CN102372887A - Thermally curing resin composition for protective film - Google Patents
Thermally curing resin composition for protective film Download PDFInfo
- Publication number
- CN102372887A CN102372887A CN2011101963686A CN201110196368A CN102372887A CN 102372887 A CN102372887 A CN 102372887A CN 2011101963686 A CN2011101963686 A CN 2011101963686A CN 201110196368 A CN201110196368 A CN 201110196368A CN 102372887 A CN102372887 A CN 102372887A
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- Prior art keywords
- methyl
- silane
- acid
- protective membrane
- compsn
- Prior art date
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- 0 *C1CC2OC2CC1 Chemical compound *C1CC2OC2CC1 0.000 description 2
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
-
- 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
Disclosedly the present invention relates to a kind of thermally curable resin composition that is used for protective membrane, it comprises that the silane-modified epoxy resin that contains alkoxyl group is as staple.
Background technology
A kind of chromatic liquid crystal display equipment is handled with solvent, acid solution or alkaline solution in its preparation process, or in forming the transparent electrode layer process, at high temperature handles the part surface of this equipment through spraying method.Sometimes, when transparent electrode layer was corroded into the shape of expectation, aforesaid device was exposed under the severe condition of acid solution or alkaline solution.Because heat or the chemical substance in treating processes, used cause damage to pixel, a kind of protective membrane of being made up of the film that can resist above processing need be provided in order to stop.
Be accompanied by display equipment such as liquid-crystal display (LCD) and become big trend, the substrate size of use is also in continuous increase.Therefore, color filter layer should be a planar, and in order to obtain large-scale LCD, is vital to the exploitation of the protective membrane material of color filter layer planarity.
Can be divided into ultraviolet UV type of use and thermofixation type although be used for the compsn of protective membrane according to curing, normally used when increasing the area of LCD is the thermofixation type, has limitation because in single stage method, implement the UV radiation.
Because the compsn that is used for protective membrane is coated with being different from the substrate of filter material fully; And glass, the color filter layer of bottom and column spacer (column spacer) or the ITO electrode on top outer with substrate contact, so guarantee that the bond strength between the upper and lower is vital.
In addition; Though the protection film strength has also become an important physical properties when increasing the LCD area; But still press for the compsn that is used for protective membrane that exploitation can be guaranteed protective membrane intensity and bond strength simultaneously, because these two physical propertiess are inversely proportional to each other.
Summary of the invention
The invention provides a kind of thermally curable resin composition that is used for protective membrane, it has splendid bond strength when keeping the required film toughness of protective membrane.
The present invention also provides a kind of protective membrane by the thermally curable resin composition preparation that is used for protective membrane.
The present invention provides a kind of liquid crystal display that also comprises this protective membrane again.
Embodiment of the present invention provide and mainly have been included in the silane-modified epoxy resin that contains alkoxyl group that the present invention is used for the thermally curable resin composition of protective membrane, and said compsn comprises the silane-modified epoxy resin that contains alkoxyl group that the organoalkoxysilane reaction represented based on the epoxy compounds that contains silyl that passes through Chemical formula 1 is represented and the Chemical formula 2 of solids content gross weight meter about 0.5 to about 30 weight % makes:
R
1And R
2Identical or different, be C
1-C
6Alkyl or C
1-C
6Alkoxyl group,
R
3, R
4, R
5And R
6Be same to each other or different to each other, be C
1-C
6Alkyl, and
R
7Be selected from C
1-C
6Alkyl, C
2-C
6Thiazolinyl, C
2-C
6Thiazolinyl alkyl, C
1-C
6Mercaptoalkyl and C
6-C
12Aryl.
The silane-modified epoxy resin that contains alkoxyl group also can make through the organoalkoxysilane reaction that the epoxy compounds that contains silyl and the Chemical formula 2 of chemical formula 3 expressions are represented:
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
6Thiazolinyl alkyl, C
1-C
6Mercaptoalkyl and C
6-C
12Aryl, and
n
1And n
2Respectively do for oneself 1 or 2, and n
1+ n
2=3.
The silane-modified epoxy resin that contains alkoxyl group through with about 5: 1 to about 1: 1, be preferably about 5: 1 and mix the epoxy compounds and the organoalkoxysilane that contain silyl and prepare to about 3: 1 weight ratio.
With reference to polystyrene standards, the weight-average molecular weight that contains the silane-modified epoxy resin of alkoxyl group can be about 1,000 to about 10,000.
The epoxy compounds that contains silyl that Chemical formula 1 is represented can be that one or more are selected from following compound: 3-glycidoxy-propyltrimethoxy silane, 3-epoxypropoxy triethoxyl silane, 3-epoxypropoxy methyl dimethoxysilane, 3-epoxypropoxy methyldiethoxysilane, 3; 4-epoxycyclohexyl ethyl trimethoxy silane and 3; 4-epoxycyclohexyl ethyl triethoxysilane, but be not limited thereto.
The epoxy compounds that contains silyl of chemical formula 3 expressions can be that one or more are selected from following compound: 3-(N; The N-diglycidyl) TSL 8330, N-glycidyl-N; N-two [3-(methyl dimethoxy oxygen base silyl) propyl group] amine and N-glycidyl-N; N-two [3-(trimethoxysilyl) propyl group] amine, but be not limited thereto.
The organoalkoxysilane that Chemical formula 2 is represented can be that one or more are selected from following compound: methyltrimethoxy silane, Union carbide A-162, methyl tripropoxy silane, methyl three butoxy silanes, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl Trimethoxy silane, n-propyl triethoxyl silane, sec.-propyl Trimethoxy silane, sec.-propyl triethoxyl silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, 3-sulfydryl propyl trimethoxy silicane and 3-sulfydryl propyl-triethoxysilicane; Or their partial condensate, but be not limited thereto.
The thermally curable resin composition that is used for protective membrane can also comprise binder resin and solvent.
This binder resin is the unsaturated compound that contains epoxide group, ethylenically unsaturated compounds and as the multipolymer of other polymerisable monomers of optional compound.
The unsaturated compound that contains epoxide group can be to be selected from glycidyl allyl ether, 5-norbornylene-2-methyl-2-carboxylic acid glycidyl ester (interior type 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-Yi Jibingxisuan 6, the aliphatic unsaturated compound that contains epoxide group of 7-epoxy heptyl ester and (methyl) vinylformic acid methyl glycidyl ester, or be selected from the alicyclic unsaturated compound that contains epoxide group by following chemical formula 4 to 6 expression compounds; Or its mixture, but be not limited thereto.
