CN102372887B - Thermally curing resin composition for protective film - Google Patents
Thermally curing resin composition for protective film Download PDFInfo
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- CN102372887B CN102372887B CN201110196368.6A CN201110196368A CN102372887B CN 102372887 B CN102372887 B CN 102372887B CN 201110196368 A CN201110196368 A CN 201110196368A CN 102372887 B CN102372887 B CN 102372887B
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Classifications
-
- 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
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
-
- 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
- C08G59/20—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 epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
Abstract
The invention relates to a thermally curing resin composition including a silane modified epoxy resin containing an alkoxy as a main component and used for a protective film, a color filter protective film made of the composition and a liquid crystal display device containing the color filter protective film. In the invention, the thermally curing resin composition used for the protective film comprises the silane modified epoxy resin containing the alkoxy as a main component, so that the thermally curing resin composition possesses very good film intensity and adhesive strength, and accordingly, the color filter protective film can be used in the liquid crystal display device effectively.
Description
Technical field
Disclosed the present invention relates to a kind of thermally curable resin composition for the protection of film, and it comprises silane-modified epoxy resin containing alkoxyl group as main component.
Background technology
A kind of chromatic liquid crystal display equipment processes with solvent, acid solution or alkaline solution in its preparation process, or is forming by spraying method the part surface at high temperature processing this equipment in transparent electrode layer process.Sometimes, when transparent electrode layer is etched into the shape of expectation, under aforesaid device is exposed to the severe condition of acid solution or alkaline solution.In order to stop the heat owing to using in treating processes or chemical substance to cause damage to pixel, a kind of protective membrane be made up of the film can resisting above process need be provided.
Along with display equipment as liquid-crystal display (LCD) becomes large trend, the substrate size of use is also in continuous increase.Therefore, color filter layer should be plane, and in order to obtain large-scale LCD, the exploitation for the Protective coatings of color filter layer planarity is vital.
Although can be divided into the ultraviolet UV type of use and thermofixation type for the protection of the composition of film according to curing, normally used when increasing the area of LCD is thermofixation type, because implement UV radiation to there is limitation in single stage method.
Because be coated with completely on the substrate being different from filter material for the protection of the composition of film; and contact, so guarantee that the bond strength between the upper and lower is vital with the color filter layer of the glass outside substrate, bottom and the column spacer (column spacer) on top or ITO electrode.
In addition; although protection film strength has also become an important physical properties when increasing LCD area; but still the composition for the protection of film of protective membrane intensity and bond strength can be guaranteed in the urgent need to exploitation, because these two physical propertiess are each other in inverse ratio simultaneously.
Summary of the invention
The invention provides a kind of thermally curable resin composition for the protection of film, it, while keeping the film toughness needed for protective membrane, has splendid bond strength.
Present invention provides a kind of protective membrane prepared by the thermally curable resin composition for the protection of film.
The present invention has reoffered a kind of liquid crystal display also comprising this protective membrane.
Embodiment of the present invention provide mainly be included in the present invention for the protection of in the thermally curable resin composition of film containing the silane-modified epoxy resin of alkoxyl group, described composition to comprise based on solids content total weight about 0.5 to the obtained silane-modified epoxy resin containing alkoxyl group of the organoalkoxysilane reaction represented by the epoxy compounds containing silyl that represented by chemical formula 1 and chemical formula 2 of about 30 % by weight:
R
1and R
2identical or different, be C
1-C
6alkyl or C
1-C
6alkoxyl group,
R
3, R
4, R
5and R
6being same to each other or different to each other, is C
1-C
6alkyl, and
R
7be selected from C
1-C
6alkyl, C
2-C
6thiazolinyl, C
2-C
6alkenylalkyl, C
1-C
6mercaptoalkyl and C
6-C
12aryl.
The organoalkoxysilane reaction that containing the epoxy compounds of silyl and chemical formula 2 represent of silane-modified epoxy resin containing alkoxyl group also by being represented by chemical formula 3 is obtained:
R
8and R
9identical or different, be C
1-C
6alkyl or C
1-C
6alkoxyl group,
R
10, R
4, R
5and R
6identical or different, be C
1-C
6alkyl,
R
7be selected from C
1-C
6alkyl, C
2-C
6thiazolinyl, C
2-C
6alkenylalkyl, C
1-C
6mercaptoalkyl and C
6-C
12aryl, and
N
1and n
2be 1 or 2 separately, and n
1+ n
2=3.
Silane-modified epoxy resin containing alkoxyl group by with about 5: 1 to about 1: 1, epoxy compounds containing silyl of the weight ratio mixing that is preferably about 5: 1 to about 3: 1 and organoalkoxysilane and prepare.
With reference to polystyrene standards, the weight-average molecular weight of the silane-modified epoxy resin containing alkoxyl group can be about 1, and 000 to about 10,000.
The epoxy compounds containing silyl that chemical formula 1 represents can be that one or more are selected from following compound: 3-glycidoxy-propyltrimethoxy silane, 3-epoxypropoxy triethoxyl silane, 3-glycidoxypropyl dimethoxysilane, 3-glycidoxypropyl diethoxy silane, 3,4-epoxycyclohexylethyl Trimethoxy silane and 3,4-epoxycyclohexylethyl triethoxyl silane, but be not limited thereto.
The epoxy compounds containing silyl that chemical formula 3 represents can be that one or more are selected from following compound: 3-(N, N-diglycidyl) TSL 8330, N-glycidyl-N, N-bis-[3-(methyl dimethoxy oxygen base silyl) propyl group] amine and N-glycidyl-N, N-bis-[3-(trimethoxysilyl) propyl group] amine, but be not limited thereto.
The organoalkoxysilane that chemical formula 2 represents can be that one or more are selected from following compound: methyltrimethoxy silane, Union carbide A-162, methyl tripropoxy silane, methyl three butoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl Trimethoxy silane, n-propyl triethoxyl silane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, 3-mercaptopropyi Trimethoxy silane and 3-Mercaptopropyltriethoxysilane, or their partial condensate, but be not limited thereto.
Thermally curable resin composition for the protection of film can also comprise binder resin and solvent.
This binder resin is the multipolymer of unsaturated compound containing epoxide group, ethylenically unsaturated compounds and optionally other polymerisable monomers of compound.
Unsaturated compound containing epoxide group can be selected from glycidyl allyl ether, 5-norbornylene-2-methyl-2-carboxylic acid glycidyl ester (inner mold and external form mixture), 1, 2-epoxy-5-hexene, 1, 2-epoxy-9-decene, (methyl) glycidyl acrylate, α-ethyl (methyl) glycidyl acrylate, α-n-propyl (methyl) glycidyl acrylate, α-normal-butyl (methyl) glycidyl acrylate, (methyl) vinylformic acid 3, 4-epoxy butyl ester, (methyl) vinylformic acid 4, 5-epoxy pentyl ester, (methyl) vinylformic acid 5, 6-epoxy heptyl ester, α-ethylacrylate 6, the aliphatic unsaturated compound containing epoxide group of 7-epoxy heptyl ester and (methyl) vinylformic acid methylglycidyl esters, or be selected from the alicyclic unsaturated compound containing epoxide group being represented compound by following chemical formula 4 to 6, or its mixture, but be not limited thereto.
