CN1269921C - Settability resin combination - Google Patents

Abstract

Provided are a curable resin composition which can form a coat having excellent heat resistance and transparency, a color filter prepared from the composition which is free from the defect of pattern or the residue after development, and a display device using the color filter. The curable resin composition comprises a polymer component; and a curing component which comprises at least one kind of compound selected from the group consisting of a compound having a radical polymerizable double bond and a compound having an epoxy group, wherein the polymer component is a polymer obtained by polymerizing a monomer component comprising a compound represented by the formula I essentially. In the formula I, R1 and R2 are independently H or a C1-C25 hydrocarbon group capable of being substituted.

Description

Curable resin composition and uses thereof

[technical field]

The present invention relates to novel curable resin combination and uses thereof.

[background technology]

So far, curable resin composition as good heat resistance, for example, (for example proposed to contain resin combination that the monomer component that will contain 2-(hydroxyalkyl) acrylate carries out the polymkeric substance that contains lactonic ring of polymerization, lactone cyclisation system and cure component, with reference to patent documentation 1) or contain the polymkeric substance that the monomer component polymerization that will contain maleimide makes and the resin combination (for example, with reference to patent documentation 2,3) of cure component.

[patent documentation 1] spy opens the 2002-303975 communique

[patent documentation 2] spy opens flat 04-130128 communique

[patent documentation 3] spy opens flat 10-31308 communique

[summary of the invention]

Yet, contain in the resin combination of polymkeric substance of the former 2-(hydroxyalkyl) acrylate origin, the tendency that polymerizability is low, residual monomer is many when having the system polymkeric substance, in addition owing to produce water or alcohol during the lactone cyclisation, so these residual monomers or water or alcohol might bring detrimentally affect to the rerum natura of solidified nature or cured film.And, because the lactonic ring of polymkeric substance that contains lactonic ring for example, is used for the occasion of purposes such as alkali developable erosion resistant in the easy open loop of alkaline condition, because of development conditions also exists cured portion damaged, the problem that graphics shape is not good and so on.In addition, in the resin combination of the polymkeric substance of the maleimide origin that contains the latter, because the maleimide based polymer contains nitrogen-atoms, so exist polymkeric substance to be coloured to the transparent inadequate problem of yellow～tawny cured film.This transparent problem is obvious especially in the thick occasion of the film thickness of cured film, and also has further painted problem if implement heat treated.

Therefore, the present invention's problem that will solve be to provide can form be coated with all fabulous curable resin composition of film heat resistance and the transparency, with colour filter and the display unit of using this curable resin composition.

The inventor studies with great concentration in order to solve above-mentioned problem.Found that and contain the polymkeric substance that to form as this ad hoc structure compound of the ether dipolymer polymerization of 2-(hydroxyalkyl) acrylate and the resin combination of cure component can solve aforementioned problems at one stroke, thereby finished the present invention.

Promptly, curable resin composition of the present invention, it is characterized in that, be the curable resin composition that contains component of polymer (A) and be selected from the cure component (B) of at least a kind of formation in compound (b1) with free-radical polymerised pair of key and the compound (b2) with epoxy group(ing), aforementioned polymer composition (A) is that the compound that will represent with following general expression (1) is the polymkeric substance (a) that necessary monomer component polymerization forms.

(in the formula (1), R ¹With R ²Respectively separately, the expression hydrogen atom maybe can have substituent C ₁-C ₂₅Alkyl.)

Colour filter of the present invention is characterized in that, is provided with on substrate in the colour filter of curing resin layer formation, and the resin combination that forms aforementioned curing resin layer is aforementioned curable resin composition of the present invention.

Display unit of the present invention is characterized in that, uses substrate to be provided with in the display unit of the colour filter that curing resin layer forms, and the resin combination that forms aforementioned curing resin layer is a curable resin composition of the present invention.

Curable resin composition of the present invention is can form to be coated with film heat resistance and all fabulous resin combination of the transparency, for example, can be adapted at using in the purposes of erosion resistant, various coating agent, coating etc.In addition, according to the present invention, can provide does not have the good colour filter of figure quality damaged or the development residue.According to the present invention, brightness and purity of color height also are provided, do not produce the good display unit of display quality such as color spot.

[embodiment]

Curable resin composition of the present invention is to contain following general expression (1)

(in the formula (1), R ¹With R ²Respectively separately, the expression hydrogen atom maybe can have substituent C ₁-C ₂₅Alkyl.) compound (below, also claim " ether dipolymer " sometimes) of expression be necessary monomer component polymeric polymkeric substance (a) component of polymer (A) as necessary composition.Therefore, curable resin composition of the present invention becomes and can form cured coating film thermotolerance and all good resin combination of the transparency.Aforementioned ether dipolymer was carried out cyclization when this estimation was polymerization, formed the cause of tetrahydrofuran (THF) ring structure in the structural unit of ether dipolymer origin.