R
11, R
13And R
15Identical or different, be Wasserstoffatoms or C
1-C
6Alkyl; And R
12, R
14And R
16Identical or different, be C
1-C
6Alkylidene group.
Ethylenically unsaturated compounds can comprise also that one or more are selected from following functional group: hydroxyl, silyl, show tart functional group, carboxyl and carboxylic acid anhydride group through hydrolytic action.
The example that contains the ethylenically unsaturated compounds of hydroxyl can comprise (methyl) vinylformic acid 2-hydroxyl ethyl ester.
The example that contains the ethylenically unsaturated compounds of silyl can comprise vinyl trialkyl oxysilane such as vinyltriethoxysilane etc., or (methyl) acryloyl-oxy base silane such as vinyl three ('beta '-methoxy oxyethyl group) silane, methyl ethylene dimethoxy silane, β-(methyl) acryloxy ethyl trimethoxy silane, β-(methyl) acryloxy ethyl triethoxysilane, 3-(methyl) acryloxy propyl trimethoxy silicane, 3-(methyl) acryloxy propyl-triethoxysilicane, γ-(methyl) acryloxy propyl group methyl dimethoxysilane, γ-(methyl) acryloxy propyl-dimethyl methoxy silane, γ-(methyl) acryloxy propyl group methyldiethoxysilane, 3-(methyl) acryloxy propyl-dimethyl Ethoxysilane and 3-(methyl) acryloxy propyl trimethoxy silicane etc.
Contain the example that shows the ethylenically unsaturated compounds of tart functional group through hydrolytic action and can comprise (methyl) vinylformic acid tetrahydrochysene 2H-pyrans-2-base ester, (methyl) tert-butyl acrylate etc.
The example that contains the ethylenically unsaturated compounds of 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 that contains the ethylenically unsaturated compounds of anhydride group can comprise (methyl) acrylic anhydride, crotonic anhydride, itaconic anhydride, MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE acid anhydride, monomethyl MALEIC ANHYDRIDE, isoprene sulphonic acid anhydride, styrene sulfonic acid acid anhydride, norbornylene-2-carboxylic acid anhydride etc.
As other polymerisable monomers; As long as can all can use ad lib with unsaturated compound that contains epoxide group or ethylenically unsaturated compounds monomer polymerized known in the art; The example of indefiniteness can comprise that (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 encircle (methyl) propenoate of pentyl esters, caprolactone modification, vinylbenzene, 4-methoxy styrene, 4-vinyl toluene, 1,3-butadiene, isoprene etc.
With reference to polystyrene standards, the weight-average molecular weight of binder resin (Mw) can be about 2,000 to about 100,000.
Solvent can comprise that one or more are selected from following compound: methylethylketone, pimelinketone, THF, methyl acetic acid cellosolve, 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, ETHYLE ACETATE, ethyl lactate and 3-ethoxyl ethyl propionate, but be not limited thereto.
The thermally curable resin composition that is used for protective membrane can comprise also that one or more are selected from other following additives: polyfunctional monomer, bonding agent, tensio-active agent and hot stopper.
The thermally curable resin composition solid amount that is used for protective membrane can be about 1 to about 60 weight %, is preferably about 5 when particularly considering the coating ability to about 40 weight %.
The invention provides a kind of thermally curable resin composition that is used for the single component type of protective membrane.
The invention provides a kind of filter protective membrane by the thermally curable resin composition preparation that is used for protective membrane.
The present invention provides a kind of liquid crystal display that comprises this filter protective membrane again.
Embodiment
The preferred embodiments of the invention will combine accompanying drawing to do more detailed description below.But the scheme implementation that the present invention can be multi-form, and should not be limited to the embodiment that proposes here.Or rather, it is more fully complete for this is disclosed that these embodiments are provided, and scope of the present invention is fully conveyed to those skilled in the art.
Below will combine accompanying drawing that an exemplary of the present invention is described.
The present invention relates to a kind of thermally curable resin composition that is used for protective membrane, it comprises the silane-modified epoxy resin that contains alkoxyl group.
Usually be used in the overlay of conventional filter by the protective membrane of the thermally curable resin composition preparation that is used for protective membrane, structurally this overlay is between color filter layer and column spacer or ITO electrode.Therefore the protective membrane that is used for overlay should have splendid bond strength with outer glass, substrate intermediary color filter layer and column spacer or the ITO electrode of substrate, possesses splendid film toughness simultaneously.
The bond strength and the film toughness of protective membrane are inversely proportional to, and therefore are difficult to strengthen simultaneously this two kinds of physical propertiess.In the present invention, this problem will be resolved through the thermally curable resin composition that is used for protective membrane that use comprises the silane-modified epoxide group that contains alkoxyl group.
When the thermally curable resin composition that is used for protective membrane comprises the silane-modified epoxy resin that contains alkoxyl group of the present invention, in the film toughness that keeps this protective membrane and other physical propertiess, the bond strength of the resist that can guarantee to form by said composition.This is to comprise alkoxyl group and these two functional groups of epoxide group because contain the silane-modified epoxy resin of alkoxyl group; It can be linked together through chemical action with the binder resin of the thermally curable resin composition that is used for protective membrane; And make and to cause the condensation reaction with sticker, thereby form chemical bonding with the substrate that places the upper and lower with acid.
In addition; The molecular weight of the conventional bonding agent of molecular weight ratio of silane-modified epoxy resin that contains alkoxyl group is big; Therefore in the film toughness of the binder resin in being kept for the thermally curable resin composition of protective membrane, can improve thermofixation protective membrane and upper and lower layer between bond strength.
The silane-modified epoxy resin that contains alkoxyl group of the present invention can be prepared by any in following two optional responses.
First reaction is the reaction that is taken place by the organoalkoxysilane that the epoxy compounds that contains silyl of formula 1 expression and Chemical formula 2 are represented, makes the silane-modified epoxy resin that contains 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
6Thiazolinyl alkyl, C
1-C
6Mercaptoalkyl and C
6-C
12Aryl.
Second reaction is the organoalkoxysilane that the epoxy compounds that contains silyl and the Chemical formula 2 of chemical formula 3 expressions are represented to be reacted obtain containing the silane-modified epoxide group of 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
6Thiazolinyl alkyl, C
1-C
6Mercaptoalkyl and C
6-C
12Aryl,
n
1And n
2Respectively do for oneself 1 or 2, and n
1+ n
2=3.