R
11, R
13and R
15identical or different, be hydrogen atom or C
1-C
6alkyl; And R
12, R
14and R
16identical or different, be C
1-C
6alkylidene group.
Ethylenically unsaturated compounds also can comprise one or more and be selected from following functional group: hydroxyl, silyl, the functional group being shown acidity by hydrolytic action, carboxyl and carboxylic acid anhydride group.
The example of the ethylenically unsaturated compounds containing hydroxyl can comprise (methyl) vinylformic acid 2-hydroxyl ethyl ester.
The example of the ethylenically unsaturated compounds containing silyl can comprise vinyl trialkyl oxysilane as vinyltriethoxysilane etc., or (methyl) acryloxy silane is as vinyl three ('beta '-methoxy oxyethyl group) silane, methylvinyldimethoxysilane, β-(methyl) acryloyl-oxyethyl Trimethoxy silane, β-(methyl) acryloyl-oxyethyl triethoxyl silane, 3-(methyl) acryloxypropyl Trimethoxy silane, 3-(methyl) acryloxypropyl triethoxyl silane, γ-(methyl) acryloxypropyl dimethoxysilane, γ-(methyl) acryloxypropyl dimethyl methoxy silane, γ-(methyl) acryloxypropyl diethoxy silane, 3-(methyl) acryloxypropyl dimethylethoxysilane and 3-(methyl) acryloxypropyl Trimethoxy silane etc.
Example containing the ethylenically unsaturated compounds being shown acid functional group by hydrolytic action can comprise (methyl) vinylformic acid tetrahydrochysene 2H-pyrans-2-base ester, (methyl) tert-butyl acrylate etc.
The example of the ethylenically unsaturated compounds containing carboxyl can comprise (methyl) vinylformic acid, butenoic acid, methylene-succinic acid, maleic acid, FUMARIC ACID TECH GRADE, monomethyl maleic acid, isoprene sulfonic acid, styrene sulfonic acid, norbornylene-2-carboxylic acid etc.
The example of the ethylenically unsaturated compounds containing anhydride group can comprise (methyl) acrylic anhydride, crotonic anhydride, itaconic anhydride, MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE acid anhydride, monomethyl MALEIC ANHYDRIDE, isoprene sulfonic acid acid anhydride, styrene sulfonic acid acid anhydride, norbornylene-2-carboxylic acid anhydride etc.
As other polymerisable monomers, known in the art, as long as the monomer that can be polymerized with the unsaturated compound containing epoxide group or ethylenically unsaturated compounds all can use ad lib, the example of indefiniteness can comprise (methyl) benzyl acrylate, (methyl) phenyl acrylate, (methyl) cyclohexyl acrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid two ring pentyl ester, (methyl) acrylate of caprolactone modification, vinylbenzene, 4-methoxy styrene, 4-vinyl toluene, 1, 3-divinyl, isoprene etc.
With reference to polystyrene standards, the weight-average molecular weight (Mw) of binder resin can be about 2, and 000 to about 100,000.
Solvent can comprise one or more and be selected from following compound: methylethylketone, pimelinketone, tetrahydrofuran (THF), methyl cellosolve acetate, ethyl acetic acid cellosolve, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic ester, ethylene glycol butyl ether, 2-methoxy ethyl ether, ethylene glycol ethyl ethers ylmethyl ether, ethylene glycol diethyl ether, ethyl acetate, ethyl lactate and 3-ethoxyl ethyl propionate, but is not limited thereto.
Thermally curable resin composition for the protection of film also can comprise one or more and be selected from other following additives: polyfunctional monomer, bonding agent, tensio-active agent and hot stopper.
Can be about 1 to about 60 % by weight for the protection of the amount of solid in the thermally curable resin composition of film, when particularly considering coatability, be preferably about 5 to about 40 % by weight.
The invention provides a kind of thermally curable resin composition of the single component type for the protection of film.
The invention provides a kind of colour filter protective membrane prepared by the thermally curable resin composition for the protection of film.
Invention further provides a kind of liquid crystal display comprising this colour filter protective membrane.
Embodiment
The preferred embodiments of the invention will be described in more detail below by reference to the accompanying drawings.But the present invention can scheme implementation in different forms, and should not be limited to the embodiment proposed here.Or rather, provide these embodiments to be to make the disclosure more fully complete, and scope of the present invention is fully conveyed to those skilled in the art.
Below with reference to accompanying drawing, an exemplary of the present invention is described.
The present invention relates to a kind of thermally curable resin composition for the protection of film, it comprises the silane-modified epoxy resin containing alkoxyl group.
The protective membrane prepared by the thermally curable resin composition for the protection of film is used in the overlay of conventional color filter usually, and structurally this overlay is between color filter layer and column spacer or ITO electrode.Therefore should there is splendid bond strength with the glass outside substrate, color filter layer in the middle of substrate and column spacer or ITO electrode for the protective membrane in overlay, possess splendid film toughness simultaneously.
Bond strength and the film toughness of protective membrane are inversely proportional to, and are therefore difficult to strengthen this two kinds of physical propertiess simultaneously.In the present invention, the thermally curable resin composition for the protection of film of the silane-modified epoxide group comprised containing alkoxyl group by use is resolved by this problem.
When the thermally curable resin composition for the protection of film comprises the silane-modified epoxy resin containing alkoxyl group of the present invention, while the film toughness keeping this protective membrane and other physical propertiess, the bond strength of the protective layer formed by said composition can be ensured.This is because the silane-modified epoxy resin containing alkoxyl group comprises alkoxyl group and this Liang Ge functional group of epoxide group; can be linked together by chemical action with for the protection of the binder resin in the thermally curable resin composition of film; and make can cause the condensation reaction with binding agent with acid, thus form chemical bonding with the substrate being placed in upper and lower.
In addition; the molecular weight of the molecular weight ratio conventional binder auxiliary agent of the silane-modified epoxy resin containing alkoxyl group is large; while the film toughness of the binder resin therefore in the thermally curable resin composition being kept for protective membrane, the bond strength between thermofixation protective membrane and the layer of upper and lower can be improved.
Silane-modified epoxy resin containing alkoxyl group of the present invention can be prepared by any one in two optional responses below.
