermal printer (thermal transfer printer) is generally known as an image generating apparatus performing printing by pressing a print head against a platen provided in the form of a roll or the like. For example, Japanese Patent Laying-Open No. 6-122246 (1994) discloses such a thermal printer (thermal transfer printer).
The aforementioned Japanese Patent Laying-Open No. 6-122246 discloses a thermal printer pressing a print head against a platen roller by urging the printing head portion downward with a spring.
However, the conventional thermal printer disclosed in the aforementioned Japanese Patent Laying-Open No. 6-122246 is provided with no mechanical portion for automatically separating the print head from the platen roller, and hence it is disadvantageously necessary to manually lift up the print head, in order to separate the same from the platen roller.
In this regard, a print head printer provided with a mechanical portion for automatically separating a print head from a printer is proposed in general, as disclosed in Japanese Patent Laying-Open No. 5-309905 (1993), Japanese Patent Laying-Open No. 6-15852 (1994), Japanese Patent Laying-Open No. 6-191066 (1994) or Japanese Patent Laying-Open No. 9-188027 (1997), for example.
The aforementioned Japanese Patent Laying-Open No. 5-309905 discloses a print head, pressed against a platen with urging force of a spring, provided with a mechanical portion (head portion retraction means) formed by a gear wheel, a follower plate and an arm for moving the print head oppositely to the platen against the urging force of the spring.
Each of the aforementioned Japanese Patent Laying-Open No. 6-15852, Japanese Patent Laying-Open No. 6-191066 and Japanese Patent Laying-Open No. 9-188027 discloses a thermal printer, having a print head mounted on an arm synchronously rotating with a cam, capable of pressing and separating the print head against and from a platen roller by rotating the cam thereby rotating the arm. In this thermal printer, coupling arms coupling a support shaft rotatably supporting the print head and the print head with each other are provided on both ends of the print head for rotating the print head about the support shaft by engaging the coupling arms with the arm synchronously rotating with the cam.
In the conventional thermal printer disclosed in the aforementioned Japanese Patent Laying-Open No. 5-309905, however, the number of components is disadvantageously increased due to the mechanical portion (head portion retraction means) formed by the gear wheel, the follower plate and the arm separately provided for moving the print head oppositely to the platen in order to separate the print head from the platen.
In the conventional thermal printer having the print head mounted on the arm synchronously rotating with the cam disclosed in each of the aforementioned Japanese Patent Laying-Open No. 6-15852, Japanese Patent Laying-Open No. 6-191066 and Japanese Patent Laying-Open No. 9-188027, the arm presses only one of the coupling arms of the print head and applies pressing force to only the corresponding end of the print head if the thermal printer has only a single cam since the arm engaging with the cam engages with the coupling arms, and hence the print head cannot be uniformly pressed against the platen roller. In order to uniformly press the print head against the platen roller, therefore, two cams must be provided on both ends of the print head for pressing both ends of a coupling portion of the print head. More specifically, the cams must be arranged on both ends of the print head, and arms synchronously rotating with the cams must also be provided on both ends of the print head. Consequently, the number of components is disadvantageously increased in the conventional thermal printer disclosed in each of the aforementioned Japanese Patent Laying-Open No. 6-15852, Japanese Patent Laying-Open No. 6-191066 and Japanese Patent Laying-Open No. 9-188027, although the print head can be automatically separated from the platen roller. Further, the size of the thermal printer is disadvantageously increased due to the cams arranged on both ends of the print head.