CN1311037C - Resin composition and protective film - Google Patents

Resin composition and protective film Download PDF

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Publication number
CN1311037C
CN1311037C CNB2005100712083A CN200510071208A CN1311037C CN 1311037 C CN1311037 C CN 1311037C CN B2005100712083 A CNB2005100712083 A CN B2005100712083A CN 200510071208 A CN200510071208 A CN 200510071208A CN 1311037 C CN1311037 C CN 1311037C
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composition
acid
protective membrane
weight parts
multipolymer
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CN1683461A (en
Inventor
马场厚
丹羽一明
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JSR Corp
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JSR Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds

Abstract

A kind of resin composition contains a copolymer [A] of an unsaturated compound containing an epoxy group and an olefinic unsaturated compound other than it, a reaction product [B] of an epoxy resin containing a hydroxy group and an alkoxysilane, and a compound [C] capable of cationic polymerization except components [A] and [B], and a protective film formed therewith to provide a protective film for a photo device having high surface hardness and excellent in various resistances such as heat and pressure resistances, acid resistance, alkali resistance, and sputtering resistance.

Description

Resin combination and protective membrane
The present patent application is that application number is the dividing an application of application for a patent for invention of CN03131286.1 (applying date is on May 14th, 2003).
Technical field
The present invention relates to curable resin composition, form method, and the protective membrane of protective membrane.More particularly, relate to be suitable as be used to form liquid crystal display device (LCD) with colour filter and charge coupled cell (CCD) with colour filter etc. go up the material of used protective membrane curable resin composition, use said composition to form the method for protective membrane and the protective membrane that forms with said composition.
Background technology
LCD and CCD isoradial device adopt solvent, acid or alkaline solution etc. to carry out the dip treating of display element in its manufacturing processed.In addition, when adopting sputter to form the wiring electrode layer, element surface is exposed under the high temperature partly.Therefore, handle deterioration or damage because of this class, be provided with by the protective membrane that has the film of tolerance to constitute to these processing on the surface of element in order to prevent element.
Such protective membrane requires to have each following performance: to the matrix that will form this protective membrane or bottom and the layer tack height that forms on protective membrane; film itself is level and smooth and tough; the transparency is arranged; thermotolerance and photostabilization height;, flavescence painted, albefaction iso-metamorphism through not causing for a long time, water tolerance, solvent resistance, acid resistance and alkali resistance excellence or the like.As the material that is used to form the protective membrane that satisfies these various characteristicses, known have the spy open the disclosed thermoset composition that contains polymkeric substance of flat 5-78453 communique with glycidyl.
In addition, when using such protective membrane as the protective membrane of the colour filter of color liquid crystal display arrangement and charge coupled cell, general requirement can make the step difference planarization that is caused by the colour filter that forms on the bottom substrate.
Again; color liquid crystal display arrangement; the color liquid crystal display device of STN (Super Twisted Nematic) mode or TFT (Thin Film Transister) mode for example; in order to keep the box gap of liquid crystal layer equably, applying panel on the basis of the pad (spacer) that scatters globule (beads) shape on the protective membrane.Then by thermo-compressed sealing material encapsulated liquid crystals box.But can see the recessed phenomenon of protective membrane of the part that has globule this moment under heat and pressure, the disorder of box gap becomes problem.
When especially making the color liquid crystal display device of STN mode, must the utmost point carry out the applying tolerance range of colour filter and counter substrate closely, so claimed film has the step difference planarization performance and the heat-resisting withstand voltage properties of high degree.
In addition, in recent years, adopt and form cloth line electrode (indium tin oxide on the protective membrane that sputters at colour filter; ITO) film also is used the patterned mode of ITO with strong acid and highly basic etc.Therefore, protective membrane surface local ground when sputter exposes to the open air at high temperature, or carries out multiple medicine and handle.Therefore, also requirement can tolerate these and handles and when medicine is handled and the tack of cloth line electrode, ITO is not peeled off from protective membrane.
In order to form such protective membrane; use has the thermoset composition of the protective membrane that adopts simple and easy method can form the hardness excellence convenient suitable; but can form except satisfying general the requiring the performance as protective membrane such as transparency, also satisfy the protective membrane of above-mentioned every performance and also do not know as the material of the excellent storage stability of composition.
Disclosure of an invention
The present invention finishes according to above situation.
The objective of the invention is to; even provide surface low matrix; also can on this matrix, form the high cured film of flatness, and be fit to very much the resin combination of use for the optical device that forms various patience excellences such as surface hardness height, heat-resisting resistance to pressure, acid resistance, alkali resistance, anti-sputter with protective membrane.
Another object of the present invention is that the formation method of the protective membrane that has used above-mentioned composition of the present invention is provided.
Another other purposes of the present invention are, the protective membrane that is formed by above-mentioned composition is provided.
Another other purposes of the present invention and advantage are clear and definite by the following description.
According to the present invention, above-mentioned purpose of the present invention and advantage, the first, reach by a kind of resin combination, it is characterized in that, contain
[A] (a1) contains the multipolymer (below, claim multipolymer [A] sometimes) of the unsaturated compound of the epoxy group(ing) ethylene series unsaturated compound different with (a1) composition with (a2).
[B] (b1) contains the Resins, epoxy of hydroxyl and (b2) reactant of organoalkoxysilane, and
The cationically polymerizable compound that [C] is different with [B] composition with [A] composition.
According to the present invention, above-mentioned purpose of the present invention and advantage, the second, reach by a kind of resin combination, it is characterized in that, contain
[E] (e1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, (e2) contain the unsaturated compound of epoxy group(ing) and (e3) with (e1) composition and (e2) multipolymer of the different ethylene series unsaturated compound of composition (below, claim multipolymer [E] sometimes),
[B] (b1) contains the Resins, epoxy of hydroxyl and (b2) reactant of organoalkoxysilane, and
The cationically polymerizable compound that [F] is different with [E] composition with [B] composition.
According to the present invention, above-mentioned purpose of the present invention and advantage, the 3rd; formation method by a kind of protective membrane reaches, and it is characterized in that, above-mentioned [A] composition, [B] composition, [C] composition and [D] solidifying agent are mixed; its mixture of coating is handled with heat and/or radioactive rays then on substrate.
In addition; according to the present invention; above-mentioned purpose of the present invention and advantage; the 4th; formation method by a kind of protective membrane reaches, and it is characterized in that, above-mentioned [E] composition, [B] composition, [F] composition are reached the compound that acid takes place by heat and/or radioactive rays [G]; its mixture of coating is handled with heat and/or radioactive rays then on substrate.
Again, according to the present invention, above-mentioned purpose of the present invention and advantage, the 5th, reach by the protective membrane that forms by above-mentioned resin combination of the present invention.
The optimum implementation of invention
Below, the present invention is described in detail in detail.At first, resin combination of the present invention is described.
Multipolymer [A1
The multipolymer [A] that the present invention uses is the multipolymer that (a1) contains the unsaturated compound of the epoxy group(ing) ethylene series unsaturated compound different with (a1) composition with (a2).
The unsaturated compound that above-mentioned (a1) contains epoxy group(ing) is the compound that has epoxy group(ing) and polymerizability carbon-to-carbon double bond in a molecule.Particularly for example, can enumerate glycidyl acrylate, glycidyl methacrylate, α-Yi Jibingxisuan glycidyl ester, α-n-propyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, vinylformic acid-3,4-epoxy butyl ester, methacrylic acid-3,4-epoxy butyl ester, vinylformic acid-6,7-epoxy heptyl ester, methacrylic ester-6,7-epoxy heptyl ester, α-Yi Jibingxisuan-6,7-epoxy heptyl ester, neighbour-vinyl benzyl glycidyl ether ,-vinyl benzyl glycidyl ether, right-vinyl benzyl glycidyl ether etc.
Consider from the thermotolerance that improves copolyreaction and gained protective membrane, the viewpoint of hardness; among these; preferred glycidyl methacrylate, the methacrylic acid-6 of using, 7-epoxy heptyl ester, neighbour-vinyl benzyl glycidyl ether ,-vinyl benzyl glycidyl ether, right-vinyl benzyl glycidyl ether etc.The unsaturated compound that these (a1) contain epoxy group(ing) can be used alone or in combination.
The ethylene series unsaturated compound that above-mentioned (a2) is different with (a1) composition is the compound that does not have epoxy group(ing) and have the polymerizability carbon-to-carbon double bond.Particularly for example, can enumerate alkyl methacrylates such as methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, the secondary butyl ester of methacrylic acid, methacrylic tert-butyl acrylate;
Alkyl acrylate such as methyl acrylate, isopropyl acrylate;
Cyclohexyl methyl acrylate, methacrylic acid 2-methyl cyclohexane ester, cyclohexyl methacrylate, methacrylic acid three ring [5.2.1.0 2,6] methacrylic acid cyclic alkyl esters such as decane-8-base ester (being methacrylic acid dicyclo amyl group ester (the sour ジ シ of メ Network リ Le Network ロ ペ Application ニ Le) as trivial name in this technical field), methacrylic acid dicyclo amyl group 2-ethoxyethyl acetate (ジ シ Network ロ ペ Application ニ Le オ キ シ エ チ メ Network リ レ one ト), the different Fo Er ester of methacrylic acid;
Cyclohexyl acrylate, vinylformic acid 2-methyl cyclohexane ester, cyclohexyl acrylate, vinylformic acid three ring [5.2.1.0 2,6] vinylformic acid cyclic alkyl esters such as decane-8-base ester (in this technical field, as trivial name vinylformic acid dicyclo amyl group ester), vinylformic acid dicyclo amyl group 2-ethoxyethyl acetate, the different Fo Er ester of vinylformic acid;
Aryl methacrylate such as phenyl methacrylate, benzyl methacrylate; Vinylformic acid such as phenyl acrylate, benzyl acrylate aryl ester;
Dicarboxylic diesters such as ethyl maleate, DEF, diethyl itaconate;
Indene derivatives such as indenes, 1-methyl indenes;
Dicarbapentaborane imide derivatives such as phenyl maleimide, benzyl maleimide, cyclohexyl maleimide, N-succinimido-3-maleimide benzoic ether, N-succinimido-4-maleimide butyric ester, N-succinimido-6-maleimide capronate, N-succinimido-3-maleimide propionic ester, N-(9-acridyl) maleimide; Hydroxyalkyl acrylates such as 2-hydroxyethyl methacrylate, methacrylic acid 2-hydroxy propyl ester; And vinylbenzene, alpha-methyl styrene ,-vinyl toluene, p-methylstyrene, Vinyl toluene, p-methoxystyrene, vinyl cyanide, methacrylonitrile, vinylchlorid, vinylidene chloride, acrylamide, Methacrylamide, vinyl-acetic ester, 1,3-divinyl, isoprene, 2,3-dimethyl-1,3-butadiene etc.