Transmittance and bond strength for the enhance protection film; The amount of silane-modified epoxy resin that contains alkoxyl group is based on total thermally curable resin composition solid meter that is used for protective membrane that contains epoxy resin; Its amount is preferably about 0.5 to about 30 weight %, the silane-modified epoxy resin that contains alkoxyl group based on total solids meter more preferably about 0.5 to about 20 weight %, most preferably its amount is for about 1 to about 15 weight %.
The silane-modified epoxy resin that contains alkoxyl group of the present invention is by epoxy compounds that contains silyl and organoalkoxysilane pure condensation reaction to take place to obtain, and has the characteristic that can obtain multiple physical properties through the ratio of adjusting two kinds of compounds.
Consider the easy property of stability in storage and synthetic, the epoxy compounds that contains silyl and organoalkoxysilane preferably with about 5: 1 to about 1: 1 weight ratio, more preferably mixed to about 3: 1 weight ratio with about 5: 1.
The weight-average molecular weight that contains the silane-modified epoxide group of alkoxyl group of the present invention is about 1,000 to about 10,000, and it demonstrates consistency and bond strength enhanced effect with sticker in this scope.
The epoxy compounds that contains silyl that Chemical formula 1 is represented does not limit; So long as the normally used the type compound in this area can use; The non-limitative example of this compound can comprise a kind of 3-of being selected from glycidoxy-propyltrimethoxy silane, 3-epoxypropoxy triethoxyl silane, 3-epoxypropoxy methyl dimethoxysilane, 3-epoxypropoxy methyldiethoxysilane, 3; 4-epoxycyclohexyl ethyl trimethoxy silane and 3, the compound of 4-epoxycyclohexyl ethyl triethoxysilane.
Not restriction of the epoxy compounds that contains silyl to spendable chemical formula 3 expressions; So long as the normally used the type compound in this area gets final product; The non-limitative example of this compound can comprise a kind of 3-of being selected from (N; The N-diglycidyl) TSL 8330, N-glycidyl-N, N-two [3-(methyl dimethoxy oxygen base silyl) propyl group] amine and N-glycidyl-N, the compound of N-two [3-(trimethoxysilyl) propyl group] amine.
The organoalkoxysilane that spendable Chemical formula 2 is represented does not limit; So long as the normally used the type compound in this area gets final product; The non-limitative example of this compound can comprise that one or more are selected from following organoalkoxysilane: methyltrimethoxy silane, Union carbide A-162, methyl tripropoxy silane, methyl three butoxy silanes, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl Trimethoxy silane, n-propyl triethoxyl silane, sec.-propyl Trimethoxy silane, sec.-propyl triethoxyl silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, 3-sulfydryl propyl trimethoxy silicane and 3-sulfydryl propyl-triethoxysilicane, or its partial condensate.
The thermally curable resin composition that is used for protective membrane of the present invention comprises silane-modified epoxy resin, binder resin, the solvent that contains alkoxyl group, also can comprise other additives when needing.
This binder resin is the unsaturated compound that contains epoxide group, ethylenically unsaturated compounds and as the multipolymer of other polymerisable monomers of optional compound.
To the spendable not restriction of unsaturated compound that contains epoxide group; So long as the normally used the type compound in this area gets final product; 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 (interior type 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-Yi Jibingxisuan 6; The aliphatic unsaturated compound that contains epoxide group of 7-epoxy heptyl ester and (methyl) vinylformic acid methyl glycidyl ester, or be selected from the alicyclic unsaturated compound that contains that epoxide group is arranged of following chemical formula 4 to 6 represented compounds or its mixture.
R
11, R
13And R
15Identical or different, be Wasserstoffatoms or C
1-C
6The straight 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, inferior normal-butyl, isobutylidene, inferior sec.-butyl and inferior n-pentyl, but are not limited thereto.
But for the filter protective membrane as LCD, this compound need have splendid transparency, therefore can use leucocompound.
The amount that contains the unsaturated compound of epoxide group counts about 10 to about 90 weight % based on the gross weight of binder resin, and preferred about 20 to about 70 weight % especially.When the amount of the unsaturated compound that contains epoxide group during less than about 10 weight %, solidify insufficiently, therefore the physical strength of formed heat reactive resin film, chemical resistant properties, thermotolerance etc. are easy to deterioration.When the amount of the unsaturated compound that contains epoxide group during greater than about 90 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 can comprise also that one or more are selected from following functional group: hydroxyl, silyl, show tart functional group, carboxyl and carboxylic acid anhydride group through hydrolytic action.
Show tart functional group through hydrolytic action and refer to decompose in specific range of temperatures (be preferably about 150 ℃ to about 250 ℃ TR)---promptly under this temperature, carrying out the back baking that is used for the thermally curable resin composition of protective membrane of the present invention---and generate sour group, the acid of generation can react with the epoxide group in the unsaturated compound that contains epoxide group.
To the not restriction of spendable ethylenically unsaturated compounds, so long as the normally used the type compound in this area gets final product.
Specifically, the example that contains the ethylenically unsaturated compounds of hydroxyl can comprise (methyl) vinylformic acid 2-hydroxyl ethyl ester etc.
The example that contains the ethylenically unsaturated compounds of silyl can comprise vinyl trialkyl oxysilane such as vinyltrimethoxy silane, vinyltriethoxysilane etc., or (methyl) acryloyl-oxy base silane such as vinyl three ('beta '-methoxy oxyethyl group) silane, methyl ethylene dimethoxy silane, β-(methyl) acryloxy ethyl trimethoxy silane, β-(methyl) acryloxy ethyl triethoxysilane, 3-(methyl) acryloxy propyl trimethoxy silicane, 3-(methyl) acryloxy propyl-triethoxysilicane, γ-(methyl) acryloxy propyl group methyl dimethoxysilane, γ-(methyl) acryloxy propyl-dimethyl methoxy silane, γ-(methyl) acryloxy propyl group methyldiethoxysilane, 3-(methyl) acryloxy propyl-dimethyl Ethoxysilane, 3-(methyl) acryloxy propyl trimethoxy silicane etc.
Contain the example that shows the ethylenically unsaturated compounds of tart functional group through hydrolytic action and can comprise (methyl) vinylformic acid tetrahydrochysene 2H-pyrans-2-base ester, (methyl) tert-butyl acrylate etc.