The reaction that first reaction organoalkoxysilane that to be the epoxy compounds containing silyl that represented by chemical formula 1 below represent with chemical formula 2 occurs, obtains the silane-modified epoxy resin containing alkoxyl group thus.
R
1and R
2identical or different, be C
1-C
6alkyl or C
1-C
6alkoxyl group,
R
3, R
4, R
5and R
6identical or different, be C
1-C
6alkyl, and
R
7be selected from C
1-C
6alkyl, C
2-C
6thiazolinyl, C
2-C
6alkenylalkyl, C
1-C
6mercaptoalkyl and C
6-C
12aryl.
Second reaction is that organoalkoxysilane that the epoxy compounds containing silyl that represented by chemical formula 3 and chemical formula 2 represent reacts the silane-modified epoxide group obtained containing alkoxyl group.
R
8and R
9identical or different, be C
1-C
6alkyl or C
1-C
6alkoxyl group,
R
10, R
4, R
5and R
6identical or different, be C
1-C
6alkyl,
R
7be selected from C
1-C
6alkyl, C
2-C
6thiazolinyl, C
2-C
6alkenylalkyl, C
1-C
6mercaptoalkyl and C
6-C
12aryl,
N
1and n
2be 1 or 2 separately, and n
1+ n
2=3.
For strengthening transmittance and the bond strength of protective membrane; the amount of the silane-modified epoxy resin containing alkoxyl group is based on total thermally curable resin composition solid meter for the protection of film containing epoxy resin; its amount is preferably about 0.5 to about 30 % by weight, and the silane-modified epoxy resin containing alkoxyl group is more preferably about 0.5 to about 20 % by weight based on total solids, most preferably it is measured as about 1 to about 15 % by weight.
Silane-modified epoxy resin containing alkoxyl group of the present invention is obtained by the epoxy compounds containing silyl and the condensation reaction of organoalkoxysilane generation alcohol, and the ratio had by adjusting two kinds of compounds can obtain the feature of multiple physical properties.
Consider the easiness of stability in storage and synthesis, the epoxy compounds containing silyl and organoalkoxysilane are preferably with the weight ratio of about 5: 1 to about 1: 1, more preferably mix with the weight ratio of about 5: 1 to about 3: 1.
The weight-average molecular weight of the silane-modified epoxide group containing alkoxyl group of the present invention is about 1,000 to about 10,000, and within the scope of this, it presents the effect strengthened with the consistency of binding agent and bond strength.
The epoxy compounds containing silyl that chemical formula 1 represents is not limited, as long as the normally used the type compound in this area can use, the non-limitative example of this compound can comprise one and be selected from 3-glycidoxy-propyltrimethoxy silane, 3-epoxypropoxy triethoxyl silane, 3-glycidoxypropyl dimethoxysilane, 3-glycidoxypropyl diethoxy silane, 3, the compound of 4-epoxycyclohexylethyl Trimethoxy silane and 3,4-epoxycyclohexylethyl triethoxyl silane.
The epoxy compounds containing silyl that spendable chemical formula 3 represents is not limited, as long as the normally used the type compound in this area, the non-limitative example of this compound can comprise one and be selected from 3-(N, N-diglycidyl) TSL 8330, N-glycidyl-N, the compound of N-bis-[3-(methyl dimethoxy oxygen base silyl) propyl group] amine and N-glycidyl-N, N-bis-[3-(trimethoxysilyl) propyl group] amine.
The organoalkoxysilane that spendable chemical formula 2 represents is not limited, as long as the normally used the type compound in this area, the non-limitative example of this compound can comprise one or more and be selected from following organoalkoxysilane: methyltrimethoxy silane, Union carbide A-162, methyl tripropoxy silane, methyl three butoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl Trimethoxy silane, n-propyl triethoxyl silane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, 3-mercaptopropyi Trimethoxy silane and 3-Mercaptopropyltriethoxysilane, or its partial condensate.
Thermally curable resin composition for the protection of film of the present invention comprises silane-modified epoxy resin, binder resin, solvent containing alkoxyl group, also can comprise other additives when needing.
This binder resin is the multipolymer of unsaturated compound containing epoxide group, ethylenically unsaturated compounds and optionally other polymerisable monomers of compound.
Do not limit the spendable unsaturated compound containing epoxide group, as long as the normally used the type compound in this area, the non-limitative example of this compound can comprise and is selected from glycidyl allyl ether, 5-norbornylene-2-methyl-2-carboxylic acid glycidyl ester (inner mold and external form mixture), 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene, (methyl) glycidyl acrylate, α-ethyl (methyl) glycidyl acrylate, α-n-propyl (methyl) glycidyl acrylate, α-normal-butyl (methyl) glycidyl acrylate, (methyl) vinylformic acid 3,4-epoxy butyl ester, (methyl) vinylformic acid 4,5-epoxy pentyl ester, (methyl) vinylformic acid 5,6-epoxy heptyl ester, α-ethylacrylate 6, the aliphatic unsaturated compound containing epoxide group of 7-epoxy heptyl ester and (methyl) vinylformic acid methylglycidyl esters, or the alicyclic of epoxide group that have being selected from compound represented by following chemical formula 4 to 6 contains unsaturated compound, or its mixture.
R
11, R
13and R
15identical or different, be hydrogen atom or C
1-C
6straight or branched alkyl, concrete example can be selected from methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, sec-butyl and n-pentyl, but is not limited thereto.
R
12, R
14and R
16identical or different, be C
1-C
6straight or branched alkylidene group, concrete example can be selected from methylene radical, ethylidene, propylidene, isopropylidene, sub-normal-butyl, isobutylidene, sub-sec-butyl and sub-n-pentyl, but is not limited thereto.
But in order to be used as the colour filter protective membrane of LCD, this compound need have splendid transparency, therefore can use leucocompound.
The amount of the unsaturated compound containing epoxide group is about 10 to about 90 % by weight based on the total weight of binder resin, particularly preferably about 20 to about 70 % by weight.When the amount of the unsaturated compound containing epoxide group is less than about 10 % by weight, solidify insufficient, the physical strength, chemical resistant properties, thermotolerance etc. of therefore formed heat reactive resin film are easy to deterioration.When the amount of the unsaturated compound containing epoxide group is greater than about 90 % by weight, the amount relative deficiency of other ethylenically unsaturated compounds and other polymerisable monomers, causes resin film to be not enough to show the physical properties of expectation.
Ethylenically unsaturated compounds also can comprise one or more and be selected from following functional group: hydroxyl, silyl, the functional group being shown acidity by hydrolytic action, carboxyl and carboxylic acid anhydride group.
Show acid functional group by hydrolytic action and refer to specific range of temperatures (being preferably in the temperature range of about 150 DEG C to about 250 DEG C) group that---namely carrying out the rear baking of the thermally curable resin composition for the protection of film of the present invention at such a temperature---decomposition generates acid, the acid of generation can react with containing the epoxide group in the unsaturated compound of epoxide group.