Consider from the stable on heating viewpoint of copolyreaction and gained protective membrane; optimization styrene, methacrylic tert-butyl acrylate, methacrylic acid dicyclo amyl group ester, p-methoxystyrene, vinylformic acid 2-methyl cyclohexane ester, 1,3-butadiene, phenyl maleimide, cyclohexyl ester etc. among these.
These compounds (a2) can individually or be used in combination.
As the concrete example of multipolymer [A], for example can enumerate the styrene/methacrylic acid glycidyl ester copolymer, styrene/acrylic glycidyl ester copolymer, methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester/glycidyl methacrylate copolymer, methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester/glycidyl acrylate multipolymer, vinylbenzene/cyclohexyl maleimide/glycidyl methacrylate copolymer, vinylbenzene/phenyl maleimide/glycidyl methacrylate copolymer, styrene/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester/methacrylic ester glycidyl ester copolymer, vinylbenzene/methacrylic ester-6,7-epoxy heptyl ester multipolymer, methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester/methacrylic acid-6,7-epoxy heptyl ester multipolymer, vinylbenzene/cyclohexyl maleimide/methacrylic acid-6,7-epoxy heptyl ester multipolymer etc.
Preferred example among these can be enumerated styrene/methacrylic acid glycidyl ester copolymer, methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester/glycidyl methacrylate copolymer, vinylbenzene/cyclohexyl maleimide/glycidyl methacrylate copolymer, styrene/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester/glycidyl methacrylate copolymer etc.
Multipolymer [A] can use individually or more than 2 kinds together.
Multipolymer [A], per 100 weight part multipolymers [A] contain by compound (a1) deutero-and constitute preferred 1～90 weight part in unit, more preferably 40～90 weight parts.
Multipolymer [A] by the weight-average molecular weight of polystyrene conversion (below, claim " Mw " sometimes) preferably 3,000～100,000, is more preferably 3,000～50,000, most preferably is 3,000～20,000.
Multipolymer [A] can contain above-mentioned (a1) unsaturated compound of epoxy group(ing) and (a2) ethylene series unsaturated compound in the presence of appropriate solvent and polymerization starter, synthesizes by for example radical polymerization is incompatible.
As the employed solvent of synthetic copolymer [A], for example, can enumerate alcohols such as methyl alcohol, ethanol; Ethers such as tetrahydrofuran (THF); Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether; Ethylene glycol alkyl oxide acetate esters such as methyl acetic acid cellosolve, ethyl acetic acid cellosolve; Diethylene Glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene Glycol ethyl methyl ether; Propylene-glycol monoalky lether classes such as propylene glycol monomethyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether; Propylene glycol alkyl ether acetic acid ester classes such as propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic ester, propylene glycol propyl ether acetic ester, propylene glycol butyl ether acetic ester; Propylene glycol alkyl ether propionic acid esters such as propylene glycol monomethyl ether acetate, propylene-glycol ethyl ether propionic ester, propylene glycol propyl ether propionic ester, propylene glycol butyl ether propionic ester; Toluene, dimethylbenzene etc. aromatic hydrocarbon based; Ketones such as methylethylketone, pimelinketone, 4-hydroxy-4-methyl-2 pentanone, methyl isoamyl ketone; And methyl acetate, ethyl acetate, propyl acetate, butylacetate, the 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy methyl acetate, hydroxyl ethyl acetate, the oxyacetic acid butyl ester, methyl lactate, ethyl lactate, propyl lactate, n-Butyl lactate, the 3-hydroxy methyl propionate, 3-hydroxy-propionic acid ethyl ester, 3-hydroxy-propionic acid propyl ester, 3-hydroxy-propionic acid butyl ester, 2-hydroxy-3-methyl methyl-butyrate, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid propyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, the ethoxyacetic acid propyl ester, the ethoxyacetic acid butyl ester, the propoxy-methyl acetate, the propoxy-ethyl acetate, the propoxy-propyl acetate, the propoxy-butylacetate, the butoxy acetic acid methyl esters, the butoxy acetic acid ethyl ester, the butoxy acetic acid propyl ester, the butoxy acetic acid butyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2-butoxy methyl propionate, 2-butoxy ethyl propionate, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxy-methyl propionate, 3-propoxy-ethyl propionate, 3-propoxy-propyl propionate, 3-propoxy-butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate, ester classes such as 3-butoxy propyl ester butyl ester.
Solvent can use individually or more than 2 kinds together.
Preferred Diethylene Glycol class, propylene glycol alkyl acetate esters, most preferably ethylene glycol ethyl methyl ether, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic ester among these.
As making the employed initiator of multipolymer [A], can use generally as radical polymerization initiator and compound known, for example, can enumerate 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo-azo-compounds such as (4-methoxyl group-2,4-methyl pentane nitriles); Organo-peroxides such as benzoyl peroxide, lauroyl peroxide, the peroxidation trimethylacetic acid tert-butyl ester, 1,1 '-two (tert-butyl hydroperoxide) hexanaphthene; And hydrogen peroxide., also superoxide can be used with reductive agent, during with superoxide as the oxidation-reduction type initiator as radical polymerization initiator.
[B] (b1) contains the Resins, epoxy of hydroxyl and (b2) reactant of organoalkoxysilane
[B] composition that uses among the present invention is that (b1) contains the Resins, epoxy of hydroxyl and (b2) reactant of organoalkoxysilane.
Close the Resins, epoxy of hydroxyl as (b1), for example, can enumerate bisphenol-type epoxy resin, phenolic resin varnish type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, wire aliphatic epoxy resin and alicyclic epoxy resin, and biphenyl type epoxy resin etc.Preferred bisphenol-type epoxy resin and the phenolic resin varnish type epoxy resin of using among these.
Above-mentioned bisphenol-type epoxy resin can make by the reaction of halogenated epoxides such as bisphenols and epoxy chloropropane or Alpha-Methyl epoxy chloropropane.
As above-mentioned bisphenols, for example, can enumerate phenol or 2, the oxidation resultant that the resultant of reaction of aldehydes such as 6-dihalo phenol and formaldehyde, acetaldehyde, acetone, methyl phenyl ketone, pimelinketone, benzophenone or ketone and dihydroxy phenyl thioether make through acid oxidase, Resorcinol etherification reaction resultant to each other etc.In these bisphenol-type epoxy resins, the most widely-used bisphenol-type epoxy resin that preferably particularly uses dihydroxyphenyl propane, bisphenol S, Bisphenol F or their hydrogenation thing to make as bisphenols.
In addition, bisphenol-type epoxy resin have can with the hydroxyl of (b2) described later organoalkoxysilane reaction.All molecules of not pattern of wants bisphenol-type epoxy resin have this hydroxyl, get final product if having hydroxyl as bisphenol-type epoxy resin integral body.For example, bisphenol A type epoxy resin is with following formula (I) expression,
M is the integer more than 0 in the formula, and the average number of repeat unit of m is 0.1-34, but if to contain m be more than 1, then also can contain suitable m and be 0.
These bisphenol-type epoxy resins for example also can make the phosphorus compound reaction, make phosphorus modified bisphenol type Resins, epoxy and use.
Above-mentioned phenolic resin varnish type epoxy resin for example, can make halogenated epoxide and phenolic aldehyde line style resin, cresols line style resin reaction make.
Above-mentioned glycidyl ester type epoxy resin can make by other basic acid classes and the epichlorohydrin reaction that makes phthalic acid etc.
Above-mentioned glycidyl amine type epoxy resin for example can make polyamines classes such as diaminodiphenyl-methane, tricarbimide and epichlorohydrin reaction make.
Above-mentioned wire aliphatic epoxy resin and alicyclic epoxy resin, for example peracid treatment olefines such as available peracetic acid and making.
Above-mentioned biphenyl type epoxy resin for example can make phenol and epichlorohydrin reaction make.
(b1) contain the structure of Resins, epoxy of hydroxyl according to (b1) different and different for the ideal value of epoxy equivalent (weight) that contains the Resins, epoxy of hydroxyl.Can suitably select to use according to purposes.Usually, poor with the tack of substrate sometimes when making protective membrane when using excessively little (b1) composition of epoxy equivalent (weight), so preferably the epoxy equivalent (weight) of (b1) composition is more than 180.
On the other hand, when using excessively big (b1) composition of epoxy equivalent (weight), owing to when react with (b2) described later organoalkoxysilane, produce gelation sometimes, preferably the epoxy equivalent (weight) of (b1) composition is below 5,000.
Further preferred epoxy equivalent (weight) is 200～400.
In addition, as above-mentioned (b2) organoalkoxysilane, can use general used in sol-gel method.
For example, can exemplify and use formula R 1 pSi (OR 2) 4-p(in the formula, p represents 0 or 1 integer for the compound of expression or its partial condensate.R 1Expression can have the C with the direct-connected functional group of carbon atom 1～C 6Alkyl, C 1～C 6Aryl or C 2～C 6The unsaturated aliphatic residue, R 2Expression hydrogen atom or C 1～C 6Alkyl, a plurality of R is arranged 2Can distinguish identical also can be different).As relevant R 1Above-mentioned functional group, for example, can enumerate vinyl, sulfydryl, epoxy group(ing), glycidoxy etc.
In addition, so-called " partial condensate " is meant the condenses that a part of condensation of the alkoxyl group in the organoalkoxysilane that will represent with above-mentioned formula makes.This class partial condensate can be by making above-mentioned organoalkoxysilane hydrolysis in the presence of acid or alkali and water.