Below, (a) describes to aforementioned polymer.

Represent in the aforementioned general expression (1) of aforementioned ether dipolymer, as using R ¹With R ²That represents can have substituent C ₁-C ₂₅Alkyl do not have particular restriction.For example, can enumerate a straight chain shape or a catenate alkyl of methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, tert-pentyl, stearyl, lauryl, 2-ethylhexyl etc.; The aryl of phenyl etc.; The ester ring type base of cyclohexyl, tert-butylcyclohexyl, bicyclic pentadiene, three ring decyls, isobornyl, adamantyl, 2-methyl-2-adamantyl etc.; The alkyl that replaces with the alkoxyl group of 1-methoxyethyl, 1-ethoxyethyl etc.; The alkyl that replaces with the aryl of benzyl etc. etc.Consider the difficult uncle who breaks away under acid or heat effect of most preferable, ethyl, cyclohexyl, benzyl etc. and so on or the substituting group of secondary carbon from stable on heating viewpoint among these.In addition, R ¹With R ²Can be substituting group of the same race, also can be different substituting groups.

Concrete example as aforementioned ether dipolymer, for example, can enumerate dimethyl-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, diethyl-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, two (n-propyl)-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, two (sec.-propyl)-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, two (normal-butyl)-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, two (isobutyl-)-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, two (tertiary butyl)-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, two (tert-pentyl)-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, two (stearyl)-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, two (lauryl)-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, two (2-ethylhexyls)-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, two (1-methoxyethyls)-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, two (1-ethoxyethyl)-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, dibenzyl-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, phenylbenzene-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, dicyclohexyl-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, two (tert-butylcyclohexyl)-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, two (bicyclic pentadiene)-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, two (three ring decyls)-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, two (isobornyl)-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, two adamantyls-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, two (2-methyl-2-adamantyl)-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate etc.Dimethyl-2 most preferably among these, 2 '-[hydroxyl two (methylene radical)] two-2-acrylate, diethyl-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, dicyclohexyl-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate, dibenzyl-2,2 '-[hydroxyl two (methylene radical)] two-2-acrylate.These ether dipolymers can be a kind, also can be more than 2 kinds.

The ratio of the aforementioned ether dipolymer when obtaining aforementioned polymer (a) in the monomer component does not have particular restriction, but generally is the 2-60 weight % in the total monomer composition, preferably 5-55 weight %, 5-50 weight % preferably again.When the amount of ether dipolymer is too many, when polymerization, be difficult to obtain low-molecular-weight polymkeric substance, or easily gelation, and very little the time, the film performance of the transparency and thermotolerance etc. is possible insufficient.

Aforementioned polymer (a) preferably has the polymkeric substance of acidic group.Therefore, the curable resin composition that makes can become the curable resin composition of the crosslinking reaction (hereinafter to be referred as " acid-curable epoxide ") that can utilize acidic group and epoxy reaction to generate ester bond or become the composition that uncured portion can be developed in alkaline developer.Do not have particular restriction as aforementioned acidic group, for example, can enumerate carboxyl, phenol hydroxyl, acid anhydride etc.These acidic groups can be a kind, also can be more than 2 kinds.

To in aforementioned polymer (a), introduce acidic group, for example, at least a kind of monomer that is selected from the monomer that can give acidic group after the monomer of acidic group and the polymerization (following claim sometimes " introducing the monomer that acidic group is used ") can be carried out polymerization as monomer component.In addition, when the monomer that can give acidic group after the polymerization was introduced acidic group as monomer component, it was necessary for example giving the processing that this acidic group described later uses after the polymerization.

As the monomer that aforementioned acidic group is arranged, for example, can enumerate (methyl) vinylformic acid or methylene-succinic acid etc. has the monomer of carboxyl, N-hydroxy phenyl maleimide etc. to have monomer, maleic anhydride or the itaconic anhydride etc. of phenol hydroxyl that monomer of acid anhydride etc. is arranged, (methyl) vinylformic acid most preferably among these.As the monomer that can give acidic group after the aforementioned polymerization, for example, can enumerate (methyl) vinylformic acid 2-hydroxy methacrylate etc. and have the monomer of hydroxyl, (methyl) glycidyl acrylate etc. has the monomer of epoxy group(ing), (methyl) vinylformic acid 2-ethyl isocyanate etc. that monomer of isocyanate group etc. is arranged.Introducing the monomer that these acidic groups are used, can be a kind, also can be more than 2 kinds.

Monomer component when obtaining aforementioned polymer (a) also contains when introducing the monomer that aforementioned acidic group uses, and this is monomeric to contain the proportional particular restriction that do not have, and can be 5-70 weight %, 10-60 weight % preferably in the total monomer composition.

Aforementioned polymer (a) preferably has the polymkeric substance of free-radical polymerised pair of key.Therefore, aforementioned polymer (a) becomes compound (b1) with free-radical polymerised pair of key of aftermentioned or the polymkeric substance that becomes double cure component (b).