Spendable ethylenically unsaturated compounds is not limited, as long as the normally used the type compound in this area.
Specifically, the example of the ethylenically unsaturated compounds containing hydroxyl can comprise (methyl) vinylformic acid 2-hydroxyl ethyl ester etc.
The example of the ethylenically unsaturated compounds containing silyl can comprise vinyl trialkyl oxysilane as vinyltrimethoxy silane, vinyltriethoxysilane etc., or (methyl) acryloxy silane is as vinyl three ('beta '-methoxy oxyethyl group) silane, methylvinyldimethoxysilane, β-(methyl) acryloyl-oxyethyl Trimethoxy silane, β-(methyl) acryloyl-oxyethyl triethoxyl silane, 3-(methyl) acryloxypropyl Trimethoxy silane, 3-(methyl) acryloxypropyl triethoxyl silane, γ-(methyl) acryloxypropyl dimethoxysilane, γ-(methyl) acryloxypropyl dimethyl methoxy silane, γ-(methyl) acryloxypropyl diethoxy silane, 3-(methyl) acryloxypropyl dimethylethoxysilane, 3-(methyl) acryloxypropyl Trimethoxy silane etc.
Example containing the ethylenically unsaturated compounds being shown acid functional group by hydrolytic action can comprise (methyl) vinylformic acid tetrahydrochysene 2H-pyrans-2-base ester, (methyl) tert-butyl acrylate etc.
The example of the ethylenically unsaturated compounds containing carboxyl can comprise (methyl) vinylformic acid, butenoic acid, methylene-succinic acid, maleic acid, FUMARIC ACID TECH GRADE, monomethyl maleic acid, isoprene sulfonic acid, styrene sulfonic acid, norbornylene-2-carboxylic acid etc.
The example of the ethylenically unsaturated compounds containing anhydride group can comprise (methyl) acrylic anhydride, crotonic anhydride, itaconic anhydride, MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE acid anhydride, monomethyl MALEIC ANHYDRIDE, isoprene sulfonic acid acid anhydride, styrene sulfonic acid acid anhydride, norbornylene-2-carboxylic acid anhydride etc.
The amount of ethylenically unsaturated compounds is about 5 to about 50 % by weight based on the total weight of binder resin, is particularly preferably about 10 to about 40 % by weight.When the amount of ethylenically unsaturated compounds is less than about 5 % by weight, the solidification expected can not fully be carried out.When the amount of ethylenically unsaturated compounds is greater than about 50 % by weight, this binder resin is not easily polymerized due to stability degradation in the course of the polymerization process.
In addition, when needing, except above component, binder resin of the present invention can comprise other polymerisable monomers.
As other polymerisable monomers, monomer known in the art can be used, as long as the monomer that can be polymerized with the unsaturated compound containing epoxide group or ethylenically unsaturated compounds.
Non-limitative example can comprise: aliphatic series or aromatic series (methyl) acrylate, as (methyl) benzyl acrylate, (methyl) phenyl acrylate, (methyl) cyclohexyl acrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid two ring pentyl ester etc.; (methyl) acrylate of caprolactone modification, as TONE M-100, TONE M-101, TONE M-201 (product of DOW chemical company), FM-1, FM-2, FM-3 (product of Daicel UCB Co.Ltd) etc.; Styrene monomer, as vinylbenzene, 4-methoxy styrene, 4-vinyl toluene etc.; Based on the compound of conjugated diolefine, as 1,3-butadiene or isoprene etc.
In order to the physical properties (as physical strength, tackiness, planarity (planarizability) and similarity) of the heat reactive resin film prepared by thermally curable resin composition suitably can be controlled, other different polymerisable monomers can be used, and the amount of this monomer is based on binder resin meter of the present invention, be preferably about 1 to about 50 % by weight.
With reference to polystyrene standards, the weight-average molecular weight (Mw) of binder resin of the present invention is about 2,000 to about 100,000 suitably, is particularly preferably about 3,000 to about 50,000.When molecular weight about 2, when 000 or less, the film properties for the protection of the thermally curable resin composition of film is easy to deterioration.When molecular weight about 100, when 000 or larger, the multipolymer obtained may not easily process and planarity may deterioration.
As the solvent comprised in thermally curable resin composition of the present invention, solvent known in the art can be used.The non-limitative example of solvent can comprise: alkyl ketone, as methylethylketone, pimelinketone etc.; Ethers, as tetrahydrofuran (THF) etc.; Ethylene glycol alkylether acetates, as methyl cellosolve acetate, ethyl acetic acid cellosolve, ethylene glycol monomethyl ether acetate etc.; Propylene glycol alkyl ether acetic acid ester, as propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic ester etc.; Glycols, as ethylene glycol butyl ether, 2-methoxy ethyl ether, ethylene glycol ethyl ethers ylmethyl ether, ethylene glycol diethyl ether etc.; Ester class, as ethyl acetate, ethyl lactate and 3-ethoxyl ethyl propionate etc.; Or its binding substances etc.
Do not limit for the protection of other additives in the thermally curable resin composition of film optionally adding according to other application targets; as long as the normally used the type compound in this area, other application targets described as film performance, with the clinging power, chemical stability etc. of substrate.When ground does not affect as planarity, transmittance, thermotolerance etc., the non-limitative example of other additives spendable has polyfunctional monomer, bonding agent, tensio-active agent, hot stopper etc.
Spendable polyfunctional monomer is not limited, as long as it is the compound containing 2 to 6 unsaturated functional groups.The non-limitative example of this monomer can comprise: multifunctional (methyl) acrylate, as two (methyl) vinylformic acid glycol ester, two (methyl) vinylformic acid propylene glycol ester, two (methyl) vinylformic acid 1, 3-butanediol ester, two (methyl) vinylformic acid DOPCP, two (methyl) vinylformic acid 1, 6-hexylene glycol ester, three (methyl) vinylformic acid trishydroxymethyl propyl ester, tetramethylolmethane two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate etc.
This unsaturated functional group adopts the polyfunctional monomer containing 2 to 6 functional groups, is because each functional group of polyfunctional monomer can be cross-linked to form reticulated structure with another polyfunctional monomer, thus enhances intensity and the chemical resistant properties of cured film.
Based on 100 parts by weight binder resin meter, the amount of spendable polyfunctional monomer is about 1 to about 200 weight part, is preferably about 5 to about 100 weight parts.The molecular weight of crosslinkable polyfunctional monomer lower than the molecular weight of binder resin of the present invention, and effectively can strengthen planarity.Particularly, when using the polyfunctional monomer in above-mentioned scope, there is splendid film generative capacity, and the film formed does not glue.