As the concrete example of such (b2) organoalkoxysilane, can enumerate the tetraalkoxysilane class of tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilan, four butoxy silanes and so on; Methyltrimethoxy silane, Union carbide A-162, methyl tripropoxy silane, methyl three butoxy silanes, ethyl trimethoxy silane, ethyl triethoxysilane, the n-propyl Trimethoxy silane, the n-propyl triethoxyl silane, the sec.-propyl Trimethoxy silane, the sec.-propyl triethoxyl silane, vinyltrimethoxy silane, vinyltriethoxysilane, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane, phenyltrimethoxysila,e, phenyl triethoxysilane, 3,4-epoxycyclohexyl ethyl trimethoxy silane, 3, the trialkoxysilanes of 4-epoxycyclohexyl ethyl triethoxysilane and so on; Or their partial condensate etc.
Tetramethoxy-silicane or the alkyl trimethoxy preferably represented among these with following formula (2)
The partial condensate of silane.
Figure C20051007120800111
In the formula, R 3Be methoxyl group or C 1～C 6Alkyl, n be that the integer more than 1, the average number of repeat unit of n are 1～7.
The number-average molecular weight of the partial condensate of this tetramethoxy-silicane or alkyl trimethoxysilane preferred about 260～2,000.Further preferred about 260～890.The partial condensate of this tetramethoxy-silicane or alkyl trimethoxysilane, with the reaction of (b1) composition in because unreacted (b2) composition is not outside methyl alcohol evaporates the system of flowing to, so also preferably use on operation.In addition, such partial condensate does not have the toxicity as its corresponding monomer existence, considers preferred from this viewpoint yet.
In the aforementioned formula (2), the value (n) of average number of repeat unit is preferred below 11, and is further preferred below 7.Solvability variation when this value surpasses 11 is not dissolved in the Resins, epoxy of (b1) hydroxyl or organic solvent easily, so the tendency that reduces with (b1) reactivity of the Resins, epoxy of hydroxyl is arranged.
[B] composition can make by the Resins, epoxy of aforementioned (b1) hydroxyl and (b2) dealcoholization condensation reaction of organoalkoxysilane.(b1) contain the Resins, epoxy of hydroxyl and (b2) usage ratio of organoalkoxysilane, if in gained [B] composition the such ratio of in fact remaining alkoxyl group, then be not particularly limited, the weight (weight ratio) that but the silicon-dioxide converted weight of preferred (b2) organoalkoxysilane/(b1) contains the Resins, epoxy of hydroxyl is 0.01～3 scope.
But (b1) Resins, epoxy of hydroxyl is under the situation of the high molecular weight resin of epoxy equivalent (weight) more than about 400, because the carrying out of dealcoholization causes the high viscosityization or the gelation of solution sometimes.Can avoid this unfavorable condition so adopt method as described below.
1. for make (b1) contain hydroxyl Resins, epoxy hydroxyl equivalent or (b2) the normal either party of alkoxyl group of organoalkoxysilane become many, adjust aforementioned equivalence ratio and make it less than 1 or surpass 1 for well.Particularly aforementioned equivalence ratio be adjusted into less than more than 0.8 or 1.2 for well, most preferably be to be adjusted to more than 1.2.
2. adopt the method that makes dealcoholization stop to wait midway in reaction to prevent high viscosityization, gelation.For example, can adopt the moment, make reactant be tied to form reflux system, regulate the quantity of methyl alcohol of from reaction system, heating up in a steamer, or cooling reaction system make the method for reaction end etc. in high viscosityization.
The manufacturing of above-mentioned [B] composition, for example by adding aforementioned each composition, the limit is heated up in a steamer the pure limit of heating generation and is carried out dealcoholization condensation reaction and carry out.Preferred 50～130 ℃ of temperature of reaction is more preferably 70～110 ℃, total reaction time preferably 1～15 hour.This reaction is carried out under anhydrous condition to good in fact in order to prevent the polycondensation of (b2) organoalkoxysilane self.In addition, this reaction is in order to shorten the reaction times, also can be in the unvaporized scope of Resins, epoxy of (b1) hydroxyl, under reduced pressure carry out.
In addition, during above-mentioned dealcoholization condensation reaction, in order to promote to react the catalyzer that does not make the open loop of oxyethane ring among the known catalyzer of to use over.As this catalyzer, for example, can enumerate the metal of lithium, sodium, potassium, rubidium, caesium, magnesium, calcium, barium, strontium, zinc, aluminium, titanium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, cadmium, manganese and so on; The oxide compound of these metals, organic acid salt, halogenide, alkoxide etc.Preferred especially organotin, organic acid tin among these, dibutyl tin laurate, stannous octoate etc. are effective specifically.
In addition, above-mentioned reaction also can be carried out in solvent.If contain the Resins, epoxy of hydroxyl and (b2) organoalkoxysilane as solvent dissolving (b1), and not with the organic solvent of their reactions, then do not have particular restriction.As the organic solvent of this class, for example, can enumerate non-proton property polar solvents such as dimethyl formamide, N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), methylethylketone.
As the silane-modified epoxy resin that contains alkoxyl group, be fit to the commercially available product of use, can enumerate waste river chemical industry (strain) system commodity: コ Application Port セ ラ Application E-101, E-102, E-201, E-202, E-211, E-212 etc.
Among these, waste river chemical industry (strain) system commodity: コ Application Port セ ラ Application E-201, E-202, E-212, the preferred use because the protective membrane of gained has high surface hardness.
The cationically polymerizable compound that [C] is different with [B] composition with [A] composition
As [C] that use among the present invention cationically polymerizable compound different with [B] composition with [A] composition, for example, can enumerate intramolecularly has oxetanyl, 3 more than 2, the compound of 4-epoxycyclohexyl or epoxy group(ing).
Concrete example as such [C] cationically polymerizable compound can be listed below.
The compound that above-mentioned oxetanyl more than 2 is arranged as intramolecularly, for example, can enumerate 3,7-two (3-oxetanyl)-5-oxa-nonane, 3,3 '-(1,3-(2-methine) propane two bases two (oxygen methylene radical)) two-(3-ethyl trimethylene oxide), 1,4-two [(3-ethyl-3-trimethylene oxide ylmethoxy) methyl] benzene, 1,2-two [(3-ethyl-3-trimethylene oxide ylmethoxy) methyl] ethane, 1,3-two [(3-ethyl-3-trimethylene oxide ylmethoxy) methyl] propane, ethylene glycol bisthioglycolate (3-ethyl-3-trimethylene oxide ylmethyl) ether, dicyclopentenyl two (3-ethyl-3-trimethylene oxide ylmethyl) ether, triethylene glycol two (3-ethyl-3-trimethylene oxide ylmethyl) ether, TEG two (3-ethyl-3-trimethylene oxide ylmethyl) ether, tristane two basic dimethylenes two (3-ethyl-3-trimethylene oxide ylmethyl) ether, trimethylolpropane tris (3-ethyl-3-trimethylene oxide ylmethyl) ether, 1,4-two (3-ethyl-3-trimethylene oxide ylmethoxy) butane, 1,6-two (3-ethyl-3-trimethylene oxide ylmethoxy) hexane, tetramethylolmethane three (3-ethyl-3-trimethylene oxide ylmethyl) ether, tetramethylolmethane four (3-ethyl-3-trimethylene oxide ylmethyl) ether, polyoxyethylene glycol two (3-ethyl-3-trimethylene oxide ylmethyl) ether, Dipentaerythritol six (3-ethyl-3-trimethylene oxide ylmethyl) ether, Dipentaerythritol five (3-ethyl-3-trimethylene oxide ylmethyl) ether, Dipentaerythritol four (3-ethyl-3-trimethylene oxide ylmethyl) ether, the reactant of Dipentaerythritol six (3-ethyl-3-trimethylene oxide ylmethyl) ether and γ-Ji Neizhi, the reactant of Dipentaerythritol five (3-ethyl-3-trimethylene oxide ylmethyl) ether and γ-Ji Neizhi, ditrimethylolpropane four (3-ethyl-3-trimethylene oxide ylmethyl) ether, the reactant of dihydroxyphenyl propane two (3-ethyl-3-trimethylene oxide ylmethyl) ether and oxyethane, the reactant of dihydroxyphenyl propane two (3-ethyl-3-trimethylene oxide ylmethyl) ether and propylene oxide, the reactant of Hydrogenated Bisphenol A two (3-ethyl-3-trimethylene oxide ylmethyl) ether and oxyethane, Hydrogenated Bisphenol A two (3-ethyl-3-trimethylene oxide ylmethyl) ether and propylene oxide reaction thing, the reactant of Bisphenol F two (3-ethyl-3-trimethylene oxide ylmethyl) ether and oxyethane etc.
Have more than 23 as above-mentioned intramolecularly, the compound of 4-epoxycyclohexyl, for example, can enumerate 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5,5 '-spiral shell-3, the 4-epoxy) hexanaphthene--two a  alkane, two (3,4-epoxycyclohexyl methyl) adipic acid ester, two (3,4-epoxy-6-methyl cyclohexane ylmethyl) adipic acid ester, 3,4-epoxy-6-methylcyclohexyl-3 ', 4 '-epoxy-6 '-the methylcyclohexanecarboxylic acid ester, methylene radical two (3, the 4-epoxy cyclohexane), dicyclo amyl group diepoxide, two (3 of ethylene glycol, 4-epoxycyclohexyl methyl) ether, ethylene (3, the 4-epoxycyclohexane carboxylate), in ester modified 3,4-epoxycyclohexyl methyl-3 ', 4 '-epoxycyclohexane carboxylate etc.
As the above-mentioned compound that 2 above epoxy group(ing) are arranged, for example, can enumerate the 2-glycidyl ethers of the various bisphenol cpds of bisphenol A diglycidyl ether, Bisphenol F diglycidylether, bisphenol-S diglycidyl ether, Hydrogenated Bisphenol A diglycidylether, A Hydrogenated Bisphenol A F diglycidylether, Hydrogenated Bisphenol A D diglycidylether, brominated bisphenol A diglycidylether, brominated bisphenol F diglycidylether, brominated bisphenol S diglycidylether and so on;
1,4-butanediol diglycidyl ether, 1, the poly epihydric alcohol ethers of the polyvalent alcohol of 6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether and so on;
The poly epihydric alcohol ethers of the polyether glycol that aliphatic polyols such as ethylene glycol, propylene glycol, glycerol and the alkylene oxide addition more than a kind or 2 kinds make; Phenol novolak type epoxy resin; The cresols phenolic resin varnish type epoxy resin; Polynary phenol-type epoxy resin; The 2-glycidyl ester class of aliphatic long-chain diprotic acid; The glycidyl ester class of higher fatty acid; Epoxidised soybean oil, epoxidised linseed oil etc.