In aforementioned polymer (a), introduce free-radical polymerised pair of key, for example, after the monomer (following title " introducing the free-radical polymerised pair of monomer that key is used " sometimes) that can give free-radical polymerised pair of key after the polymerization can being carried out polymerization as monomer component, give this as described later free-radical polymerised pair of processing that key is used.

As the monomer that can give free-radical polymerised pair of key after the aforementioned polymerization, for example, can enumerate the monomer that (methyl) vinylformic acid, methylene-succinic acid etc. have carboxyl; Maleic anhydride, itaconic anhydride etc. have acid anhydride's monomer; (methyl) glycidyl acrylate, (methyl) vinylformic acid 3,4-epoxy group(ing) cyclohexyl methyl esters, neighbour-(or-or right-) vinyl benzyl glycidyl ether etc. has the monomer of epoxy group(ing) etc.These introduce the free-radical polymerised pair of monomer that key is used, and can be a kind, also can be more than 2 kinds.

When the monomer component of system aforementioned polymer when (a) also contained the monomer of introducing aforementioned free-radical polymerised pair of key, this is monomeric to contain the proportional particular restriction that do not have, but can be 5-70 weight % in the total monomer composition, 10-60 weight % preferably.

Aforementioned polymer (a) preferably has the polymkeric substance of epoxy group(ing).Therefore, aforementioned polymer (a) becomes the compound (b2) that the aftermentioned epoxy group(ing) is arranged, and also becomes the polymkeric substance of double cure component (B).

In aforementioned polymer (a), introduce epoxy group(ing), for example, can will have the monomer (following claim sometimes " monomer that the introducing epoxy group(ing) is used ") of epoxy group(ing) to carry out polymerization as monomer component.

As the monomer that aforementioned epoxy group(ing) is arranged, for example, can enumerate (methyl) glycidyl acrylate, (methyl) vinylformic acid 3,4-epoxy group(ing) cyclohexyl methyl esters, neighbour-(or-or right-) the vinyl benzyl glycidyl ether etc.These introduce the monomer that epoxy group(ing) is used, and can be a kind, also can be more than 2 kinds.

When the monomer component of system aforementioned polymer when (a) also contained the monomer that aforementioned introducing epoxy group(ing) uses, this is monomeric to contain the proportional particular restriction that do not have, and can be 7-70 weight %, 10-60 weight % preferably in the total monomer composition.

Monomer component during system aforementioned polymer (a), except as aforementioned ether dipolymer that must composition and introduce monomer that aforementioned acidic group uses, introduce monomer that free-radical polymerised pair of key use, the monomer that the introducing epoxy group(ing) is used, but can also contain the monomer of other copolymerization as required.

But monomer as aforementioned other copolymerization, for example, can enumerate (methyl) esters of acrylic acid of (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, isopropyl methacrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, the different Fo Er ester of (methyl) vinylformic acid, (methyl) vinylformic acid DCPA, (methyl) vinylformic acid 2-hydroxy methacrylate etc.; The aromatic ethenyl compound of vinylbenzene, Vinyl toluene, alpha-methyl styrene etc.; The N-substituted maleimide of N-phenylmaleimide, N-cyclohexyl maleimide etc.; The divinyl of divinyl, isoprene etc. or replacement adiene cpd; The ethene or the substituted vinyl compound of ethene, propylene, vinylchlorid, vinyl cyanide etc.; The vinyl ester of vinyl acetate etc. etc.Consider preferred (methyl) methyl acrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, the different Fo Er ester of (methyl) vinylformic acid, (methyl) vinylformic acid DCPA, vinylbenzene among these from the stable on heating viewpoint of the good and difficult destruction of the transparency.But other monomers of these copolymerization can also can use more than 2 kinds together only with a kind.

System aforementioned polymer (a) but the time monomer component when also containing other monomers of aforementioned copolymerization, this is monomeric to contain the proportional particular restriction that do not have, preferred 95 weight % are following, more preferably below the 85 weight %.

Aforementioned polymer (a) can easily make by carrying out polymerization to the aforementioned ether dipolymer of major general as necessary aforementioned monomer composition.At this moment, side by side carry out the cyclization formation tetrahydrofuran (THF) ring structure of ether dipolymer with polymerization.

Method as aforementioned monomer composition polyreaction does not have particular restriction, can adopt over known various polymerization process, but most preferably adopts solution polymerization process.In addition, polymerization temperature and polymerization concentration (polymerization concentration=[gross weight of monomer component/(gross weight+weight of solvent of monomer component)] * 100) are according to the kind or the ratio of employed monomer component, the molecular weight of desired polymkeric substance and difference, preferable polymerization temperature 40-150 ℃, polymerization concentration 5-50%, preferable polymerization temperature 60-130 ℃ again, polymerization concentration 10-40%.