Bonding agent to strengthen the compound with the bond property of support base material, and be not particularly limited it, as long as this auxiliary agent can meet this purpose, routine uses the compound based on silane.Non-limitative example based on the compound of silane comprises methyl allyl acyloxypropyl trimethoxysilane (methcryloxypropyltrimethoxysilane), γ-glycidoxypropyltrime,hoxysilane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ mercaptopropyitrimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane and its mixture.
Consider character and the stability of film, based on 100 parts by weight binder resin meter, the consumption of bonding agent can be about 30 weight parts or less, particularly preferably about 20 weight parts or less.
Other additives comprise the component being generally used for coating solution, as tensio-active agent, hot stopper etc.The non-limitative example of tensio-active agent can comprise the tensio-active agent based on fluorine or silicon, and the non-limitative example of hot stopper can comprise Resorcinol, 4-methoxyphenol, quinine, pyrocatechol, tert-butyl catechol, thiodiphenylamine etc.
Of the present inventionly can suitably to select according to film and its object for the protection of the solids content in the thermally curable resin composition of film; Considering can coating, and the amount of said composition is preferably about 1 to about 60 % by weight, is more preferably about 5 to about 40 % by weight.
Consider the efficiency generating protective membrane, the thermally curable resin composition for the protection of film of the present invention can be single component type.
By the method that this area is conventional known, prepare thermofixation protective membrane by the thermally curable resin composition for the protection of film of the present invention.
The method preparing thermofixation protective membrane will be described according to an embodiment.
Be applied on substrate by appropriate means by the thermally curable resin composition for the protection of film, preliminary drying, to remove desolventizing and to form spendable film, dries next and forms thermofixation protective membrane.
The application process of said composition is not particularly limited, and can use spraying method, rolling method, spin-coating method, gap nozzle method etc., normally used is spin-coating method.Difference according to circumstances, can first by the method removing of some residual solvent decompressions after using before preliminary drying.
According to the composition used and application target thereof, preliminary drying and rear baking condition are different.Such as, conventional preliminary drying can carry out 0.5 to 5 minute at about 60 DEG C to about 130 DEG C.In addition, conventional rear baking can carry out 10 minutes to 2 hours at about 150 DEG C to about 250 DEG C.In addition, preliminary drying and rear baking all can a step be carried out or the two be combined carrying out respectively.In post-baking step, the formation that reacts of the epoxide group of binder resin and the acid groups be decomposed to form has cancellated protective membrane.
With protective membrane prepared by the method, there is splendid planarity, high surface hardness and splendid chemical resistant properties (as thermotolerance, acid resistance, alkali resistance etc.).Therefore, this protective membrane can be used as the Protective coatings of the colour filter for liquid crystal display.
In addition, present invention also offers a kind of liquid crystal display of colour filter containing comprising this protective membrane.This liquid crystal display comprises black matrix" (black matrix) and colour filter, and available ordinary method known in the art prepares.
Below, the present invention will be described in more detail by synthetic example and embodiment.But the present invention is not limited thereto.
the synthetic example of binder resin
synthetic example 1
The propylene glycol methyl ether acetate of the glycidyl methacrylate of the methacrylic acid of 23 weight parts, 50 weight parts, the vinylbenzene of 27 weight parts and 200 weight parts is added in the flask with nitrogen inlet, flask is heated to about 90 DEG C, add azo two valeronitrile (AVN) of 4.0 weight parts again, keep this temperature to obtain polymers soln after 6 hours.This polymers soln is added dropwise in hexane excessive in a large number formed precipitation, and by this precipitation under vacuo drying obtain binder resin.With reference to polystyrene standards, the weight-average molecular weight (Mw) of multipolymer (A1) is about 13,100.
synthetic example 2
Do not use the glycidyl methacrylate of the methacrylic acid of 23 weight parts, 50 weight parts and the vinylbenzene of 27 weight parts, use the methacrylic acid two ring pentyl ester of the glycidyl methacrylate of the methacrylic acid of 15 weight parts, 45 weight parts, the vinylbenzene of 25 weight parts and 15 weight parts to obtain multipolymer (A2) by the mode same with synthetic example 1; With reference to polystyrene standards, its weight-average molecular weight (Mw) is about 11,500.
synthetic example 3
Do not use the glycidyl methacrylate of the methacrylic acid of 23 weight parts, 50 weight parts and the vinylbenzene of 27 weight parts, use the methacrylic acid two ring pentyl ester of the methacrylic acid 2-tetrahydrochysene-2H-pyrans-2-base ester of 20 weight parts, the glycidyl methacrylate of 41 weight parts, the vinylbenzene of 21 weight parts and 18 weight parts to obtain multipolymer (A3) by the mode same with synthetic example 1; With reference to polystyrene standards, its weight-average molecular weight (Mw) is about 10,500.
the synthetic example of the silane-modified epoxy resin containing alkoxyl group
synthetic example 4
The 3-glycidoxy-propyltrimethoxy silane of 75 weight parts and the Union carbide A-162 of 25 weight parts are added in the flask with nitrogen input, the solution of 20 weight parts water solution there is to add in flask a kind of wherein introducing subsequently, in the described aqueous solution, 0.1 parts by weight of sodium hydroxide is added in 100 parts by weight of propylene glycol methyl ether acetates, then this flask is heated to 70 DEG C, keeps this temperature 6 hours.
After reaction, methyl alcohol removing hydrolysis generated in 2 hours under about 50mmHg reduces pressure, obtains the silane-modified epoxy resin (B1) containing alkoxyl group; With reference to polystyrene standards, its weight-average molecular weight (Mw) is about 3,300.
synthetic example 5
Do not use the 3-glycidoxy-propyltrimethoxy silane of 75 weight parts, use the N-glycidyl-N of 75 weight parts, N-bis-[3-(methyl dimethoxy oxygen base silyl) propyl group] amine obtains the silane-modified epoxy resin (B2) containing alkoxyl group by the mode same with synthetic example 4; With reference to polystyrene standards, its weight-average molecular weight (Mw) is about 4,100.
the synthesis comparative example of binder resin
synthesis comparative example 1
The glycidyl methacrylate of the methyl methacrylate of 50 weight parts, 50 weight parts and the pimelinketone of 270 weight parts are added in the flask with nitrogen input, flask is heated to about 80 DEG C, add the Diisopropyl azodicarboxylate of 5 weight parts again, keep this temperature obtains containing multipolymer (P1) polymers soln after 3 hours.This polymers soln is added dropwise in hexane excessive in a large number formed precipitation, and by this precipitation under vacuo drying obtain binder resin.The weight-average molecular weight (Mw) of this multipolymer (P1) is about 8,400.