The example that contains the ethylenically unsaturated compounds of 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 that contains the ethylenically unsaturated compounds of anhydride group can comprise (methyl) acrylic anhydride, crotonic anhydride, itaconic anhydride, MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE acid anhydride, monomethyl MALEIC ANHYDRIDE, isoprene sulphonic acid anhydride, styrene sulfonic acid acid anhydride, norbornylene-2-carboxylic acid anhydride etc.
The amount of ethylenically unsaturated compounds counts about 5 to about 50 weight % based on the gross weight of binder resin, is preferably about 10 especially to about 40 weight %.When the amount of ethylenically unsaturated compounds during less than about 5 weight %, the curing of expectation can not fully be carried out.When the amount of ethylenically unsaturated compounds during greater than about 50 weight %, this binder resin in polymerization process owing to stability degradation is difficult for polymerization.
In addition, when needing, binder resin of the present invention can comprise other polymerisable monomers except above component.
As other polymerisable monomers, can use monomer known in the art, so long as can get final product with unsaturated compound that contains epoxide group or ethylenically unsaturated compounds monomer polymerized.
Non-limitative example can comprise: aliphatic series or aromatic series (methyl) propenoate, like (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 esters etc.; (methyl) propenoate of caprolactone modification is like 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 is like vinylbenzene, 4-methoxy styrene, 4-vinyl toluene etc.; Based on the compound of conjugated diolefine, like 1,3-butadiene or isoprene etc.
In order suitably to control the physical properties (like physical strength, tackiness, planarity (planarizability) and similarity) that the heat reactive resin that prepared by thermally curable resin composition is filmed; Can use other different polymerisable monomers; And this monomeric amount is preferably about 1 to about 50 weight % based on binder resin meter of the present invention.
With reference to polystyrene standards, the weight-average molecular weight of binder resin of the present invention (Mw) is about 2,000 to about 100,000 suitably, is preferably about 3,000 to about 50,000 especially.When molecular weight about 2,000 or more hour, the film properties that is used for the thermally curable resin composition of protective membrane is easy to deterioration.When molecular weight about 100,000 or when bigger, the multipolymer that obtains possibly be difficult for handling and planarity maybe deterioration.
As the solvent that comprises in the thermally curable resin composition of the present invention, can use solvent known in the art.The non-limitative example of solvent can comprise: alkyl ketone, like methylethylketone, pimelinketone etc.; Ethers is like THF etc.; Terepthaloyl moietie alkyl oxide acetic ester is like methyl acetic acid cellosolve, ethyl acetic acid cellosolve, ethylene glycol monomethyl ether acetate etc.; Propylene glycol alkyl ether acetic acid ester is like propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetic ester etc.; Glycols is like ethylene glycol butyl ether, 2-methoxy ethyl ether, ethylene glycol ethyl ethers ylmethyl ether, ethylene glycol diethyl ether etc.; The ester class is like ETHYLE ACETATE, ethyl lactate and 3-ethoxyl ethyl propionate etc.; Or its binding substances etc.
To not limiting according to optional other additives that add the thermally curable resin composition that is used for protective membrane of other application targets; So long as the normally used the type compound in this area gets final product, said other application targets such as film performance, with the clinging power of substrate, chemicalstability etc.Ground does not influence under the situation like planarity, transmittance, thermotolerance etc., and the non-limitative example of spendable other additives has polyfunctional monomer, bonding agent, tensio-active agent, hot stopper etc.
To the not restriction of spendable polyfunctional monomer, as long as it is the compound that contains 2 to 6 unsaturated functional groups.This monomeric non-limitative example can comprise: multifunctional (methyl) propenoate; Like 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-pinakon ester, three (methyl) vinylformic acid trishydroxymethyl propyl ester, tetramethylolmethane two (methyl) propenoate, tetramethylolmethane three (methyl) propenoate, tetramethylolmethane four (methyl) propenoate, Dipentaerythritol five (methyl) propenoate, Dipentaerythritol six (methyl) propenoate etc.
This unsaturated functional group adopts the polyfunctional monomer that contains 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, thereby has strengthened the intensity and the chemical resistant properties of cured film.
Based on 100 weight part binder resin meters, the amount of spendable polyfunctional monomer is about 1 to about 200 weight parts, is preferably about 5 to about 100 weight parts.The molecular weight of crosslinkable polyfunctional monomer is lower than the molecular weight of binder resin of the present invention, and can effectively strengthen planarity.Particularly, during polyfunctional monomer in using above-mentioned scope, have the splendid generative capacity of filming, and cannot not filming stickingly of forming.
Bonding agent is the compound that can strengthen with the bond property of support base material, to its not special restriction, as long as this auxiliary agent can satisfy this purpose, and the compound that is based on silane of conventional use.Non-limitative example based on the compound of silane comprises methyl allyl acyloxypropyl trimethoxysilane (methcryloxypropyltrimethoxysilane), γ-glycidoxypropyltrime,hoxysilane, β-(3，4-Huan Yanghuanjiji)Yi Jisanjiayangjiguiwan, γ-Qiu Jibingjisanjiayangjiguiwan, vinyltriacetoxy silane, vinyltrimethoxy silane and its mixture.
Consider the character and the stability of filming, based on 100 weight part binder resin meters, the consumption of bonding agent can be about 30 weight parts or still less, preferred especially about 20 weight parts or still less.
Other additives comprise the component that is generally used for coating solution, like 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.
The solids content that is used for the thermally curable resin composition of protective membrane of the present invention can suitably be selected according to film and its purpose; But consider coating, the amount of said composition is preferably about 1 to about 60 weight %, more preferably about 5 to about 40 weight %.
Consider the efficient that generates protective membrane, the thermally curable resin composition that is used for protective membrane of the present invention can be the single component type.
Can prepare the thermofixation protective membrane by the thermally curable resin composition that is used for protective membrane of the present invention through the conventional known method in this area.
The method for preparing the thermofixation protective membrane will be described according to an embodiment.
The thermally curable resin composition that will be used for protective membrane through appropriate means is applied to substrate, and preliminary drying is to form the thermofixation protective membrane except that desolvating and form spendable film, next afterwards drying by the fire.
The application process of said composition does not have particular restriction, can use spraying method, rolling method, spin-coating method, gap nozzle method etc., and normally used is spin-coating method.Difference according to circumstances, solvent that can be earlier that some are residual after before preliminary drying, using is removed with the method for decompression.