As the above-mentioned commercially available product that 2 above epoxy compounds are arranged, for example, can enumerate エ ピ コ one ト 1001,1002,1003,1004,1007,1009,1010,828 (oiling シ エ Le エ Port キ シ (strain) system) etc. as bisphenol A type epoxy resin;
As bisphenol f type epoxy resin, can enumerate エ ピ コ one ト 807 (oiling シ エ Le エ Port キ シ (strain) system) etc.;
As phenol novolak type epoxy resin, can enumerate エ ピ コ one ト 152,154,157S65 (oiling シ エ Le エ Port キ シ (strain) system), EPPN201,202 (Japanese chemical drug (strain) system) etc.;
As the cresols phenolic resin varnish type epoxy resin, can enumerate EOCN102,103S, 104S, 1020,1025,1027 (Japanese chemical drug (strain) system), エ ピ コ one ト 180S75 (oiling シ エ Le エ Port キ シ (strain) system) etc.;
As polynary phenol-type epoxy resin, can enumerate エ ピ コ one ト 1032H60, XY-4000 (oiling シ エ Le エ Port キ シ (strain) system) etc.;
As cyclic aliphatic epoxy resin, can enumerate CY-175,177,179, ア ラ Le ダ イ ト CY-182,192,184 (チ バ ス ペ シ ヤ Le テ イ one ケ ミ カ Le ズ (strain) system), ERL-4234,4299,4221,4206 (U.C.C corporate system)), シ ョ one ダ イ Application 509 (clear and electrician's (strain) system), エ ピ Network ロ Application 200,400 (big Japanese ink (strain) system), エ ピ コ one ト 871,872 (oiling シ エ Le エ Port キ シ (strain) system), ED-5661,5662 (セ ラ ニ one ズ コ one テ イ Application グ (strain) system) etc.;
Can enumerate エ Port ラ イ ト 100MF (common prosperity society chemistry (strain) system), エ ピ オ one Le TMP (Japanese grease (strain) system) etc. as the aliphatic poly glycidyl ether.
Above-mentioned cationically polymerizable compound can use a kind or will be used in combination more than 2 kinds separately.
In these [C] cationically polymerizable compounds,, can enumerate phenol novolak type epoxy resin, polynary phenol-type epoxy resin as preferred example.
[D] solidifying agent
As [D] solidifying agent that uses in the composition of the present invention, for example can enumerate polycarboxylic acid, polybasic acid anhydride, and the multipolymer of unsaturated polybasic acid anhydride and ethylene series unsaturated compound.As above-mentioned polycarboxylic acid, preferred aliphat polycarboxylic acid, alicyclic polycarboxylic acid and aromatic series polycarboxylic acid.For example, can enumerate the aliphatics polycarboxylic acid of succsinic acid, pentanedioic acid, hexanodioic acid, BTCA, toxilic acid, methylene-succinic acid and so on; Hexahydro-phthalic acid, 1,2-cyclohexane dicarboxylic acid, 1,2, the alicyclic polycarboxylic acid of 4-hexanaphthene tricarboxylic acid, pentamethylene tetracarboxylic acid and so on; Phthalic acid, m-phthalic acid, terephthalic acid, trihemellitic acid, pyromellitic acid, 1,2,5, the aromatic series polycarboxylic acid of 8-naphthalene tetracarboxylic acid and so on.Among these, consider that from the viewpoint of the reactivity of solidification compound, the thermotolerance of formed cured film etc. the aromatic series polycarboxylic acid is suitable especially.
As above-mentioned polybasic acid anhydride, preferred aliphat dicarboxylic anhydride, alicyclic polycarboxylic acid dianhydride, aromatic series polybasic acid anhydride and contain the acid anhydrides of ester group.For example, can enumerate the aliphatic dicarboxylic acid acid anhydride of itaconic anhydride, succinyl oxide, citraconic anhydride, dodecenyl succinic anhydride, triphen amido formic anhydride, maleic anhydride, hexahydro phthalic anhydride, methyltetrahydro Tetra hydro Phthalic anhydride, Ha イ ミ ッ Network acid anhydrides and so on; 1,2,3,4-butane tetracarboxylic acid dianhydride, pentamethylene tetracarboxylic dianhydride's and so on alicyclic polycarboxylic acid dianhydride; The aromatic series polybasic acid anhydride of Tetra hydro Phthalic anhydride, pyromellitic acid acid anhydride, trimellitic acid 1,2-anhydride, benzophenone tetracarboxylic anhydride and so on; The anhydrous trimellitate of ethylene glycol bisthioglycolate, glycerol three anhydrous trimellitates and so on contain the ester group organic acid anhydride.Among these, aromatic series polybasic acid anhydride, especially trimellitic acid 1,2-anhydride are owing to obtaining the high cured film of thermotolerance, so most preferably.
As the unsaturated polybasic acid anhydride that uses for the multipolymer that synthesizes above-mentioned unsaturated polybasic acid anhydride and ethylene series unsaturated compound, for example can enumerate itaconic anhydride, citraconic anhydride, maleic anhydride, cis 1,2,3, more than at least a kind of the unsaturated polybasic acid anhydride of 4-tetrahydronaphthalic anhydride and so on.
Again, as the ethylene series unsaturated compound that uses for the multipolymer that synthesizes unsaturated polybasic acid anhydride and ethylene series unsaturated compound, for example, can enumerate vinylbenzene, p-methylstyrene, p-methoxystyrene, methyl methacrylate, methacrylic tert-butyl acrylate, methacrylic acid three ring [5.2.1.0 2,6] more than at least a kind of olefinically unsaturated compounds of decane-8-base ester, vinylformic acid 2-methyl cyclohexane ester, phenyl maleimide, cyclohexyl ester (シ Network ロ one キ シ Le) and so on.
The copolymerization ratio of the unsaturated polybasic acid anhydride of the unsaturated polybasic acid anhydride of per 100 weight parts and the multipolymer of ethylene series unsaturated compound, preferably the 1-80 weight part is more preferably the 10-60 weight part.By using such multipolymer can obtain the protective membrane of flatness excellence.
As the preference of the multipolymer of unsaturated polybasic acid anhydride and ethylene series unsaturated compound, can enumerate maleic anhydride/styrol copolymer, citraconic anhydride/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester copolymer etc.
In addition, the polystyrene conversion weight-average molecular weight of the multipolymer of above-mentioned unsaturated polybasic acid anhydride and ethylene series unsaturated compound, 500-50 preferably, 000, be more preferably 500-10,000.Can obtain the protective membrane of flatness excellence by the multipolymer that uses such molecular weight ranges.
Multipolymer [E]
The multipolymer that uses among the present invention [E], be (e1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, (e2) unsaturated compound that contains epoxy group(ing), and (e3) with the multipolymer of (e1) composition different ethylene series unsaturated compound with (e2) composition.
Multipolymer [E], per 100 weight part multipolymers [E] preferably contain the formation unit 5-40 weight part by compound (e1) derivative, 10-30 weight part most preferably, this constitutes the multipolymer of unit less than 5 weight parts, the tendency that exists thermotolerance, resistance to chemical reagents, surface hardness to reduce, on the other hand, surpass the multipolymer storage stability reduction sometimes of 40 weight parts.
As above-mentioned (e1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, for example, can enumerate monocarboxylic acids such as vinylformic acid, methacrylic acid, Ba Dousuan; Dicarboxylic acid such as toxilic acid, fumaric acid, citraconic acid, methylfumaric acid, methylene-succinic acid; And the acid anhydrides of these di-carboxylic acid.Among these, vinylformic acid, methacrylic acid, maleic anhydride etc. reach the viewpoint that obtains easily from copolyreaction, thermotolerance and consider preferred the use.These compound (e1) can be used alone or in combination.
Multipolymer [E], per 100 weight part multipolymers [E] preferably contain by compound (e2) deutero-formation unit 10-70 weight part, most preferably contain the 20-60 weight part.When this constitutes unit less than 10 weight parts, there are the thermotolerance of gained protective membrane, the tendency that surface hardness reduces, and when surpassing 70 weight parts, the tendency that exists the storage stability of the composition that contains such multipolymer to reduce.
Contain the unsaturated compound of epoxy group(ing) as (e2), can use and the identical compound of compound that exemplifies as the used compound (a1) of aforementioned multipolymer [A].
Multipolymer [E], per 100 weight part multipolymers [E] preferably contain by compound (e3) deutero-formation unit 10-70 weight part, most preferably contain the 20-50 weight part.When this constitutes unit less than 10 weight parts, the tendency that exists the storage stability of the composition that contains such multipolymer to reduce, and when surpassing 70 weight parts, the thermotolerance of the protective membrane of gained, surface hardness reduce sometimes.
(e3) (e1) and (e2) in addition ethylene series unsaturated compound can use and the identical compound of compound that exemplifies as the used compound (a2) of aforementioned multipolymer [A].
As the concrete example of the multipolymer that uses among the present invention [E], for example, can enumerate styrene/methacrylic acid/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester/glycidyl methacrylate copolymer,
Styrene/acrylic/vinylformic acid three ring [5.2.1.0 2,6] decane-8-base ester/glycidyl acrylate multipolymer,
Styrene/methacrylic acid/phenyl maleimide/glycidyl methacrylate copolymer,
Styrene/acrylic/phenyl maleimide/glycidyl acrylate multipolymer,
Styrene/methacrylic acid/cyclohexyl maleimide/glycidyl methacrylate copolymer,
Butadiene/methacrylic acid/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester/glycidyl methacrylate copolymer.
Divinyl/methacrylic acid/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester/glycidyl methacrylate copolymer.
Styrene/methacrylic acid/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester/methacrylic acid-6,7-epoxy heptyl ester multipolymer,
Styrene/acrylic/maleic anhydride/methacrylic acid-6,7-epoxy heptyl ester multipolymer,
Methacrylic tert-butyl acrylate/vinylformic acid/maleic anhydride/methacrylic acid-6,7-epoxy heptyl ester multipolymer.
Styrene/methacrylic acid/methyl methacrylate/glycidyl methacrylate copolymer,
P-methoxystyrene/methacrylic acid/cyclohexyl acrylate/glycidyl methacrylate copolymer etc.