synthesis comparative example 2
The methacrylic acid 2-tetrahydrochysene-2H-pyrans-2-base ester of the vinylbenzene of the glycidyl methacrylate of the methacrylic acid of 20 weight parts, 20 weight parts, 20 weight parts, 20 weight parts, the N-cyclohexylmaleimide of 20 weight parts and the propylene glycol methyl ether acetate of 200 weight parts are added in the flask with nitrogen input, be heated to about 70 DEG C, add the azo two (2 of 5 weight parts again, 4-dimethyl) valeronitrile, keep this temperature obtains containing multipolymer (P2) polymers soln after 5 hours.This polymers soln is added dropwise in hexane excessive in a large number formed precipitation, and by this precipitation under vacuo drying obtain binder resin.With reference to polystyrene standards, the weight-average molecular weight (Mw) of this multipolymer (P2) is about 10,500.
the synthesis comparative example of the silane-modified epoxy resin containing alkoxyl group
synthesis comparative example 3
The dimethoxydiphenylsilane of the 3-glycidoxy-propyltrimethoxy silane of 70 weight parts, the phenyltrimethoxysila,e of 17 weight parts and 13 weight parts is added in the flask with nitrogen input, subsequently by 20 weight parts water solution,---wherein 0.1 parts by weight of sodium hydroxide is added into 100 parts by weight of propylene glycol methyl ether acetates---to add in flask and is heated to 60 DEG C, keeps this temperature 6 hours.
After reaction, methyl alcohol removing hydrolysis generated in 2 hours under about 50mmHg reduces pressure, obtains the silane-modified epoxy resin (Q1) containing alkoxyl group; With reference to polystyrene standards, its weight-average molecular weight (Mw) is about 4,400.
synthesis comparative example 4
The propylene glycol monomethyl ether of the 3-glycidoxy-propyltrimethoxy silane of 61 weight parts, the tetramethoxy-silicane of 39 weight parts and 129 weight parts is added in the flask with nitrogen input, be heated to about 60 DEG C, then add the 11 weight parts water solution containing 0.1 weight part oxalic acid, keep this temperature 4 hours.
The silane-modified epoxy resin (Q2) that purifying obtains containing alkoxyl group is carried out by with the same mode of synthesis comparative example 3; With reference to polystyrene standards, its weight-average molecular weight (Mw) is about 13,000.
embodiment 1
Using 100 weight parts by the multipolymer (A1) of preparation in synthetic example 1, the mixing containing the silane-modified epoxy resin (B1) of alkoxyl group, the propylene glycol methyl ether acetate of 400 weight parts and the surfactant B YK331 (BYK) as 0.1 weight part of additive by preparation in synthetic example 4 of 5 weight parts; following diameter is that the strainer of about 0.2 μm filters, and obtains the thermally curable resin composition for the protection of film.
This thermally curable resin composition for the protection of film is applied on glass substrate, as preliminary drying on hot plate at about 90 DEG C dry 2 minutes, dries 30 minutes after next in an oven at about 220 DEG C, obtain the protective membrane of thickness about 2.0 μm.
embodiment 2
By method in the same manner as in Example 1 for the preparation of the thermally curable resin composition of protective membrane and protective membrane, difference is to use the multipolymer (A2) by preparation in synthetic example 2 to carry out alternative multipolymer (A1).
embodiment 3
By method in the same manner as in Example 1 for the preparation of the thermally curable resin composition of protective membrane and protective membrane, difference is to use the multipolymer (A3) by preparation in synthetic example 3 to carry out alternative multipolymer (A1).
embodiment 4
By method in the same manner as in Example 1 for the preparation of the thermally curable resin composition of protective membrane and protective membrane, difference is that gradation adds the dipentaerythritol acrylate of 30 weight parts.
embodiment 5
By method in the same manner as in Example 1 for the preparation of the thermally curable resin composition of protective membrane and protective membrane, difference is to use and substitutes silane-modified epoxy resin (B1) containing alkoxyl group by the silane-modified epoxy resin (B2) containing alkoxyl group of preparation in synthetic example 5.
comparative example 1
By method in the same manner as in Example 1 for the preparation of the thermally curable resin composition of protective membrane and protective membrane, difference is the silane-modified epoxy resin (B1) do not used containing alkoxyl group.
comparative example 2
By method in the same manner as in Example 4 for the preparation of the thermally curable resin composition of protective membrane and protective membrane, difference is the silane-modified epoxy resin (B1) do not used containing alkoxyl group.
comparative example 3
By method in the same manner as in Example 1 for the preparation of the thermally curable resin composition of protective membrane and protective membrane; difference be the multipolymer (P1) prepared by synthesis comparative example 1 of use 100 weight part, 23 weight parts by synthesis comparative example 3 prepare containing the silane-modified epoxy resin (Q1) of alkoxyl group and 1 of 33 weight parts; 2,4-benzenetricarboxylic anhydride comes alternative multipolymer (A1), silane-modified epoxy resin (B1) containing alkoxyl group and surfactant B YK331 (BYK).
comparative example 4
By method in the same manner as in Example 1 for the preparation of the thermally curable resin composition of protective membrane and protective membrane, difference is the multipolymer (P2) prepared by synthesis comparative example 2 of use 100 weight part, the silane-modified epoxy resin (Q2) containing alkoxyl group prepared by synthesis comparative example 4 of 20 weight parts, the SH-28PA of the hexahydro phthalic anhydride of 40 weight parts and 0.1 weight part as tensio-active agent is (by Toray Dow Corning Silicone Co., Ltd. produce) carry out alternative multipolymer (A1), silane-modified epoxy resin (B1) containing alkoxyl group and surfactant B YK331 (BYK).
eXPERIMENTAL EXAMPLE
1. bond strength
Use ASTM-D3359 method to carry out pressure furnace test (120 DEG C, humidity 100%, 4 hours), adopt grizzly bar adhesive tape (grid tape) method cut-off knife on protective membrane, mark 100 grizzly bars, then make it peel off with adhesive tape.Then, the grizzly bar pattern number do not come off in 100 grizzly bar patterns is measured.
2. surface hardness
ASTM-D3363 method is used to carry out the pencil hardness test of protective membrane, by its outcome record in table 1 below.
3. transmittance
The light transmission that wavelength is about 400nm forms the glass substrate of protective membrane on the surface, and by its outcome record in table 1 below.
4. stability in storage
Use capillary viscosity meter for the protection of the viscosity of the thermally curable resin composition of film.Next in 2 weeks at said composition being placed in about 25 DEG C, the velocity of variation row of initial viscosity in table 1 below.
5. processing characteristics
Different according to the type of the silane-modified epoxy resin containing alkoxyl group, the processing characteristics for the protection of the thermally curable resin composition of film arranges in Table 1.