According to the compsn and the application target thereof that use, preliminary drying is different with back baking condition.For example, conventional preliminary drying can carry out 0.5 to 5 minute under about 60 ℃ to about 130 ℃.In addition, conventional back baking can be carried out 10 minutes to 2 hours under about 150 ℃ to about 250 ℃.In addition, all a step carries out or the two is combined carrying out respectively for preliminary drying and back baking.In back baking step, the epoxide group of binder resin reacts to form with the acid groups that is decomposed to form and has cancellated protective membrane.
Protective membrane with this method preparation has splendid planarity, high surface hardness and splendid chemical resistant properties (like thermotolerance, acid resistance, alkali resistance etc.).Therefore, this protective membrane can be used as the protective membrane material of the filter that is used for liquid crystal display.
In addition, the present invention also provides a kind of liquid crystal display that contains the filter that comprises this protective membrane.This liquid crystal display comprises black matrix" (black matrix) and filter, and available ordinary method known in the art prepares.
Below, the present invention will be described in more detail through synthetic embodiment and embodiment.But the invention is not restricted to this.
The synthetic embodiment of binder resin
Synthetic embodiment 1
The methylacrylic acid of 23 weight parts, the SY-Monomer G of 50 weight parts, the vinylbenzene of 27 weight parts and the propylene glycol methyl ether acetate adding of 200 weight parts are had in the flask of nitrogen inlet; Flask is heated to about 90 ℃; Azo two valeronitriles (AVN) that add 4.0 weight parts again keep this temperature to obtain polymers soln after 6 hours.This polymers soln is added dropwise in a large amount of excessive hexanes forms deposition, and this is deposited in drying obtains binder resin under the vacuum.With reference to polystyrene standards, the weight-average molecular weight (Mw) of multipolymer (A1) is about 13,100.
Synthetic embodiment 2
Do not use the methylacrylic acid of 23 weight parts, the SY-Monomer G of 50 weight parts and the vinylbenzene of 27 weight parts, use the methylacrylic acid of 15 weight parts, the SY-Monomer G of 45 weight parts, the vinylbenzene of 25 weight parts and the methylacrylic acid two of 15 weight parts to encircle pentyl esters by obtaining multipolymer (A2) with synthetic embodiment 1 same mode; With reference to polystyrene standards, its weight-average molecular weight (Mw) is about 11,500.
Synthetic embodiment 3
Do not use the methylacrylic acid of 23 weight parts, the SY-Monomer G of 50 weight parts and the vinylbenzene of 27 weight parts, use the methylacrylic acid 2-tetrahydrochysene-2H-pyrans-2-base ester of 20 weight parts, the SY-Monomer G of 41 weight parts, the vinylbenzene of 21 weight parts and the methylacrylic acid two of 18 weight parts to encircle pentyl esters by obtaining multipolymer (A3) with synthetic embodiment 1 same mode; With reference to polystyrene standards, its weight-average molecular weight (Mw) is about 10,500.
The synthetic embodiment that contains the silane-modified epoxy resin of alkoxyl group
Synthetic embodiment 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 that has the nitrogen input; Subsequently a kind of solution that 20 weight parts water solution are arranged of wherein introducing is added in the flask; In the said aqueous solution; 0.1 weight part sodium hydroxide is added in the 100 weight part propylene glycol methyl ether acetates, then this flask is heated to 70 ℃, keeps this temperature 6 hours.
After the reaction, the methyl alcohol that in about 50mmHg reduced pressure following 2 hours, hydrolysis is generated is removed, and obtains containing the silane-modified epoxy resin (B1) of alkoxyl group; With reference to polystyrene standards, its weight-average molecular weight (Mw) is about 3,300.
Synthetic embodiment 5
Do not use the 3-glycidoxy-propyltrimethoxy silane of 75 weight parts; Use the N-glycidyl-N of 75 weight parts, N-two [3-(methyl dimethoxy oxygen base silyl) propyl group] amine is by obtaining containing the silane-modified epoxy resin (B2) of alkoxyl group with synthetic embodiment 4 same modes; With reference to polystyrene standards, its weight-average molecular weight (Mw) is about 4,100.
The synthetic Comparative Examples of binder resin
Synthetic Comparative Examples 1
The TEB 3K of 50 weight parts, the SY-Monomer G of 50 weight parts and the pimelinketone of 270 weight parts are added in the flask with nitrogen input; Flask is heated to about 80 ℃; The Diisopropyl azodicarboxylate that adds 5 weight parts again keeps this temperature to obtain containing the polymers soln of multipolymer (P1) after 3 hours.This polymers soln is added dropwise in a large amount of excessive hexanes forms deposition, and this is deposited in drying obtains binder resin under the vacuum.The weight-average molecular weight (Mw) of this multipolymer (P1) is about 8,400.
Synthetic Comparative Examples 2
The methylacrylic acid of 20 weight parts, the SY-Monomer G of 20 weight parts, the vinylbenzene of 20 weight parts, the methylacrylic acid 2-tetrahydrochysene-2H-pyrans-2-base ester of 20 weight parts, the N-cyclohexyl maleimide 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 ℃; The azo two (2 that adds 5 weight parts again; The 4-dimethyl-) valeronitrile keeps this temperature to obtain containing the polymers soln of multipolymer (P2) after 5 hours.This polymers soln is added dropwise in a large amount of excessive hexanes forms deposition, and this is deposited in drying obtains binder resin under the vacuum.With reference to polystyrene standards, the weight-average molecular weight (Mw) of this multipolymer (P2) is about 10,500.
The synthetic Comparative Examples that contains the silane-modified epoxy resin of alkoxyl group
Synthetic Comparative Examples 3
The 3-glycidoxy-propyltrimethoxy silane of 70 weight parts, the phenyltrimethoxysila,e of 17 weight parts and the dimethoxydiphenylsilane of 13 weight parts are added in the flask that has the nitrogen input;---wherein 0.1 weight part sodium hydroxide is added into 100 weight part propylene glycol methyl ether acetates---adds in the flask and is heated to 60 ℃ subsequently with 20 weight parts water solution, keeps this temperature 6 hours.
After the reaction, the methyl alcohol that in about 50mmHg reduced pressure following 2 hours, hydrolysis is generated is removed, and obtains containing the silane-modified epoxy resin (Q1) of alkoxyl group; With reference to polystyrene standards, its weight-average molecular weight (Mw) is about 4,400.
Synthetic Comparative Examples 4
The 3-glycidoxy-propyltrimethoxy silane of 61 weight parts, the tetramethoxy-silicane of 39 weight parts and the propylene glycol monomethyl ether of 129 weight parts are added in the flask that has the nitrogen input; Be heated to about 60 ℃; Add the 11 weight parts water solution that contain 0.1 weight part oxalic acid then, kept this temperature 4 hours.