Use the occasion of solvent in the polymerization of aforementioned monomer composition, can use the solvent that uses in the common Raolical polymerizable as solvent.Particularly, for example, can enumerate the ethers of tetrahydrofuran (THF), dioxan, glycol dimethyl ether, diethylene glycol dimethyl ether etc.; The ketone of acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone etc.; The ester class of vinyl acetic monomer, N-BUTYL ACETATE, propylene glycol methyl ether acetate, 3-methoxyl group butylacetic acid ester etc.; The alcohols of methyl alcohol, ethanol, Virahol, propyl carbinol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether etc.; Toluene, dimethylbenzene, ethylbenzene etc. aromatic hydrocarbon based; Chloroform, methyl-sulphoxide etc.These solvents can also can use more than 2 kinds together only with a kind.

As aforementioned solvents, most preferably the solvency power to the polymkeric substance (a) that generates is strong according to the kind of employed monomer component or ratio, this kind solvent that the viscosity of polymer fluid is low.Contain in the monomer component polymerization of ether dipolymer, the part of ether dipolymer is not carried out cyclopolymerization and is caused crosslinking reaction sometimes, surpasses a certain amount ofly if carry out the amount of the ether dipolymer of crosslinking reaction, then causes unusual polymer to quantize or gelation sometimes.Because the high more easy more crosslinking reaction that causes the ether dipolymer of viscosity of polymer fluid,, can suppress the crosslinking reaction of ether dipolymer or prevent that polymer from quantizing or gelation so the viscosity of polymer fluid is reduced by selective solvent suitably.For example, when having the monomer of aforementioned acidic group to make the polymkeric substance of acidic group as monomer component, for example, part or all of aforementioned solvents used the alcohols of the ethers, Virahol of Diethylene Glycol or dme etc. etc., then can be with the polymer fluid lowering viscousity.In addition, though the solvent that uses during by aforesaid benchmark selective polymerization, but the occasion that the solution of employed solvent different solvents is wished to get polymkeric substance (a) during as final and this polymerization, can use the mixed solvent of solvent of selecting by aforementioned benchmark and the needed solvent of finally wishing to get of solution to carry out heating up in a steamer the solvent of selecting by aforementioned benchmark after the polymerization.For example, use the alcohols of Virahol etc. or ethers as solvent during polymerization, when finally wishing to get polymkeric substance (a) as the ester class solution of propylene glycol methyl ether acetate etc., for example, can use the mixed solvent of propylene glycol methyl ether acetate and Virahol to carry out after the polymerization, heat up in a steamer Virahol, become propylene glycol methyl ether acetate solution.

When the aforementioned monomer composition is carried out polymerization, can also add normally used polymerization starter as required.There is not particular restriction as polymerization starter, for example, can enumerate the organo-peroxide of hydrogen phosphide cumene, hydrogen peroxide diisopropyl benzene, di-t-butyl peroxide, peroxidation lauryl, benzoyl peroxide, peroxidation carbonic acid tertiary butyl isopropyl ester, peroxidation caproic acid tert-pentyl-2-ethyl ester, the peroxidation caproic acid tertiary butyl-2-ethyl ester etc.; 2,2 '-azo two (isopropyl cyanide), 1,1 '-azo two (cyclohexanenitrile), 2,2 '-azo two (2, the 4-methyl pentane nitrile), dimethyl 2, the azo-compound of 2 '-azo two (2 Methylpropionic acid ester) etc. etc.These polymerization starters can also can use more than 2 kinds together only with a kind.In addition, the usage quantity of polymerization starter, can suitably set according to molecular weight of used monomeric combination or reaction conditions, desired polymkeric substance etc., there is not particular determination, but never produce gelation, can make the thousands of viewpoints to tens thousand of polymkeric substance of weight-average molecular weight and consider, be 0.1-15 weight %, 0.5-10 weight % more preferably with respect to the total monomer composition.

When the aforementioned monomer composition is carried out polymerization,, also can add normally used chain-transfer agent as required in order to regulate molecular weight.As chain-transfer agent, for example, can enumerate the mercaptan tethers transfer agent, α-Jia Jibenyixierjuwu of n-dodecane mercaptan, mercaptoacetic acid, mercaptoacetic acid methyl esters, 3-thiohydracrylic acid, 3-mercapto-propionate etc. etc., but preference chain transfer effect height, n-dodecane mercaptan, mercaptoacetic acid, the 3-thiohydracrylic acid that can reduce residual monomer, obtain easily.Use the occasion of chain-transfer agent, the usage quantity of this chain-transfer agent can suitably be set according to molecular weight of used monomeric combination or reaction conditions, desired polymkeric substance etc., there is not particular determination, but never produce gelation, can obtain the thousands of viewpoints to tens thousand of polymkeric substance of weight-average molecular weight and consider, be 0.1-15 weight %, 0.5-10 weight % more preferably with respect to the total monomer composition.