When the silane-modified epoxy resin containing alkoxyl group prepared is collosol state, the thermally curable resin composition for the protection of film comprising this resin has splendid processing characteristics.But, when the silane-modified epoxy resin containing alkoxyl group prepared is gel state, comprise the processing characteristics deterioration of the thermally curable resin composition for the protection of film of this resin.
6. consistency
Different according to the type of the silane-modified epoxy resin containing alkoxyl group, the consistency for the protection of the thermally curable resin composition of film arranges in Table 1.
When the molecular weight of the silane-modified epoxy resin containing alkoxyl group exceedes about 10; when 000; comprise the thermally curable resin composition for the protection of film of this resin and the compatibility poor of the heat reactive resin for the protection of film, obtain turbid solution or form muddy film (hazing).
7. acid resistance
About 30 DEG C time, each glass substrate forming protective membrane is in its surface immersed in the HCl aqueous solution of 5.0wt% and remove from solution after about 30 minutes, observe the outer field change of protective membrane and evaluate its acid resistance.As well (O), skin peels off or variable color is evaluated as poor (X) to white glass substrate in outer unconverted glass substrate evaluation.It the results are shown in following table 1.
8. alkali resistance
About 30 DEG C time, each glass substrate forming protective membrane is in its surface immersed in the NaOH aqueous solution of 5.0wt% and remove from solution after 30 minutes, observe the outer field change of protective membrane and evaluate its alkali resistance.As well (O), skin peels off or variable color is evaluated as poor (X) to white glass substrate in outer unconverted glass substrate evaluation.It the results are shown in following table 1.
9. solvent resistance
To be immersed by each glass substrate forming protective membrane in its surface about 40 DEG C time in nmp solution 10 minutes, its solvent resistance is evaluated in the change observing thickness.As well (O), the glass substrate that variation in thickness is greater than about 3% is evaluated as poor (X) in the glass substrate evaluation of variation in thickness about 3% or less.It the results are shown in following table 1.
[table 1]
By using the silane-modified epoxy resin containing alkoxyl group optimized according to the present invention; protective membrane in embodiment 1 to 5 has splendid bond strength; and the protective membrane in comparative example 1 and 2 does not use the silane-modified epoxy resin containing alkoxyl group, its bond strength is very poor.
In comparative example 3, at the content for the protection of the silane-modified epoxy resin containing alkoxyl group in the thermally curable resin composition of film higher than the content in embodiment 1 to 5.When the silane-modified epoxy resin usage quantity containing alkoxyl group is larger, confirm that its transmittance reduces.
In comparative example 4, during the silane-modified epoxy resin containing alkoxyl group comprised in for the preparation of the thermally curable resin composition of protective membrane, employ tetramethoxy-silicane.Use the speed of reaction of the silane-modified epoxy resin (Q2) of tetramethoxy-silicane preparation containing alkoxyl group too fast, the reaction preparing resin is not easily carried out.
In addition; the molecular weight of the silane-modified epoxy resin (Q2) containing alkoxyl group using tetramethoxy-silicane to prepare in comparative example 4 is about 10; 000 or larger; thus confirm that the consistency of itself and heat reactive resin exists to limit to, and the stability in storage comprising the thermally curable resin composition for the protection of film of this epoxy resin is deteriorated.
On the contrary, the silane-modified epoxy resin (B1 and B2) containing alkoxyl group used in embodiment 1 to 5 is all collosol state, is therefore easy to this resin to mix with the thermally curable resin composition for the protection of film.
Confirmed by these embodiments and EXPERIMENTAL EXAMPLE: protective membrane of the present invention, while maintenance film toughness and other physical propertiess, significantly can improve bond strength.
The present invention, by using the thermally curable resin composition for the protection of film of the silane-modified epoxy resin comprised containing alkoxyl group, provides a kind of colour filter protective membrane; This protective membrane can have splendid film toughness, and has splendid bond strength with color filter layer, column spacer or ITO layer that protective membrane upper and lower exists, can be used in large-scale LCD.
Disclosed theme is Illustrative and nonrestrictive above, and appended claims is intended to be encompassed in all relevant amendment in main scope of the present invention, improvement and other embodiments.Therefore, in allowed by law maximum range, scope of the present invention is determined by the admissible most broad interpretation of claims below and its equivalent alterations, and not should restrict by aforesaid detailed description or limit.
Claims (20)
1. for the protection of a thermally curable resin composition for film, comprise account for solids content gross weight 0.5 to 30 % by weight the organoalkoxysilane represented by epoxy compounds and chemical formula 2 containing silyl that chemical formula 3 is represented react and the silane-modified epoxy resin containing alkoxyl group that obtains:
chemical formula 3
chemical formula 2
R
8and R
9identical or different, be C
1-C
6alkyl or C
1-C
6alkoxyl group,
R
10, R
4, R
5and R
6identical or different, be C
1-C
6alkyl,
R
7be selected from C
1-C
6alkyl, C
2-C
6thiazolinyl, C
2-C
6alkenylalkyl, C
1-C
6mercaptoalkyl and C
6-C
12aryl,
N
1and n
2be 1 or 2 separately, and n
1+ n
2=3.
2. the composition of claim 1, wherein in the reaction generating the silane-modified epoxy resin containing alkoxyl group, the described epoxy compounds containing silyl mixes with the weight ratio of 5:1 to 1:1 with described organoalkoxysilane.
3. the composition of claim 1, wherein in the reaction generating the silane-modified epoxy resin containing alkoxyl group, the described epoxy compounds containing silyl mixes with the weight ratio of 5:1 to 3:1 with described organoalkoxysilane.
4. the composition of claim 1, wherein with reference to polystyrene standards, the weight-average molecular weight of the described silane-modified epoxy resin containing alkoxyl group is 1,000 to 10,000.
5. the composition of claim 1, the epoxy compounds containing silyl that wherein chemical formula 3 represents is that one or more are selected from following compound: 3-(N, N-diglycidyl) TSL 8330, N-glycidyl-N, N-bis-[3-(methyl dimethoxy oxygen base silyl) propyl group] amine and N-glycidyl-N, N-bis-[3-(trimethoxysilyl) propyl group] amine.
6. the composition of claim 1, the organoalkoxysilane that wherein chemical formula 2 represents is that one or more are selected from following compound: methyltrimethoxy silane, Union carbide A-162, methyl tripropoxy silane, methyl three butoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl Trimethoxy silane, n-propyl triethoxyl silane, isopropyltri-methoxysilane, isopro-pyltriethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, 3-mercaptopropyi Trimethoxy silane and 3-Mercaptopropyltriethoxysilane, or its partial condensate.
7. the composition of claim 1, the wherein said thermally curable resin composition for the protection of film comprises binder resin and solvent further.
8. the composition of claim 7, wherein said binder resin is the multipolymer of unsaturated compound containing epoxide group, ethylenically unsaturated compounds and optionally other polymerisable monomers of compound.