As preferred multipolymer among these, can enumerate styrene/methacrylic acid/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester/glycidyl methacrylate copolymer,
Styrene/methacrylic acid/phenyl maleimide/glycidyl methacrylate copolymer,
Styrene/methacrylic acid/cyclohexyl maleimide/glycidyl methacrylate copolymer,
Butadiene/methacrylic acid/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester/glycidyl methacrylate copolymer,
Divinyl/methacrylic acid/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester/glycidyl methacrylate copolymer.
Multipolymer [E] is by the weight-average molecular weight of polystyrene conversion, and preferably 3,000-100,000, further preferably 3,000-50,000, most preferably be 3,000-20,000.Have the multipolymer of the molecular weight of this scope by use, can obtain the protective membrane of flatness excellence.
Multipolymer [E], above-mentioned (e1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, (e2) can be contained epoxy group(ing) unsaturated compound, and (e3) with (e1) composition and (e2) the different ethylene series unsaturated compound of composition, in the presence of appropriate solvent and polymerization starter, synthesize by for example radical polymerization.
As can be used for multipolymer [E] synthetic solvent and polymerization starter, can use and the identical material of material that exemplifies as employed solvent and polymerization starter in aforementioned multipolymer [A] manufacturing.
The cationically polymerizable compound that [F] is different with [E] composition with [B] composition
As [F] that use among the present invention cationically polymerizable compound different with [E] composition, can use and the identical compound of enumerating as aforementioned [C] composition of compound with [B] composition.
[G] utilizes heat and/or radioactive rays that the compound of acid takes place
[G] used in the present invention composition is acid-producing agent or the temperature-sensitive acid-producing agent that radioactive rays is had susceptibility.
As the acid-producing agent that radioactive rays is had susceptibility, for example, can enumerate diaryl iodine  salt, triaryl matte salt, diaryl  salt etc., can preferably use them.In addition, as the temperature-sensitive acid-producing agent, for example, can enumerate sulfonium salt class (except aforesaid triaryl matte salt), benzothiazole  salt, ammonium salt class,  salt etc., preferred sulfonium salt class (except aforesaid triaryl matte salt), the benzothiazole  salt of using among these.
As above-mentioned diaryl iodine  salt, for example, can enumerate phenylbenzene iodine  a tetrafluoro borate, phenylbenzene iodine  hexafluoro phosphonate, phenylbenzene iodine  hexafluoro arsenate, phenylbenzene iodine  trifluoro-methanyl sulfonate, phenylbenzene iodine  trifluoroacetate, the attached tosylate of phenylbenzene iodine , 4-p-methoxy-phenyl phenyl-iodide  a tetrafluoro borate, 4-p-methoxy-phenyl phenyl-iodide  hexafluoro phosphonate, 4-p-methoxy-phenyl phenyl-iodide  hexafluoro arsenate, 4-p-methoxy-phenyl phenyl-iodide  trifluoro-methanyl sulfonate, 4-p-methoxy-phenyl phenyl-iodide  trifluoroacetate, 4-p-methoxy-phenyl phenyl-iodide  tosilate, two (4-tert-butyl-phenyl) iodine  a tetrafluoro borate, two (4-tert-butyl-phenyl) iodine  hexafluoro arsenate, two (4-tert-butyl-phenyl) iodine  trifluoro-methanyl sulfonate, two (4-tert-butyl-phenyl) iodine  trifluoroacetate, two (4-tert-butyl-phenyl) iodine  tosilate etc.The preferred phenylbenzene iodine  hexafluoro phosphonate that uses among these.
As above-mentioned triaryl matte salt, for example can enumerate the triphenylsulfonium a tetrafluoro borate, triphenylsulfonium hexafluoro phosphonate, the triphenylsulfonium hexafluoro arsenate, the triphenylsulfonium trifluoro-methanyl sulfonate, the triphenylsulfonium trifluoroacetate, the triphenylsulfonium tosilate, 4-p-methoxy-phenyl phenylbenzene sulfonium a tetrafluoro borate, 4-p-methoxy-phenyl phenylbenzene sulfonium hexafluoro phosphonate, 4-p-methoxy-phenyl phenylbenzene sulfonium hexafluoro arsenate, 4-p-methoxy-phenyl phenylbenzene sulfonium trifluoro-methanyl sulfonate, 4-p-methoxy-phenyl phenylbenzene sulfonium trifluoroacetate, 4-p-methoxy-phenyl phenylbenzene sulfonium tosilate, 4-phenyl thio-phenyl phenylbenzene a tetrafluoro borate, 4-phenyl thio-phenyl phenylbenzene hexafluoro phosphonate, 4-phenyl thio-phenyl phenylbenzene hexafluoro arsenate, 4-phenyl thio-phenyl phenylbenzene trifluoro-methanyl sulfonate, 4-phenyl thio-phenyl phenylbenzene trifluoroacetate, 4-phenyl thio-phenyl phenylbenzene tosilate etc.The preferred triphenylsulfonium trifluoro-methanyl sulfonate that uses among these.
As above-mentioned diaryl  salt, can enumerate (1-6-η-isopropyl benzene) (η-cyclopentadienyl) iron hexafluoro phosphonate etc.
As the acid-producing agent that radioactive rays is had susceptibility, the commercially available product that is fit to the acid-producing agent of use, can enumerate the commodity of ユ ニ オ Application カ one バ イ De corporate system as diaryl iodine  salt: UVI-6950, UVI-6970, UVI-6974, UVI-6990, the commodity of body ど ら chemistry (strain) system: MPI-103, BBI-103 etc.
In addition, as the triaryl matte salt, can enumerate the commodity of rising sun electrochemical industry (strain) system: ア デ カ オ プ ト マ-SP-150, SP-151, SP-170, SP-171, the commodity of Japan Cao Da (strain) system: CI-2481, CI-2624, CI-2639, CI-2064, the commodity of body ど ら chemistry (strain) system: DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103, the commodity of サ one ト マ one corporate system: CD-1010, CD-1011, CD-1012 etc.
In addition,, can enumerate the commodity of チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ (strain) system: イ Le ガ キ ユ ア-261, the commodity of Japanese chemical drug (strain) system: PCI-061T, PCI-062T, PCI-020T, PCI-022T etc. as diaryl  salt.
Among these; the commodity of ユ ニ オ Application カ one バ イ De system: UVI-6970, UVI-6974, UVI-6990; the commodity of rising sun electrochemical industry (strain) system: ア デ カ オ プ ト マ-SP-170, SP-171; the commodity of サ one ト マ one corporate system: CD-1012; the commodity of body ど ら chemistry (strain) system: MPI-103, preferred because the gained protective membrane has high surface hardness.
In the above-mentioned temperature-sensitive acid-producing agent, as the concrete example of sulfonium salt class (except that aforesaid triaryl matte salt), can enumerate the alkyl sulfonium salt of 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro arsenate, dimethyl-4-(benzyloxycarbonyloxy) phenyl sulfonium hexafluoro antimonate, dimethyl-4-(benzoyl oxygen) phenyl sulfonium hexafluoro antimonate, dimethyl-4-(benzoyl oxygen) phenyl sulfonium hexafluoro arsenate, dimethyl-3-chloro-4-acetyl oxygen phenyl sulfonium hexafluoro antimonate etc.;
The benzyl sulfonium salt of benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate, 4-acetoxyl group phenyl benzyl methyl sulfonium hexafluoro antimonate, benzyl-4-anisole ylmethyl sulfonium hexafluoro antimonate, benzyl-2-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, benzyl-3-chloro-4-hydroxy phenyl methyl sulfonium hexafluoro arsenate, 4-methoxy-benzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate etc.;
Dibenzyl-4-hydroxy phenyl sulfonium hexafluoro antimonate, dibenzyl-4-hydroxy phenyl sulfonium hexafluorophosphate, 4-acetoxyl group phenyl dibenzyl sulfonium hexafluoro antimonate, dibenzyl-4-p-methoxy-phenyl sulfonium hexafluoro antimonate, dibenzyl-3-chloro-4-hydroxy phenyl sulfonium hexafluoro arsenate, dibenzyl-3-methyl-4-hydroxyl-5-tert-butyl-phenyl sulfonium hexafluoro antimonate, benzyl-4-methoxy-benzyl-dibenzyl sulfonium salts such as 4-hydroxy phenyl sulfonium hexafluorophosphate;
P-chlorobenzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, to nitrobenzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, p-chlorobenzyl-4-hydroxy phenyl methyl sulfonium hexafluorophosphate, to nitrobenzyl-3-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, 3,5-dichloro benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, o-chlorobenzyl-substituted benzyl sulfonium salts such as 3-chloro-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate etc.
Preferred 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro arsenate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl benzyl methyl sulfonium hexafluoro antimonate, dibenzyl-4-hydroxy phenyl sulfonium hexafluoro antimonate, the 4-acetoxyl group phenyl dibenzyl sulfonium hexafluoro antimonate etc. of using among these.
As above-mentioned benzothiazole  salt, for example can enumerate 3-benzyl benzothiazole  hexafluoro antimonate, 3-benzyl benzothiazole  hexafluorophosphate, 3-benzyl benzothiazole  a tetrafluoro borate, 3-(to methoxy-benzyl) benzothiazole  hexafluoro antimonate, 3-benzyl-2-methyl-thio-benzothiazole  hexafluoro antimonate, 3-benzyl-benzyl benzothiazole  salt such as 5-chloro benzothiazole  hexafluoro antimonate.
The preferred 3-benzyl benzothiazole  hexafluoro antimonate etc. that uses among these.
As the suitable acid-producing agent that uses of temperature-sensitive acid-producing agent, for example,, the commodity of rising sun electrochemical industry (strain) system can have been bought: commercially available products such as ア デ カ オ プ ト Application CP-66, CP-77 as the alkyl sulfonium salt.
In addition, as the benzyl sulfonium salt, can enumerate the commodity of three new chemical industry (strain) system: SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, SI-100L, SI-110L.
SI-80, SI-100, SI-110 are because the protective membrane that obtains has high surface hardness preferably among these.
Composition
Below, composition of the present invention is described.
Composition of the present invention, ideal situation are to prepare by each composition is dissolved equably or disperses in appropriate solvent described later.
As the embodiment of the present composition, can enumerate each following situation.
1. be must composition with aforesaid multipolymer [A], [B] composition and [C] composition, according to circumstances contain the composition (below, claim " the 1st composition " sometimes) of any added ingredients described later.