In the aforementioned polyreaction, though consider to carry out simultaneously the cyclization of ether dipolymer, it is 100 moles of % that the cyclisation rate of the ether dipolymer of this moment not necessarily needs.

The system aforementioned polymer is used the monomer that can give aforementioned acidic group as monomer component when (a), introduces the occasion of acidic group therefrom, the processing that must give acidic group in the laggard behavior of polymerization.For used monomeric kind difference of giving acidic group is complied with in the processing of giving acidic group, for example, when using this monomer that hydroxyl arranged of (methyl) vinylformic acid 2-hydroxy methacrylate, for example, can make succinyl oxide, Tetra Hydro Phthalic Anhydride, the acid anhydrides of maleic anhydride etc. carries out addition, use (methyl) when glycidyl acrylate etc. has the monomer of epoxy group(ing), for example, can make N-methylamino phenylformic acid, N-amino methyl phenol etc. has the compound of amino and acidic group to carry out addition, perhaps, for example make the hydroxyl that produces after this sour addition of (methyl) vinylformic acid, with for example succinyl oxide, Tetra Hydro Phthalic Anhydride, the acid anhydrides of maleic anhydride etc. carries out addition, when use (methyl) vinylformic acid 2-ethyl isocyanate etc. has the monomer of isocyanate group, for example, can make 2-hydroxybutyric acid etc. have the compound of hydroxyl and acidic group to carry out addition.

The system aforementioned polymer is used the monomer that can give aforementioned free-radical polymerised pair of key as monomer component when (a), introduces the occasion of free-radical polymerised pair of key thus, the processing that must give free-radical polymerised pair of key in the laggard behavior of polymerization.For giving the processing of free-radical polymerised pair of key, according to used monomeric kind of giving free-radical polymerised pair of key and difference, for example, when using (methyl) vinylformic acid or methylene-succinic acid etc. that the monomer of carboxyl is arranged, can make (methyl) glycidyl acrylate, (methyl) vinylformic acid 3,4-epoxy group(ing) cyclohexyl methyl esters, adjacent-(or-, or right-) vinyl benzyl glycidyl ether etc. has the compound of epoxy group(ing) and free-radical polymerised pair of key to carry out addition, when using maleic anhydride or itaconic anhydride etc. that the monomer of carboxylic acid anhydride is arranged, can make (methyl) vinylformic acid 2-hydroxy methacrylate etc. have the compound of hydroxyl and free-radical polymerised pair of key to carry out addition, use (methyl) glycidyl acrylate, (methyl) vinylformic acid 3,4-epoxy group(ing) cyclohexyl methyl esters, adjacent-(or-, or right-) when vinyl benzyl glycidyl ether etc. has the monomer of epoxy group(ing), can make (methyl) vinylformic acid etc. have the compound of acidic group and free-radical polymerised pair of key to carry out addition.

The weight-average molecular weight of aforementioned polymer (a) does not have particular restriction, but 2000-200000 preferably is more preferably 5000-100000.Weight-average molecular weight surpasses at 200000 o'clock, and viscosity is too high-leveled and difficult films with formation, and during less than 2000, exists to be difficult to present abundant stable on heating tendency.

Aforementioned polymer (a) has the occasion of acidic group, acid number preferably 30-500mg KOH/g, be more preferably 50-400mg KOH/g.During the acid number of polymkeric substance (a) is not enough 30mg KOH/g, be difficult to use in alkali develops, when surpassing 500mg KOH/g, the too high existence of viscosity is difficult to form the tendency of filming.

Curable resin composition of the present invention, as component of polymer (A), as long as aforementioned polymer (a) is must, except that aforementioned polymer (a), also can be for example to contain, the known polymkeric substance of past that (methyl) acrylic resin, phenylethylene resin series, butadiene-based resin etc., common curable resin composition use.In addition, when also containing in addition polymkeric substance of aforementioned polymer (a), aforementioned polymer (a) shared amount in component of polymer (A) is preferably more than the 50 weight %.

Curable resin composition of the present invention is from compound that free-radical polymerised pair of key arranged (b1) and the resin combination of the cure component (B) that at least a kind of formation selecting the compound (b2) of epoxy group(ing) is arranged as necessary composition.Therefore, curable resin composition of the present invention can present good solidified nature.At length say, as aforementioned cure component (B) is the occasion that contains the compound (b1) with free-radical polymerised pair of key, curable resin composition of the present invention becomes the composition that adopts radical polymerization to be cured, for containing the occasion of the compound (b2) with epoxy group(ing), curable resin composition of the present invention becomes the composition that adopts cationoid polymerisation or acid-curable epoxide to be cured as aforementioned cure component (B).