By carrying out the silane-modified epoxy resin (Q2) that purifying obtains containing alkoxyl group with synthetic Comparative Examples 3 same modes; With reference to polystyrene standards, its weight-average molecular weight (Mw) is about 13,000.
Embodiment 1
Mix with the propylene glycol methyl ether acetate of the silane-modified epoxy resin that contains alkoxyl group (B1) by preparation among the synthetic embodiment 4 of the multipolymer (A1) by preparation among the synthetic embodiment 1 of 100 weight parts, 5 weight parts, 400 weight parts with as the surfactant B YK331 (BYK) of 0.1 weight part of additive; Next use diameter for the strainer of about 0.2 μ m filters, obtain being used for the thermally curable resin composition of protective membrane.
This thermally curable resin composition that is used for protective membrane is applied to glass substrate, as preliminary drying on hot plate about 90 ℃ dry 2 minutes down, next about 220 ℃ of back bakings 30 minutes down in baking oven obtain the protective membrane of the about 2.0 μ m of thickness.
Embodiment 2
By with embodiment 1 in the preparation of identical method be used for the thermally curable resin composition and the protective membrane of protective membrane, difference is to use the multipolymer (A2) by preparation among the synthetic embodiment 2 to substitute multipolymer (A1).
Embodiment 3
By with embodiment 1 in the preparation of identical method be used for the thermally curable resin composition and the protective membrane of protective membrane, difference is to use the multipolymer (A3) by preparation among the synthetic embodiment 3 to substitute multipolymer (A1).
Embodiment 4
By with embodiment 1 in the preparation of identical method be used for the thermally curable resin composition and the protective membrane of protective membrane, difference is that gradation adds the dipentaerythritol acrylate of 30 weight parts.
Embodiment 5
By with embodiment 1 in the preparation of identical method be used for the thermally curable resin composition and the protective membrane of protective membrane, difference is to use the silane-modified epoxy resin that contains alkoxyl group (B2) by preparation among the synthetic embodiment 5 to substitute the silane-modified epoxy resin (B1) that contains alkoxyl group.
Comparative Examples 1
By with embodiment 1 in the preparation of identical method be used for the thermally curable resin composition and the protective membrane of protective membrane, difference is not use the silane-modified epoxy resin (B1) that contains alkoxyl group.
Comparative Examples 2
By with embodiment 4 in the preparation of identical method be used for the thermally curable resin composition and the protective membrane of protective membrane, difference is not use the silane-modified epoxy resin (B1) that contains alkoxyl group.
Comparative Examples 3
By with embodiment 1 in the preparation of identical method be used for the thermally curable resin composition and the protective membrane of protective membrane; Difference be to use 100 weight parts the multipolymer (P1) by synthetic Comparative Examples 1 preparation, 23 weight parts by 1 of the silane-modified epoxy resin that contains alkoxyl group (Q1) of synthetic Comparative Examples 3 preparations and 33 weight parts; 2, the 4-benzenetricarboxylic anhydride substitutes multipolymer (A1), contains the silane-modified epoxy resin (B1) and the surfactant B YK331 (BYK) of alkoxyl group.
Comparative Examples 4
By with embodiment 1 in the preparation of identical method be used for the thermally curable resin composition and the protective membrane of protective membrane; Difference be to use the multipolymer (P2) by synthetic Comparative Examples 2 preparations, 20 weight parts of 100 weight parts the silane-modified epoxy resin that contains alkoxyl group (Q2) by synthetic Comparative Examples 4 preparations, 40 weight parts hexahydro phthalic anhydride and substitute multipolymer (A1), contain the silane-modified epoxy resin (B1) and the surfactant B YK331 (BYK) of alkoxyl group as the SH-28PA (by Toray Dow Corning Silicone Co., Ltd. produces) of 0.1 weight part of tensio-active agent.
EXPERIMENTAL EXAMPLE
1. bond strength
Use the ASTM-D3359 method to carry out pressure furnace test (120 ℃, humidity 100%, 4 hour), adopt grizzly bar adhesive tape (grid tape) method on protective membrane, to mark 100 grizzly bars, with adhesive tape it is peeled off again with cut-off knife.Then, measure the grizzly bar pattern number that in 100 grizzly bar patterns, does not come off.
2. surface hardness
Use the ASTM-D3363 method to carry out the pencil hardness test of protective membrane, with its outcome record in following table 1.
3. transmittance
Form the glass substrate of protective membrane on the light transmission surface of the about 400nm of wavelength, and with its outcome record in following table 1.
4. stability in storage
Use the capillary viscosimeter measurement to be used for the viscosity of the thermally curable resin composition of protective membrane.Next said composition is placed about 25 ℃ of following 2 weeks, the velocity of variation of initial viscosity is listed in the following table 1.
5. processing characteristics
Type according to the silane-modified epoxy resin that contains alkoxyl group is different, and the processing characteristics that is used for the thermally curable resin composition of protective membrane is listed in table 1.
When the silane-modified epoxy resin of preparing that contains alkoxyl group was collosol state, the thermally curable resin composition that is used for protective membrane that comprises this resin had splendid processing characteristics.But, when the silane-modified epoxy resin of preparing that contains alkoxyl group is gel state, comprise the processing characteristics deterioration of the thermally curable resin composition that is used for protective membrane of this resin.
6. consistency
Type according to the silane-modified epoxy resin that contains alkoxyl group is different, and the consistency that is used for the thermally curable resin composition of protective membrane is listed in table 1.
When the molecular weight of the silane-modified epoxy resin that contains alkoxyl group surpasses about 10; 000 o'clock; Comprise the thermally curable resin composition that is used for protective membrane and the consistency variation that is used for the heat reactive resin of protective membrane of this resin, obtain turbid solution or form muddy film (hazing).
7. acid resistance
The glass substrate that in the time of about 30 ℃, each is formed in its surface protective membrane immerses in the HCl aqueous solution of 5.0wt% to be removed from solution after about 30 minutes, observes the outer field variation of protective membrane and estimates its acid resistance.Outer unconverted glass substrate is evaluated as (O), and skin peels off or the glass substrate of variable color to white is evaluated as poor (X).Its result is listed in the following table 1.