2. each composition that contains above-mentioned the 1st composition also further contains the composition of [D] solidifying agent.
3. be must composition with multipolymer [E], [B] composition and [F] composition, according to circumstances contain any added ingredients of aftermentioned composition (below, claim sometimes " the 2nd composition ".)。
4. contain each composition of above-mentioned the 2nd composition and further contain [G] composition composition (below, claim sometimes " the 3rd composition ".)
The proportioning of each composition for example down in the 1st composition.
[B] composition with respect to multipolymer [A] 100 weight parts, preferably uses 3～200 weight parts, more preferably uses 5～100 weight parts, the further preferred amount of using 10～50 weight parts.When this was worth less than 3 weight parts, the hardness of gained protective membrane was insufficient sometimes, should be worth on the other hand when surpassing 200 weight parts, sometimes generation difficulty in the formation operation of filming.
[C] composition that is contained in the 1st composition is preferably used 3～100 weight parts with respect to multipolymer [A] 100 weight parts, more preferably uses the amount of 5～50 weight parts.Under the usage quantity of this scope, can obtain the protective membrane of sufficient hardness.
Above-mentioned the 1st composition permanent stability excellence.
After above-mentioned the 1st composition further added [D] solidifying agent in use, available method described later formed protective membrane.The protective membrane of Xing Chenging satisfies tack, surface hardness, the transparency, thermotolerance, photostabilization, anti-solvent etc. like this, and it is recessed and make the excellent performance of the step difference planarization of the colour filter that forms on the basal substrate to apply simultaneously loading under heating condition.
Further add [D] solidifying agent in the 1st composition to, preferably use under the state in being dissolved in appropriate solvent.The concentration of [D] solidifying agent 5～50 weight % preferably are more preferably 10～40 weight % in the solution, spendable here solvent, can use with the solvent phase that exemplifies as the solvent that in the manufacturing of aforementioned multipolymer [B], uses with solvent.The addition of solidifying agent is with respect to multipolymer [A] 100 weight parts, and preferably 20～60 weight parts are more preferably the 20-50 weight part.Under the usage quantity of this scope, composition presents good curing characteristics, can not damage every rerum natura of gained protective membrane.
In the 1st composition, further add the composition of [D] solidifying agent, usually 24 hours with interior for use for well.
The proportioning of each composition for example down in above-mentioned the 2nd composition.
[B] composition with respect to multipolymer [E] 100 weight parts, preferably uses 3～200 weight parts, more preferably uses 5～100 weight parts, the further preferred amount of using 10～50 weight parts.When this was worth less than 3 weight parts, the hardness of gained protective membrane was insufficient sometimes.And should be worth when surpassing 200 weight parts, in the formation operation of filming, produce difficulty sometimes.
[F] composition that is contained in the 2nd composition with respect to multipolymer [E] 100 weight parts, preferably uses 3～100 weight parts, more preferably uses the amount of 5～50 weight parts.Under the usage quantity of this scope, can obtain the protective membrane of abundant hardness.
Above-mentioned the 2nd composition can make it further to contain [G] and by heat and/or radioactive rays sour compound take place, and makes the 3rd composition.
The amount of [G] composition that is contained in the 3rd composition with respect to multipolymer [E] 100 weight parts, preferably below 20 weight parts, is more preferably 0.05～20 weight part, further 0.1～10 weight part preferably.The good curing characteristics of composition exhibiting under the usage quantity of this scope can not damage every rerum natura of gained protective membrane.
The the above-mentioned the 2nd or the 3rd composition can adopt method described later to form protective membrane.The protective membrane of Xing Chenging satisfies tack, surface hardness, the transparency, thermotolerance, photostabilization, solvent resistance etc. like this; simultaneously under heating condition, apply loading and not recessed, and the excellent performance that makes the step difference planarization of formed colour filter on the bottom substrate.
Any added ingredients
Composition of the present invention can adopt above-mentioned various schemes, but in the scope of not damaging the object of the invention, also can contain above-mentioned other compositions in addition as required, as other such compositions, for example, can enumerate tensio-active agent, bonding auxiliary agent etc.
Above-mentioned tensio-active agent is to add for the coating that improves composition.
As such tensio-active agent, for example, can enumerate fluorine is tensio-active agent; The polysiloxane series tensio-active agent; Negatively charged ion such as Voranol EP 2001 class, polyoxyethylene aryl ethers, polyoxyethylene dialkyl esters are tensio-active agent etc.
As the Voranol EP 2001 class, for example, can enumerate polyoxyethylene laurel ether, polyoxyethylene stearyl ether, polyoxyl 10 oleyl ether etc.As the polyoxyethylene aryl ethers, for example, can enumerate polyoxyethylene octyl phenyl ether, polyoxyethylene nonylplenyl ether.In addition, as the polyoxyethylene dialkyl esters, for example, can enumerate polyoxyethylene two lauryls, polyoxyethylene distearyl ester etc.
Such tensio-active agent, for example, as fluorine is tensio-active agent, the system commodity of available BM CHIMIE company: BM-1000, BM-1100, big Japanese ink chemical industry (strain) system commodity: メ ガ Off ア Star Network F142D, F172, F173, F183, Sumitomo ス リ one エ system (strain) society system commodity: Off ロ ラ one De FC-135, FC-170C, FC-430, FC-431, system commodity: the サ one Off ロ Application S-112 of Asahi Glass (strain) society, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, commercially available products such as SC-106;
As silicone type surface active agent, the beautiful organosilicon in available east (strain) system commodity: SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190, system commodity: the KP341 of SHIN-ETSU HANTOTAI's chemical industry (strain) society, new autumn fields changes into (strain) society system commodity: エ Off ト Star プ EF301, commercially available products such as EF303, EF352;
As other tensio-active agent, the commodity of available common prosperity society's chemistry (strain) society system: commercially available products such as (methyl) acrylic copolymer Port リ Off ロ one No.57, No.90.
The addition of these tensio-active agents, in the time of in adding above-mentioned the 1st composition to, per 100 weight part multipolymers [A] preferably use below 5 weight parts, more preferably use below 2 weight parts; In the time of in adding above-mentioned the 2nd composition to, per 100 weight part multipolymers [E] preferably use below 5 weight parts, more preferably use below 2 weight parts.When the amount of tensio-active agent surpassed 5 weight parts, it was coarse to be easy to generate the film of filming sometimes in painting process.
Above-mentioned bonding auxiliary agent is to add for the tack that improves formed protective membrane and substrate.
As so bonding auxiliary agent, for example, carboxyl, methacryloyl, isocyanate group, the substituent functional silanes coupling agent of epoxy group(ing) isoreactivity can have preferably been used.Can enumerate Trimethoxy silane yl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanate group propyl-triethoxysilicane, γ-glycidoxypropyltrime,hoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc. particularly.
Bonding auxiliary agent like this, when adding in above-mentioned the 1st composition, per 100 weight part multipolymers [A] preferably use below 30 weight parts, more preferably use the following amount of 25 weight parts; In the time of in adding above-mentioned the 2nd composition to, per 100 weight part multipolymers [E] preferably use below 30 weight parts, more preferably use the following amount of 25 weight parts, and when the amount of bonding auxiliary agent surpassed 30 weight parts, the thermotolerance of the protective membrane of gained was insufficient sometimes.
Solvent
Composition of the present invention, ideal situation are to modulate by each composition is dissolved equably or disperses in appropriate solvent.As employed solvent, use each composition of dissolving or dispersive composition and not with the solvent of each composition reaction.
As such solvent, can use the same solvent of solvent that exemplifies with employed solvent when making aforementioned multipolymer [A], the usage quantity of solvent, the amount of the total solids composition of per 100 weight present compositions is 1～50 weight part preferably, is more preferably the scope of 5～40 weight parts.
In addition, can and use high boiling solvent with aforesaid solvent.As can and the high boiling solvent of usefulness, for example, can enumerate the N-methylformamide, N, dinethylformamide, N-methyl formyl are for aniline, N-methylacetamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, methyl-sulphoxide, benzyl ether, two hexyl ethers, acetonyl-acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzylalcohol, jasmal, ethyl benzoate, oxalic acid diethyl ester, ethyl maleate, gamma-butyrolactone, NSC 11801, propylene carbonate, phenylacetic acid cellosolve (phenyl cellosolve acetate) etc.
And the usage quantity during with high boiling solvent, with respect to 100 weight part total solvent amounts preferably below 90 weight parts, further preferably below 80 weight parts.
Synthetic as described above composition, also available preferred aperture 0.2～3.0 μ m, more preferably the millipore filter about 0.2～0.5 μ m of aperture etc. filters the back in use.
The formation of protective membrane
Below, the method that forms protective membrane of the present invention with composition of the present invention is described.
When composition of the present invention is the 3rd composition of above-mentioned the 1st composition, the 2nd composition or the temperature-sensitive propellant that contains conduct [G] composition; said composition is coated on the substrate surface; adopt preliminary drying to remove to desolvate become film after, can form the purpose protective membrane by carrying out heat treated.
Can be used as that aforesaid substrate uses, for example, can use substrates such as glass, quartz, silicon, resin, as resin, for example can enumerate the resin of the ring-opening polymerization polymer of polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide and cyclic olefin and hydrogenation thing thereof and so on.
As coating process, for example can adopt spraying method, rolling method, method of spin coating, rod to be coated with suitable method such as method, ink jet method.
As the condition of above-mentioned preliminary drying, also different and different according to the kind of each composition and cooperation ratio etc. for example, can be adopted 70～90 ℃, the condition about 1～15 minute.
Heat treated after formation is filmed can adopt suitable heating unit such as hot plate and baking oven to implement.As treatment temp preferred about 150～250 ℃, preferably adopted 5～30 minutes when using hot plate as heating unit, preferably adopt 30～90 minutes treatment time when using baking oven.
On the other hand; composition of the present invention be contain as [G] composition to the 3rd composition of the acid-producing agent of radioactive rays sensitivity the time; said composition is coated on the substrate surface; adopt preliminary drying to remove to desolvate become film after, handle (exposure-processed) and can form the purpose protective membrane by implementing radiation exposure.Also can after exposure-processed, carry out heat treated more as required.
In this case, film with above-mentioned similarly can on substrate, formation.