As the aforementioned compound (b1) that free-radical polymerised pair of key arranged, oligopolymer and monomer are arranged, as oligopolymer, for example can enumerate unsaturated polyester, acrylic acid epoxy ester, urethane acrylate, polyester acrylate, side chain acrylic acid polymer of two keys etc. is arranged, as monomer, for example can enumerate the aromatic vinyl base system monomer of vinylbenzene, alpha-methyl styrene, alpha-chloro vinylbenzene, Vinyl toluene, Vinylstyrene, Phthalic acid, diallyl ester, phosphoric acid benzene diallyl etc.; The vinyl ester monomers of vinyl acetate, hexanedioic acid vinyl ester etc.; (methyl) acrylic monomer of (methyl) methyl acrylate, (methyl) vinylformic acid 2-hydroxy methyl, (methyl) vinylformic acid (2-oxygen-1,3-dioxolanyl-4-yl)-methyl esters etc.; Two (methyl) vinylformic acid binaryglycol ester, two (methyl) vinylformic acid propylene glycol ester, two (methyl) vinylformic acid trihydroxymethylpropanyl ester, three (methyl) vinylformic acid trihydroxymethylpropanyl ester, two (methyl) vinylformic acid pentaerythritol ester, three (methyl) vinylformic acid pentaerythritol ester, four (methyl) vinylformic acid pentaerythritol ester, two (methyl) vinylformic acid dipentaerythritol ester, three (methyl) vinylformic acid dipentaerythritol ester, four (methyl) vinylformic acid dipentaerythritol ester, five (methyl) vinylformic acid dipentaerythritol ester, six (methyl) vinylformic acid dipentaerythritol ester, multifunctional (methyl) acrylate of three (methyl) vinylformic acid three (hydroxyethyl) isocyanuric acid ester etc.; Triallyl isocyanurate; This (methyl) acrylic acid epoxy ester of (methyl) vinylformic acid and Resins, epoxy addition etc.

The aforementioned compound (b1) that free-radical polymerised pair of key arranged is proportional containing in curable resin composition of the present invention, and with respect to aforementioned polymer composition (A), preferred 5-1000 weight % is more preferably 10-600 weight %.

As aforementioned the compound (b2) of epoxy group(ing), for example arranged, (commercially available product, for example エ ピ コ one ト 828, エ ピ コ one ト 1001, エ ピ コ one ト 1002, エ ピ コ one ト are more than 1004 can to enumerate bisphenol A type epoxy resin, oiling Shell epoxy system etc.), bisphenol f type epoxy resin (commercially available product, for example エ ピ コ one ト 807, EP4001, EP-4002, more than the EP-4004, oiling Shell epoxy system etc.), phenol lacquer resins type Resins, epoxy (commercially available product, for example more than the EPPN-201, Japanese chemical drug system; EP-152, more than the EP-154, oiling Shell epoxy system; More than the DEN-438, Dow Chemical system etc.), cresols lacquer resins type Resins, epoxy (commercially available product, for example EOCN-102S, EOCN-1020, more than the EOCN-104S, Japan's chemical drug system etc.), tris-phenol type Resins, epoxy (commercially available product, for example EPPN-501, EPPN-502, more than the EPPN-503, Japanese chemical drug system etc.), alicyclic epoxy resin (commercially available product, for example セ ロ キ サ イ De 2021P, more than the セ ロ キ サ イ De EHPE, ダ イ セ Le chemical industry system etc.).Copolymerization mould assembly Resins, epoxy (commercially available product, for example CP-15, CP-30, CP-50M, more than the CP-20MA, Japan's grease system etc.), fluorenes Resins, epoxy (commercially available product, ESF-300 Nippon Steel chemistry system etc. for example), triglycidyl isocyanurate (commercially available product, TEPIC daily output chemistry system etc. for example), phenylbenzene glycidyl ether (commercially available product, for example YX-4000 oiling Shell epoxy system etc.) etc.

The aforementioned compound (b2) that epoxy group(ing) arranged is proportional containing in curable resin composition of the present invention, with respect to the preferred 5-1000 weight % of aforementioned polymer composition (A), be more preferably 10-600 weight %.

In the curable resin composition of the present invention, when aforementioned cure component (B) is the compound (b1) that free-radical polymerised pair of key arranged, also preferably contain be selected from optical free radical propellant (c1) and the hot radical propellant (c2) at least a kind as polymerization starter (C).At length say, when containing optical free radical propellant (c1) as polymerization starter (C), curable resin composition of the present invention for example by the luminous energy of irradiation ultraviolet radiation etc., becomes and can adopt radical polymerization to carry out the composition of photocuring (this scheme is as scheme (i)).At this moment, especially aforementioned polymer (a) is when the polymkeric substance of acidic group is arranged, and curable resin composition of the present invention for example can be suitable for making colour filter or optical waveguide etc. as alkali developable minus erosion resistant.And when containing hot radical propellant (c2) as polymerization starter (C), curable resin composition of the present invention by giving heat energy, becomes the composition (this scheme as scheme (ii)) that can adopt radical polymerization to carry out thermofixation.Scheme (i), scheme (ii) also can use respectively optical free radical propellant (c1) and hot radical propellant (c2) both as polymerization starter.In addition, when aforementioned cure component (B) is the compound (b1) that free-radical polymerised pair of key arranged, even do not conform to the occasion that aforementioned polymerization starter (C) arranged, curable resin composition of the present invention, by giving the high energy radioactive rays energy of x ray, electron beam etc., or give heat energy and become and to adopt radical polymerization and cured compositions (this scheme as scheme (iii)).