8. alkali resistance
The glass substrate that in the time of about 30 ℃, each is formed in its surface protective membrane immerses in the NaOH aqueous solution of 5.0wt% to be removed from solution after 30 minutes, observed the outer field variation of protective membrane and estimated its alkali resistance.Outer unconverted glass substrate is evaluated as (O), and skin peels off or the glass substrate of variable color to white is evaluated as poor (X).Its result is listed in the following table 1.
9. solvent resistance
The glass substrate that in the time of about 40 ℃, each is formed in its surface protective membrane immersed in the nmp solution 10 minutes, observed the variation of thickness and estimated its solvent resistance.Variation in thickness about 3% or littler glass substrate are evaluated as (O), and variation in thickness is evaluated as poor (X) greater than about 3% glass substrate.Its result is listed in the following table 1.
[table 1]
Through using the silane-modified epoxy resin that contains alkoxyl group of optimization according to the present invention; Protective membrane among the embodiment 1 to 5 has splendid bond strength; And the protective membrane in Comparative Examples 1 and 2 does not have to use the silane-modified epoxy resin that contains alkoxyl group, and its bond strength is very poor.
In Comparative Examples 3, be higher than the content among the embodiment 1 to 5 at the content of the silane-modified epoxy resin that contains alkoxyl group of the thermally curable resin composition that is used for protective membrane.When the silane-modified epoxy resin usage quantity that contains alkoxyl group is big, confirm that its transmittance reduces.
In Comparative Examples 4, preparation be used for that the thermally curable resin composition of protective membrane comprises contain the silane-modified epoxy resin of alkoxyl group the time used tetramethoxy-silicane.It is too fast to use the tetramethoxy-silicane preparation to contain the speed of reaction of silane-modified epoxy resin (Q2) of alkoxyl group, makes the reaction of preparation resin be difficult for carrying out.
In addition; Using the molecular weight of the silane-modified epoxy resin that contains alkoxyl group (Q2) of tetramethoxy-silicane preparation in the Comparative Examples 4 is about 10; 000 or bigger; Thereby there is limitation in the consistency that confirms itself and heat reactive resin, and comprises the stability in storage variation of the thermally curable resin composition that is used for protective membrane of this epoxy resin.
On the contrary, the silane-modified epoxy resin that contains alkoxyl group (B1 and B2) that uses among the embodiment 1 to 5 all is collosol state, therefore is easy to this resin is mixed with the thermally curable resin composition that is used for protective membrane.
Confirm through these embodiment and EXPERIMENTAL EXAMPLE: protective membrane of the present invention can significantly improve bond strength when keeping film toughness and other physical propertiess.
The present invention can comprise the thermally curable resin composition that is used for protective membrane of the silane-modified epoxy resin that contains alkoxyl group through use, and a kind of filter protective membrane is provided; This protective membrane can have splendid film toughness, and with color filter layer, column spacer or ITO layer that the protective membrane upper and lower exists splendid bond strength is arranged, and can be used in the large-scale LCD.
Above disclosed theme be Illustrative and nonrestrictive, appended claims is intended to be encompassed in all relevant modification, improvement and other embodiments in the purport scope of the present invention.Therefore, in allowed by law maximum range, scope of the present invention is equal to the admissible the most wide in range explanation decision of alternative by following claims and its, and should not restricted or limit by foregoing detailed description.
Claims (21)
1. thermally curable resin composition that is used for protective membrane comprises the silane-modified epoxy resin that contains alkoxyl group that organoalkoxysilane reaction that about 0.5 to about 30 weight % the epoxy compounds that contains silyl that passes through Chemical formula 1 is represented that accounts for the solids content gross weight and Chemical formula 2 are represented makes:
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
6Thiazolinyl alkyl, C
1-C
6Mercaptoalkyl and C
6-C
12Aryl.
2. thermally curable resin composition that is used for protective membrane, comprise account for the solids content gross weight about 0.5 to about 30 weight % pass through the organoalkoxysilane that the epoxy compounds that contains silyl of chemical formula 3 expressions and Chemical formula 2 are represented is reacted the silane-modified epoxy resin that contains alkoxyl group that makes:
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
6Thiazolinyl alkyl, C
1-C
6Mercaptoalkyl and C
6-C
12Aryl,
n
1And n
2Respectively do for oneself 1 or 2, and n
1+ n
2=3.
3. claim 1 or 2 compsn wherein contain in the reaction of silane-modified epoxy resin of alkoxyl group in generation, and the said epoxy compounds that contains silyl and said organoalkoxysilane mixed to about 1: 1 weight ratio with about 5: 1.
4. claim 1 or 2 compsn wherein contain in the reaction of silane-modified epoxy resin of alkoxyl group in generation, and the said epoxy compounds that contains silyl and said organoalkoxysilane mixed to about 3: 1 weight ratio with about 5: 1.
5. claim 1 or 2 compsn, wherein with reference to polystyrene standards, the said weight-average molecular weight that contains the silane-modified epoxide group of alkoxyl group is about 1,000 to about 10,000.
6. the compsn of claim 1; The epoxy compounds that contains silyl that wherein Chemical formula 1 is represented is that one or more are selected from following compound: 3-glycidoxy-propyltrimethoxy silane, 3-epoxypropoxy triethoxyl silane, 3-epoxypropoxy methyl dimethoxysilane, 3-epoxypropoxy methyldiethoxysilane, 3; 4-epoxycyclohexyl ethyl trimethoxy silane and 3,4-epoxycyclohexyl ethyl triethoxysilane.
7. the compsn of claim 2; Wherein the epoxy compounds that contains silyl of chemical formula 3 expressions is that one or more are selected from following compound: 3-(N; The N-diglycidyl) TSL 8330, N-glycidyl-N; N-two [3-(methyl dimethoxy oxygen base silyl) propyl group] amine and N-glycidyl-N, N-two [3-(trimethoxysilyl) propyl group] amine.
8. claim 1 or 2 compsn; Wherein the organoalkoxysilane represented of Chemical formula 2 is that one or more are selected from following compound: methyltrimethoxy silane, Union carbide A-162, methyl tripropoxy silane, methyl three butoxy silanes, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl Trimethoxy silane, n-propyl triethoxyl silane, sec.-propyl Trimethoxy silane, sec.-propyl triethoxyl silane, phenyltrimethoxysila,e, phenyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, 3-sulfydryl propyl trimethoxy silicane and 3-sulfydryl propyl-triethoxysilicane, or its partial condensate.
9. claim 1 or 2 compsn, the wherein said thermally curable resin composition that is used for protective membrane further comprises binder resin and solvent.