As spendable radioactive rays in above-mentioned radiation exposure is handled, for example, can enumerate visible rays, ultraviolet ray, far ultraviolet rays yue, electron rays, X ray etc.Among these, most preferably contain the ultraviolet ray of 190～450nm wavelength light.
Exposure preferably 100～20,000J/m 2, be more preferably 100～10,000J/m 2, further preferably 100～5,000J/m 2
The thickness of the protective membrane of Xing Chenging 0.1～8 μ m preferably is more preferably 0.1～6 μ m like this, further 0.1～4 μ m preferably.Moreover when protective membrane of the present invention formed on the substrate that the colour filter step difference is arranged, above-mentioned thickness was interpreted as apart from the thickness of colour filter topmost.
Protective membrane of the present invention; by following embodiment as can be seen; be suitable as and satisfy tack, surface hardness, the transparency, thermotolerance, photostabilization, solvent resistance etc.; even it is not recessed simultaneously to apply loading under heated condition yet, and make the optical device protective membrane of excellent performance of the step difference planarization of formed colour filter on the basal substrate.
Embodiment
Below, exemplify synthesis example, embodiment is described more specifically the present invention, but the present invention is not limited to following embodiment.
The manufacturing of multipolymer [A]
Below, the Production Example of multipolymer used in the present invention [A] is shown in synthesis example 1 and 2.
Synthesis example 1
In the flask that has cooling tube, stirrer, add 2,2 '-Diisopropyl azodicarboxylate, 6 weight parts, 2,4-phenylbenzene-4-methyl-1-pentene 6 weight parts and propylene glycol methyl ether acetate 200 weight parts.Then add glycidyl methacrylate 80 weight parts and vinylbenzene 20 weight parts, carry out nitrogen replacement after, slowly begin to stir.Make the temperature of solution be raised to 95 ℃, kept this temperature 4 hours, make the polymers soln that contains multipolymer (A-1), the solid component concentration of resulting polymers solution is 33.0 weight %.In addition, the weight-average molecular weight (Mw) of multipolymer (A-1) is 8,000.
Synthesis example 2
In the flask that has cooling tube, stirrer, add 2,2-Diisopropyl azodicarboxylate 6 weight parts, 2,4-phenylbenzene-4-methyl-1-pentene 10.0 weight parts and propylene glycol monoethyl ether acetate 200 weight parts.Then add glycidyl methacrylate 50 weight parts and methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester 50 weight parts, carry out nitrogen replacement after, slowly begin to stir.Make solution temperature be raised to 95 ℃, kept this temperature 4 hours, make the polymers soln that contains multipolymer (A-2).The solid component concentration of resulting polymers solution is 33.0 weight %, and in addition, the weight-average molecular weight (Mw) of multipolymer (A-2) is 6,000.
The manufacturing of multipolymer [E]
Below, the Production Example of multipolymer used in the present invention [E] is shown in synthesis example 3 and 4.
Synthesis example 3
In the flask that has cooling tube, stirrer, add 2,2 '-azo two (2, the 4-methyl pentane nitrile), 5 weight parts, diethylene glycol methyl ethyl ether 200 weight parts.Then add vinylbenzene 25 weight parts, methacrylic acid 20 weight parts, glycidyl methacrylate 45 weight parts and methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester 10 weight parts, carry out nitrogen replacement after, slowly begin to stir.Make the temperature of solution be raised to 70 ℃, kept this temperature 5 hours, make the polymers soln that contains multipolymer (E-1).The solid component concentration of resulting polymers solution is 33.0 weight %.In addition, the weight-average molecular weight (Mw) of multipolymer (E-1) is 6,000.
Synthesis example 4
In the flask that has cooling tube, stirrer, add 2,2 '-azo two (2, the 4-methyl pentane nitrile), 5 weight parts, diethylene glycol methyl ethyl ether 200 weight parts.Then add vinylbenzene 18 weight parts, methacrylic acid 20 weight parts, glycidyl methacrylate 40 weight parts and cyclohexyl maleimide 22 weight parts, carry out slowly beginning to stir behind the nitrogen replacement.Make solution temperature be raised to 70 ℃, kept this temperature 5 hours, make the polymers soln that contains multipolymer (E-2).The solid component concentration of resulting polymers solution is 33.0 weight %.In addition, the weight-average molecular weight (Mw) of multipolymer (E-2) is 12,000.
The modulation of the 1st composition and evaluation
Embodiment 1
In the solution (amount that is equivalent to multipolymer (A-1) 100 weight parts (solids component)) of the multipolymer (A-1) that contains above-mentioned synthesis example 1 gained, add " コ Application Port セ ラ Application E-202 " (trade(brand)name as [B] composition, waste river chemical industry (strain) system) 20.0 weight parts, bisphenol-A phenolic varnish type Resins, epoxy " エ ピ コ one ト 157S65 " (trade(brand)name as [C] composition, oiling シ エ Le エ Port キ シ (strain) system) 10.0 weight parts, γ-glycidoxypropyltrime,hoxysilane 15 weight parts as bonding auxiliary agent, reach SH-28PA (eastern beautiful organosilicon (strain) system) 0.1 weight part as tensio-active agent, after adding propylene glycol methyl ether acetate again and making solid component concentration become 20%, millipore filter with aperture 0.5 μ m filters, and modulates the 1st composition.
The formation of protective membrane
In synthetic composition as described above, add trimellitic acid 1,2-anhydride 35 weight parts that make as [D] composition and be dissolved in the solution that become in the 65 weight part Diethylene Glycol MEEs, the modulation protective membrane forms uses composition.Here synthetic composition is a water white transparency.
With spinner above-mentioned composition is coated on SiO 2After on the dipping glass substrate, 80 ℃ of preliminary dryings formed and film in 5 minutes on hot plate, again in baking oven 230 ℃ of following heat treated 60 minutes, form the protective membrane of thickness 2.0 μ m.
The evaluation of protective membrane
1. Tou Mingxing evaluation
To having the substrate of the protective membrane that forms as described above, measure the transmissivity of 400～800nm with spectrophotometer (150-20 type two-beam (Hitachi (strain) system)).The minimum value of the transmissivity of 400～800nm is shown in table 1.This value is 95% when above, we can say that the transparency of protective membrane is good.
2. the evaluation of heat-resisting dimensional stability
To having the substrate of the protective membrane that forms as described above, in baking oven, heated 1 hour down at 250 ℃, measure the thickness before and after heating.The heat-resisting dimensional stability of calculating by following formula is shown in table 1.This value is 95% when above, we can say that heat-resisting dimensional stability is good.
Heat-resisting dimensional stability=(thickness after the heating)/(thickness before the heating) * 100 (%)
3. the evaluation of heat-resisting discolouration
To having the substrate of the protective membrane that forms as described above, in baking oven, heated 1 hour down, with the above-mentioned transparency of 1. similarly measuring before and after heating at 250 ℃.The heat-resisting discolouration of calculating by following formula is shown in table 1.This value is 95% to we can say that heat-resisting discolouration is good when above.
Transmissivity (%) after transmissivity (%)-heating before heat-resisting discolouration=heating
4. the mensuration of surface hardness
To having the substrate of the protective membrane that forms as described above, the surface hardness that the 8.4.1 pencil eraser of employing JIS K-5400-1990 is drawn the test determination protective membrane.This value is shown in table 1.This value we can say that for 4H or when harder than 4H surface hardness is good.
5. the dynamic mensuration of (dynamic) small hardness
To having the substrate of the protective membrane that forms as described above; use the dynamic micro-hardness tester DVH-210 in Tianjin, island (Shimadzu Seisakusho Ltd.'s (strain) system); by the indentation test of 115 ° of triangle pressure heads of corner angle (Hull gram resin type), in loading 0.1gf, speed 0.0145gf/sec., 5 seconds hold-times, temperature the dynamic small hardness of measuring protective membrane under the condition determination of 23 ℃ and 140 ℃.Show the result in table 1.
6. the evaluation of tack
To having as described above the substrate of the protective membrane that forms, carry out pressure cooking test (120 ℃, humidity 100%, 4 hour) after, adopt the 8.5.3 sticking power checker adhesive tape method of JIS K-5400-1900 to estimate the tack of protective membrane (to SiO 2Tack).Residual number of squares in 100 grids is shown in table 1.
In addition, to the evaluation of the tack of Cr, except replacing SiO with the Cr substrate 2Outside the dipping glass substrate, other and the above-mentioned protective membrane that similarly forms thickness 2.0 μ m adopt above-mentioned checker adhesive tape method similarly to estimate.Show the result in table 1.
7. the evaluation of smooth voltinism
With spinner at SiO 2Coating pigment is colored resist (trade(brand)name " JCRRED 689 ", " JCR GREEN 706 " " CR 8200B ", more than by ジ エ イ エ ス ア one Le (strain) system) on the dipping glass substrate, forms for 150 seconds at 90 ℃ of preliminary dryings on hot plate and films.Then, by the pattern mask of regulation, with the exposure machine PLA 510F of Canon (Canon Inc.'s system), irradiation ghi line (strength ratio of wavelength 436nm, 405nm, 365nm=2.7: 2.5: 4.8) is 2000J/m by i line conversion exposure 2, carry out video picture with 0.05% potassium hydroxide aqueous solution, washed for 60 seconds with ultrapure water after, again in baking oven 230 ℃ of heat treated 30 minutes, form red, green, and blue three colour band shape colour filters (bandwidth 100 μ m).
Measure to form substrate surface concavo-convex of this colour filter with surfaceness meter " α-ス テ Star プ " (trade(brand)name, テ Application コ one Le corporate system), the result is 1.0 μ m.Measure under wherein square, as to measure the n=5 that the counts condition at measured length 2,000 μ m, measurement range 2,000 μ m.That is, make 2 directions of the stripline long axis direction of measuring stripline short-axis direction that direction is the red, green, blue direction and red, green, blue same color, under n=5, all directions are measured (total n number is 10).
Form with behind the composition with spinner coating said protection film in the above, on hot plate, formed in 5 minutes and film at 90 ℃ of preliminary dryings, again in baking oven 230 ℃ of following heat treated 60 minutes, the thickness that forms above colour filter is the protective membrane of 2.0 μ m.