As aforementioned lights free radical generating agent (c1), for example, can enumerate the benzoin and the alkyl ether thereof of benzoin, benzoin methyl ether, benzoin ether etc.; Methyl phenyl ketone, 2,2-dimethoxy-2-phenyl methyl phenyl ketone, 1, the acetophenones of 1-dichloroacetophenone etc.; The anthraquinone class of 2-methylanthraquinone, 2-amyl anthraquinone, 2-tertiary butyl anthraquinone, 1-chloroanthraquinone etc.; 2,4-dimethyl thioxanthone, 2, the thioxanthene ketone of 4-di-isopropyl thioxanthone, 2-clopenthixal ketone etc.; The ketal class of acetyl benzophenone dimethyl ketal, benzyl dimethyl ketal etc.; The benzophenone of benzophenone etc.; 2-methyl isophthalic acid-[4-(methyl sulphur) phenyl]-2-morpholino-acetone-1 or 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1; Acylphosphine oxide class and xanthones etc.

Curable resin composition of the present invention contains the occasion of aforementioned lights free radical generating agent (c1), and should (c1) contain is proportional, with respect to the preferred 0.1-50 weight of the total amount % of component of polymer (A) and cure component (B), be more preferably 0.5-30 weight %.

As aforementioned hot free radical generating agent (c2), for example, can enumerate the organo-peroxide of hydrogen phosphide cumene, dicumyl peroxide, di-t-butyl peroxide, peroxidation lauryl, benzoyl peroxide, peroxidation carbonic acid tertiary butyl isopropyl ester, the peroxidation caproic acid tertiary butyl-2-ethyl ester, peroxidation caproic acid tert-pentyl-2-ethyl ester etc.; 2,2 '-azo two (isopropyl cyanide), 1,1 '-azo two (cyclohexanenitrile), 2,2 '-azo two (2, the 4-methyl pentane nitrile), dimethyl 2, the azo-compound of 2 '-azo (2 Methylpropionic acid ester) etc. etc.

Curable resin composition of the present invention contains the occasion of aforementioned hot free radical generating agent (c2), is somebody's turn to do containing of (c2) of proportional total amount with respect to component of polymer (A) and cure component (B), and preferably 0.1-50 weight % is more preferably 0.5-30 weight %.

In the curable resin composition of the present invention, aforementioned cure component (B) is the occasion of compound (c2) that epoxy group(ing) is arranged, preferably also contains be selected from light acid propellant (c3) and the hot acid propellant (c4) at least a kind as polymerization starter (C).At length say, contain light acid propellant (c3) and be the occasion of polymerization starter (C), curable resin composition of the present invention for example by the luminous energy of irradiation ultraviolet radiation etc., becomes and can adopt cationoid polymerisation to carry out the composition (this scheme as scheme (iv)) of photocuring.At this moment, especially aforementioned polymer (a) is when the polymkeric substance of acidic group is arranged, and curable resin composition of the present invention is as alkali developable minus erosion resistant, for example applicable to making colour filter or optical waveguide etc.And contain the occasion of hot acid propellant (c4) as polymerization starter, and curable resin composition of the present invention, by giving heat energy, (this scheme is as scheme (v)) to become the composition that can adopt cationoid polymerisation to carry out thermofixation.Scheme (iv), scheme (v), also can use respectively light acid propellant (c3) and hot acid propellant (c4) both as polymerization starter.In addition, aforementioned cure component (B) is the occasion of compound (b2) that epoxy group(ing) is arranged, even do not contain the occasion of aforementioned polymerization starter (C), aforementioned polymer (a) is the polymkeric substance that acidic group is arranged, perhaps also contain the multifunctional occasion that contains the compound of acidic group or also contain the polymkeric substance of acidic group of trimellitic acid, trimellitic acid 1,2-anhydride, methyl methacrylate/Sipacril 2739OF, phenylethylene/maleic anhydride copolymer and so on, curable resin composition of the present invention, (this scheme is as scheme (vi)) by giving the composition that heat energy becomes acid-curable epoxide.

As aforementioned lights acid-producing agent (c3), for example, can enumerate the diaryl group iodized salt class of phenylbenzene iodine trifluoroacetate, phenylbenzene iodine trifluoro-methanyl sulfonate, 4-p-methoxy-phenyl benzene iodine trifluoro-methanyl sulfonate, 4-p-methoxy-phenyl benzene iodine trifluoroacetate etc.; The triaryl matte salt of triphenylsulfonium trifluoro-methanyl sulfonate, triphenylsulfonium trifluoroacetate, 4-p-methoxy-phenyl hexichol sulfonium trifluoro-methanyl sulfonate, 4-p-methoxy-phenyl hexichol sulfonium trifluoroacetate, 4-phenyl thio-phenyl phenylbenzene trifluoro-methanyl sulfonate, 4-phenyl thio-phenyl phenylbenzene trifluoroacetate etc. etc.