9. the composition of claim 8, unsaturated compound wherein containing epoxide group is selected from glycidyl allyl ether, 5-norbornylene-2-methyl-2-carboxylic acid glycidyl ester, 1, 2-epoxy-5-hexene, 1, 2-epoxy-9-decene, (methyl) glycidyl acrylate, α-ethyl (methyl) glycidyl acrylate, α-n-propyl (methyl) glycidyl acrylate, α-normal-butyl (methyl) glycidyl acrylate, (methyl) vinylformic acid-3, 4-epoxy butyl ester, (methyl) vinylformic acid-4, 5-epoxy pentyl ester, (methyl) vinylformic acid-5, 6-epoxy heptyl ester, α-ethylacrylate-6, the aliphatic unsaturated compound containing epoxide group of 7-epoxy heptyl ester and (methyl) vinylformic acid methylglycidyl esters, or be selected from the alicyclic unsaturated compound containing epoxide group of following chemical formula 4 to 6 expression compound, or its mixture,
chemical formula 4
chemical formula 5
chemical formula 6
R
11, R
13and R
15identical or different, be hydrogen atom or C
1-C
6alkyl; And R
12, R
14and R
16identical or different, be C
1-C
6alkylidene group.
10. the composition of claim 8, wherein said ethylenically unsaturated compounds also comprises one or more and is selected from following functional group: hydroxyl, silyl, show acid functional group, carboxyl and carboxylic acid anhydride group from (methyl) vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester and (methyl) tert-butyl acrylate by hydrolytic action.
The composition of 11. claims 10, wherein said ethylenically unsaturated compounds is that one or more are selected from following compound: as (methyl) vinylformic acid 2-hydroxyl ethyl ester of the ethylenically unsaturated compounds containing hydroxyl;
Ethylenically unsaturated compounds containing silyl, be selected from vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane, methylvinyldimethoxysilane, β-(methyl) acryloyl-oxyethyl Trimethoxy silane, β-(methyl) acryloyl-oxyethyl triethoxyl silane, 3-(methyl) acryloxypropyl triethoxyl silane, γ-(methyl) acryloxypropyl dimethoxysilane, γ-(methyl) acryloxypropyl dimethyl methoxy silane, γ-(methyl) acryloxypropyl diethoxy silane, 3-(methyl) acryloxypropyl dimethylethoxysilane and 3-(methyl) acryloxypropyl Trimethoxy silane,
Containing the ethylenically unsaturated compounds being shown acid functional group by hydrolytic action, be selected from (methyl) vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester and (methyl) tert-butyl acrylate;
Ethylenically unsaturated compounds containing carboxyl, is selected from (methyl) vinylformic acid, butenoic acid, methylene-succinic acid, maleic acid, FUMARIC ACID TECH GRADE, monomethyl maleic acid and norbornylene-2-carboxylic acid; And
Ethylenically unsaturated compounds containing carboxylic acid anhydride group, is selected from (methyl) acrylic anhydride, crotonic anhydride, itaconic anhydride, MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE acid anhydride, monomethyl MALEIC ANHYDRIDE and norbornylene-2-carboxylic acid anhydride.
The composition of 12. claims 8, wherein said ethylenically unsaturated compounds is selected from isoprene sulfonic acid acid anhydride, styrene sulfonic acid acid anhydride, isoprene sulfonic acid and styrene sulfonic acid.
The composition of 13. claims 8, wherein other polymerisable monomers are that one or more are selected from following compound: (methyl) benzyl acrylate, (methyl) phenyl acrylate, (methyl) cyclohexyl acrylate, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid two ring pentyl ester, (methyl) acrylate of caprolactone modification, vinylbenzene, 4-methoxy styrene, 4-vinyl toluene, 1, 3-divinyl and isoprene.
The composition of 14. claims 7, wherein with reference to polystyrene standards, the weight-average molecular weight (Mw) of described binder resin is 2,000 to 100,000.
The composition of 15. claims 7, wherein said solvent is that one or more are selected from following compound: methylethylketone, pimelinketone, tetrahydrofuran (THF), methyl cellosolve acetate, ethyl acetic acid cellosolve, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic ester, ethylene glycol butyl ether, 2-methoxy ethyl ether, ethylene glycol ethyl ethers ylmethyl ether, ethylene glycol diethyl ether, ethyl acetate, ethyl lactate and 3-ethoxyl ethyl propionate.
The composition of 16. claims 7, the wherein said thermally curable resin composition for the protection of film also comprises one or more and is selected from other following additives: polyfunctional monomer, bonding agent, tensio-active agent and hot stopper.
The composition of 17. claims 1, the amount of the wherein said thermally curable resin composition solid for the protection of film is 1 to 60 % by weight.
The composition of 18. claims 1, the wherein said thermally curable resin composition for the protection of film is single component type.
19. 1 kinds of colour filter protective membranes, are prepared by the thermally curable resin composition for the protection of film of claim 1.
20. 1 kinds of liquid crystal displays, comprise the colour filter protective membrane of claim 19.
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| KR10-2010-0067078 | 2010-07-12 | ||
| KR20100067078 | 2010-07-12 | ||
| KR1020110059707A KR101261621B1 (en) | 2010-07-12 | 2011-06-20 | Thermally curable resin composition for over coat |
| KR10-2011-0059707 | 2011-06-20 |
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| TWI477556B (en) * | 2012-06-11 | 2015-03-21 | Chi Mei Corp | Curable resin composition, protective film and liquid crystal display device including the same |
| KR101599955B1 (en) * | 2012-12-21 | 2016-03-04 | 제일모직 주식회사 | Photosensitive resin composition for color filter and color filter using the same |
| KR20140105967A (en) | 2013-02-25 | 2014-09-03 | 삼성전자주식회사 | Lighting control system and controling method for the same |
| KR101599108B1 (en) * | 2013-09-26 | 2016-03-02 | 주식회사 엘지화학 | Curable composition, cured film manufactured by using the curable composition and display device having the same |
| JP6139374B2 (en) * | 2013-10-24 | 2017-05-31 | セイコーインスツル株式会社 | Coating agent, coating film, and manufacturing method of coating agent |
| JP6819051B2 (en) * | 2015-03-04 | 2021-01-27 | 住友化学株式会社 | Curable resin composition |
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| KR20120006445A (en) | 2012-01-18 |
| JP2014043580A (en) | 2014-03-13 |
| KR20130039320A (en) | 2013-04-19 |
| JP5429757B2 (en) | 2014-02-26 |
| KR101261621B1 (en) | 2013-05-07 |
| JP2012021155A (en) | 2012-02-02 |
| CN102372887A (en) | 2012-03-14 |
| JP5881049B2 (en) | 2016-03-09 |
| KR101336307B1 (en) | 2013-12-02 |
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