To the substrate of protective membrane is arranged, measure the concavo-convex of protective membrane surface with contact determining film thickness device α-ス テ Star プ (テ Application コ one Le Japanese firm system) on the colour filter of above-mentioned such formation.Measure under wherein square, as to measure the n=5 that the counts condition at mensuration long 2,000 μ m, measurement range 2,000 μ m.Promptly, make 2 directions of the stripline long axis direction of measuring stripline short-axis direction that direction is the red, green, blue direction and red, green, blue same color, under n=5, all directions are measured (total n number is 10), 10 mean values of the highest part of each each mensuration and the difference of height (nm) of lowermost portion are shown in table 1.This value is below the 300 μ m, we can say to claim that smooth voltinism is good.
Embodiment 2～7 and comparative example 1,2
As described in Table 1 except the kind and the amount of each composition of making composition, the described solvent of use table 1 replaces propylene glycol methyl ether acetate also to meet outside the described solid component concentration of table 1, and other are the modulation group compound similarly to Example 1.
In its composition, adding makes trimellitic acid 1,2-anhydride 35 weight parts of conduct [D] composition be dissolved in the solution that is become in the 65 weight part Diethylene Glycol MEEs, and the modulation protective membrane forms uses composition.Here the outward appearance with synthetic composition is shown in table 1.
Use synthetic as described above protective membrane to form and use composition, form protective membrane similarly to Example 1, estimate.Show the result in table 1.
Moreover in table 1, the addition of each composition is a weight part, and corresponding composition is not added in "-" expression in the table.
In addition, the abbreviation of [B] composition, [C] composition, solvent is expressed as follows respectively.
B-1: silane-modified epoxy resin " コ Application Port セ ラ Application E-202 " (trade(brand)name, waste river chemical industrial company system)
B-2: silane-modified epoxy resin " コ Application Port セ ラ Application E-201 " (trade(brand)name, waste river chemical industrial company system)
B-3: silane-modified epoxy resin " コ Application Port セ ラ Application E-101 " (trade(brand)name, waste river chemical industrial company system)
B-4: silane-modified epoxy resin " コ Application Port セ ラ Application E-212 " (trade(brand)name, waste river chemical industrial company system)
C-1: bisphenol-A phenolic varnish type Resins, epoxy " oiling シ エ Le エ Port キ シ corporate system trade(brand)name: エ ピ コ one ト 157S65)
C-2: bisphenol-A phenolic varnish type Resins, epoxy " oiling シ エ Le エ Port キ シ corporate system trade(brand)name: エ ピ コ one ト 828)
S-1: propylene glycol methyl ether acetate
S-2: Diethylene Glycol monomethyl ethylhexoate
Table 1
The modulation of the 2nd composition and evaluation
Embodiment 8
In the solution (amount that is equivalent to multipolymer (E-1) 100 weight parts (solids component)) of the multipolymer (E-1) that makes by above-mentioned synthesis example 3 that contains conduct [E] composition, mix silane-modified epoxy resin " コ Application Port セ ラ Application E-202 " (trade(brand)name as [B] composition, famine river chemical industrial company system) 20.0 weight parts, bisphenol-A phenolic varnish type Resins, epoxy " oiling シ エ Le エ Port キ シ corporate system trade(brand)name: 10.0 weight parts エ ピ コ one ト 157S65); reach SH-28PA (eastern beautiful organosilicon corporate system) 0.1 weight part; after the interpolation propylene glycol methyl ether acetate makes solid component concentration become 20.0 weight %; the millipore filter with aperture 0.5 μ m filters, and prepares the 2nd composition as [F] composition as tensio-active agent.
Here the outward appearance of Zhi Bei composition is a water white transparency.
The formation of protective membrane and evaluation
The composition of preparation as described above is coated on SiO with spinner 2After on the dipping glass substrate, on hot plate, film, in baking oven, formed protective membrane in 60 minutes again 230 ℃ of following heat treated in the formation in 5 minutes of 80 ℃ of preliminary dryings.
In addition, the same with embodiment 1 described method, on the substrate that forms colour filter, with the above-mentioned protective membrane that similarly forms.
With substrate, estimate similarly to Example 1 with these protective membranes.Show the result in table 2.
Embodiment 9,10 and comparative example 3,4
Press table 2 described except the kind of each composition of composition and amount, and beyond the described solvent replacement of table 2 propylene glycol methyl ether acetate, other prepare composition similarly to Example 8.
Here the outward appearance of the composition of preparation is shown in table 2.
Use the composition of preparation as described above, form protective membrane similarly to Example 8, estimate.Show the result in table 2.
The 3rd preparation of compositions and evaluation
Embodiment 11
In the solution (amount that is equivalent to multipolymer (E-1) 100 weight parts (solids component)) that contains as [E] composition by the multipolymer (E-2) of above-mentioned synthesis example 4 gained, mix silane-modified epoxy resin " コ Application Port セ ラ Application E-202 " (trade(brand)name as [B] composition, famine river chemical industrial company system) 20.0 weight parts, trimethylolpropane tris (3-ethyl-3-trimethylene oxide ylmethyl) ether 15.0 weight parts as [F] composition, benzyl-2-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate 2 weight parts as [G] composition, reach SH-28PA (eastern beautiful organosilicon corporate system) 0.1 weight part as tensio-active agent, after the interpolation diethylene glycol dimethyl ether makes solid component concentration become 20.0 weight %, millipore filter with aperture 0.5 μ m filters, and prepares the 3rd composition.
Here the outward appearance of the composition of preparation is shown in table 2.
Use the composition of preparation as described above to form protective membrane similarly to Example 8, estimate.Show the result in table 2.
Embodiment 12
Except the kind of each composition of composition and amount press table 2 described, other prepare composition similarly to Example 8.
Here the outward appearance of composition with preparation is shown in table 2.
Above-mentioned composition solution is coated on SiO with spinner 2After on the dipping glass substrate, 80 ℃ on hot plate preliminary drying 5 minutes form and film.
Then, film with the exposure machine PLA 501F of Canon (Canon Inc.'s system) to formed, irradiation ghi line (strength ratio of wavelength 436nm, 405nm, 365nm=2.7: 2.5: 4.8) is 2000J/m by i line conversion exposure 2In baking oven, formed protective membrane in 60 minutes again 230 ℃ of heat treated.
In addition, with embodiment 1 described method similarly forming on the substrate of colour filter, with above-mentioned each operation of similarly implementing coating, preliminary drying, exposure and heating, form protective membrane.
With the substrate that these protective membranes are arranged, estimate similarly to Example 6.Evaluation result is shown in table 2.
Embodiment 13
Except making 300J/m in the exposure among the embodiment 12 2In addition, other similarly obtain result shown in the table 2.
Moreover the addition of each composition is a weight part in the table 2, and corresponding composition is not added in "-" expression in the table.
In addition, the abbreviation of [B] composition, [F] composition, [G] composition and solvent is expressed as follows respectively.
B-1: silane-modified epoxy resin " コ Application Port セ ラ Application E-202 " (trade(brand)name, waste river chemical industrial company system)
B-2: silane-modified epoxy resin " コ Application Port セ ラ Application E-201 " (trade(brand)name, waste river chemical industrial company system)
B-3: silane-modified epoxy resin " コ Application Port セ ラ Application E-101 " (trade(brand)name, waste river chemical industrial company system)
F-1: bisphenol-A phenolic varnish type Resins, epoxy " oiling シ エ Le エ Port キ シ corporate system trade(brand)name: エ ピ コ one ト 157S65)
F-2: trimethylolpropane tris (3-ethyl-3-trimethylene oxide ylmethyl) ether
G-1: benzyl-2-methyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate
G-2: triphenylsulfonium trifluoro-methanyl sulfonate
S-3: propylene glycol methyl ether acetate
S-4: diethylene glycol dimethyl ether
Table 2
Figure C20051007120800351
As mentioned above; according to the present invention; can obtain to be suitable as and satisfy the past as the desired various characteristics of protective membrane; specifically; tack, surface hardness, the transparency, heat-resisting dimensional stability, heat-resisting discolouration, anti-sputter apply simultaneously the also not recessed and optical device of excellent performance that makes the planarization of bottom substrate colour filter step difference of loading with the composition of protection film formation material, and the protective membrane that formed by said composition under heating status.

Claims (4)

1. resin combination is characterized in that: contain:
[E] multipolymer, per 100 weight part multipolymers [E], contain: constitute unit 5～40 weight parts by (e1) methacrylic acid deutero-, constitute unit 10～70 weight parts and be selected from vinylbenzene by (e2) glycidyl methacrylate deutero-by (e3), the methacrylic acid tertiary butyl ester, methacrylic acid two cyclopentyl esters, to methoxy styrene, 2-methylcyclohexyl acrylate, 1, the 3-divinyl, at least a olefines unsaturated compound deutero-of phenyl maleimide and cyclohexyl maleimide constitutes unit 10～70 weight parts
[B] (b1) any one contains the organoalkoxysilane that the Resins, epoxy of hydroxyl and (b2) following formula represent or the reactant of its partial condensate in bisphenol-type epoxy resin and the phenolic resin varnish type epoxy resin,
R 1 pSi(OR 2) 4-p
In the formula, p represents 0 or 1 integer, R 1Expression C 1～C 6Alkyl, have the C with the direct-connected functional group of carbon atom 1～C 6Alkyl, C 1～C 6Aryl or C 2～C 6The unsaturated aliphatic residue, R 2Expression hydrogen atom or C 1～C 6Alkyl, a plurality of R 2Can distinguish identical also can be different; And
[F] have 2 above oxetanyls at intramolecularly, more than 23,4-epoxycyclohexyl or 2 above epoxy group(ing) and the cationically polymerizable compound different with [E] composition with [B] composition.
2. the described resin combination of claim 1 also contains the compound that acid takes place by heat and/or radioactive rays [G].
3. the formation method of a protective membrane; it is characterized in that: claim 1 described [E] composition, [B] composition, [F] composition are reached the compound that acid takes place by heat and/or radioactive rays [G]; its mixture is coated on the substrate, handles with heat and/or radioactive rays then.
4. a protective membrane adopts the described resin combination of claim 2 to form.
CNB2005100712083A 2002-05-14 2003-05-14 Resin composition and protective film Expired - Fee Related CN1311037C (en)

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CN110268328B (en) * 2017-03-31 2022-02-08 东友精细化工有限公司 Blue photosensitive resin composition, color filter and image display device manufactured by using the same
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KR20030088356A (en) 2003-11-19
CN1458209A (en) 2003-11-26

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