10. the compsn of claim 9, wherein said binder resin are the unsaturated compound that contains epoxide group, ethylenically unsaturated compounds and as the multipolymer of other polymerisable monomers of optional compound.
11. the compsn of claim 10; The unsaturated compound that wherein contains epoxide group is to be selected from glycidyl allyl ether, 5-norbornylene-2-methyl-2-carboxylic acid glycidyl ester (interior type 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-Yi Jibingxisuan 6, the aliphatic unsaturated compound that contains epoxide group of 7-epoxy heptyl ester and (methyl) vinylformic acid methyl glycidyl ester; Or be selected from the alicyclic unsaturated compound that contains epoxide group that following chemical formula 4 to 6 is represented compounds, or its mixture;
R
11, R
13And R
15Identical or different, be Wasserstoffatoms or C
1-C
6Alkyl; And R
12, R
14And R
16Identical or different, be C
1-C
6Alkylidene group.
12. the compsn of claim 10, wherein said ethylenically unsaturated compounds comprise that also one or more are selected from following functional group: hydroxyl, silyl, show tart functional group, carboxyl and carboxylic acid anhydride group through hydrolytic action.
13. being one or more, the compsn of claim 12, wherein said ethylenically unsaturated compounds be selected from following compound: as (methyl) vinylformic acid 2-hydroxyl ethyl ester of the ethylenically unsaturated compounds that contains hydroxyl;
The ethylenically unsaturated compounds that contains silyl is selected from vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane, methyl ethylene dimethoxy silane, β-(methyl) acryloxy ethyl trimethoxy silane, β-(methyl) acryloxy ethyl triethoxysilane, 3-(methyl) acryloxy propyl trimethoxy silicane, 3-(methyl) acryloxy propyl-triethoxysilicane, γ-(methyl) acryloxy propyl group methyl dimethoxysilane, γ-(methyl) acryloxy propyl-dimethyl methoxy silane, γ-(methyl) acryloxy propyl group methyldiethoxysilane, 3-(methyl) acryloxy propyl-dimethyl Ethoxysilane and 3-(methyl) acryloxy propyl trimethoxy silicane;
Contain the ethylenically unsaturated compounds that shows tart functional group through hydrolytic action, be selected from (methyl) vinylformic acid tetrahydrochysene-2H-pyrans-2-base ester and (methyl) tert-butyl acrylate;
The ethylenically unsaturated compounds that contains carboxyl is selected from (methyl) vinylformic acid, butenoic acid, methylene-succinic acid, maleic acid, FUMARIC ACID TECH GRADE, monomethyl maleic acid, isoprene sulfonic acid, styrene sulfonic acid and norbornylene-2-carboxylic acid; And
The ethylenically unsaturated compounds that contains anhydride group is selected from (methyl) acrylic anhydride, crotonic anhydride, itaconic anhydride, MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE acid anhydride, monomethyl MALEIC ANHYDRIDE, isoprene sulphonic acid anhydride, styrene sulfonic acid acid anhydride and norbornylene-2-carboxylic acid anhydride.
14. the compsn of claim 10; Wherein other polymerisable monomers are that one or more are selected from following compound: (methyl) propenoate, vinylbenzene, 4-methoxy styrene, 4-vinyl toluene, 1,3-butadiene and the isoprene of (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 esters, caprolactone modification.
15. the compsn of claim 9, wherein with reference to polystyrene standards, the weight-average molecular weight of said binder resin (Mw) is about 2,000 to about 100,000.
16. being one or more, the compsn of claim 9, wherein said solvent be selected from following compound: methylethylketone, pimelinketone, THF, methyl acetic acid cellosolve, 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, ETHYLE ACETATE, ethyl lactate and 3-ethoxyl ethyl propionate.
17. the compsn of claim 9, the wherein said thermally curable resin composition that is used for protective membrane comprise that also one or more are selected from other following additives: polyfunctional monomer, bonding agent, tensio-active agent and hot stopper.
18. the compsn of claim 1, the wherein said thermally curable resin composition solid amount that is used for protective membrane are about 1 to about 60 weight %.
19. the compsn of claim 1, the wherein said thermally curable resin composition that is used for protective membrane is the single component type.
20. a filter protective membrane is prepared by the thermally curable resin composition that is used for protective membrane of claim 1.
21. a liquid crystal display comprises the filter protective membrane of claim 20.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20100067078 | 2010-07-12 | ||
| KR10-2010-0067078 | 2010-07-12 | ||
| KR10-2011-0059707 | 2011-06-20 | ||
| KR1020110059707A KR101261621B1 (en) | 2010-07-12 | 2011-06-20 | Thermally curable resin composition for over coat |
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| CN103483753A (en) * | 2012-06-11 | 2014-01-01 | 奇美实业股份有限公司 | Curable resin composition, protective film and liquid crystal display element containing the protective film |
| CN106867011A (en) * | 2017-01-18 | 2017-06-20 | 国网吉林省电力有限公司电力科学研究院 | A kind of silicon rubber powder surface modifier and preparation method thereof |
| CN107915843A (en) * | 2017-11-14 | 2018-04-17 | 万华化学集团股份有限公司 | A kind of modified MQ silicones and preparation method thereof |
| WO2019041923A1 (en) * | 2017-08-30 | 2019-03-07 | 京东方科技集团股份有限公司 | Composition for flat layer, preparation method therefor, flat layer material, display substrate and display device |
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| 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 |
| JP6819052B2 (en) * | 2015-03-04 | 2021-01-27 | 住友化学株式会社 | Curable resin composition |
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| CN103483753A (en) * | 2012-06-11 | 2014-01-01 | 奇美实业股份有限公司 | Curable resin composition, protective film and liquid crystal display element containing the protective film |
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| WO2019041923A1 (en) * | 2017-08-30 | 2019-03-07 | 京东方科技集团股份有限公司 | Composition for flat layer, preparation method therefor, flat layer material, display substrate and display device |
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| CN107915843B (en) * | 2017-11-14 | 2020-08-28 | 万华化学集团股份有限公司 | Modified MQ silicon resin and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20120006445A (en) | 2012-01-18 |
| KR101261621B1 (en) | 2013-05-07 |
| JP2012021155A (en) | 2012-02-02 |
| JP5881049B2 (en) | 2016-03-09 |
| JP2014043580A (en) | 2014-03-13 |
| KR101336307B1 (en) | 2013-12-02 |
| CN102372887B (en) | 2015-01-21 |
| JP5429757B2 (en) | 2014-02-26 |
| KR20130039320A (en) | 2013-04-19 |
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