Curable resin composition of the present invention contains the occasion of aforementioned lights acid-producing agent (c3), and should (c3) contain is proportional with respect to the total amount of component of polymer (A) with cure component (B), preferably 0.1-50 weight %, be more preferably 0.5-30 weight %.

As aforementioned hot acid-producing agent (c4), for example, can enumerate the salt of sulfonium salt, benzothiazolium salt, ammonium salt, phosphonium salt etc. etc., wherein, most preferably sulfonium salt and benzothiazolium salt.Concrete example as sulfonium salt and benzothiazolium salt, for example, can enumerate 4-acetoxyl group phenyl dimethyl sulfonium hexafluoro antimonate, benzyl-4-hydroxy phenyl methyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl benzyl methyl sulfonium hexafluoro antimonate, dibenzyl-4-hydroxy phenyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl benzyl sulfonium hexafluoro antimonate, 3-benzyl benzothiazole hexafluoro antimonate etc.In addition, these hot acid propellants also can play the light acid propellant effect.

Curable resin composition of the present invention contains the occasion of aforementioned hot acid-producing agent (c4), and should (c4) contain proportionally measured preferably 0.1-50 weight %, is more preferably 0.5-30 weight % with respect to the component of polymer (A) and the total of cure component (B).

Curable resin composition of the present invention also can contain the solvent as thinner as required.

As aforementioned solvents, so long as with aforementioned polymer composition (A), cure component (B) and make it each composition uniform dissolution of the polymerization starter (C) that contains as required and then do not have particular restriction with the solvent of each composition reaction.Particularly, for example, can enumerate the ethers of tetrahydrofuran (THF), three alkane, glycol dimethyl ether, diethylene glycol dimethyl ether etc.; The ketone of acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone etc.; The ester class of ethyl acetate, butylacetate, propylene glycol methyl ether acetate, 3-methoxyl group butylacetic acid ester etc.; The alcohols of methyl alcohol, ethanol, Virahol, propyl carbinol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether etc.; Toluene, dimethylbenzene, ethylbenzene etc. aromatic hydrocarbon based; Chloroform, methyl-sulphoxide etc.In addition, the amount of solvent can suitably be set by the optimum viscosity when using resin combination.

Curable resin composition of the present invention, except aforementioned polymer composition (A), aforementioned cure component (B), aforementioned polymerization starter (C), aforementioned solvents, so long as in the scope of not destroying effect of the present invention, also can contain for example aluminium hydroxide, talcum powder, clay, barium sulfate etc. weighting agent, dyestuff, pigment, defoamer, coupling agent, be coated with known additives such as flat agent, sensitizer, releasing agent, lubricant, softening agent, oxidation inhibitor, UV light absorber, fire retardant, polymerization retarder, tackifier, dispersion agent.

Curable resin composition of the present invention, can by will as aforementioned polymer composition (A) that must composition and aforementioned cure component (B) (but, as previously mentioned, aforementioned polymer (a) is the occasion of double cure component (B) also, must composition only be component of polymer (A).) and make it the aforementioned polymerization starter (C) that contains or aforementioned solvents or other additive as required and mix equably and be prepared.

The curable resin composition transparency of the present invention, good heat resistance, for example applicable to the purposes of erosion resistant, various coating agent, coating etc., especially polymkeric substance (a) has the occasion of acidic group, can be suitable as the minus erosion resistant of making the alkali developable that colour filter or optical waveguide use and use.In addition, because the tetrahydrofuran (THF) ring structure in polymkeric substance (a) structure also has good pigment-dispersing, so applicable to the colour filter colored curable resin composition.

Colour filter of the present invention is the colour filter that is provided with curing resin layer on substrate, and the resin combination that forms aforementioned curing resin layer is aforementioned curable resin composition of the present invention.Aforementioned so-called colour filter is to have that image colorization is needed, have 3 natural colored fine patterns at least on the transparency carrier and distinguish the spectral filter of the black matrix sheet of these factors, as 3 primary colors, generally use red (R), green (G), blue (B).As the parts that constitute colour filter; 3 primary colors (RGB) picture element, resin black egative film, protective membrane, column spacer are arranged particularly; but colour filter of the present invention, at least 1 of each parts who constitutes this colour filter can be the parts that aforementioned curable resin composition is solidified to form.

Colour filter of the present invention; 3 primary colors (RGB) picture element and the curing resin layer that forms the resin black egative film; preferably by aforementioned schemes (i), (iv) in polymkeric substance (a) be to have the curable resin composition of the polymkeric substance occasion of acidic group to form; protective membrane and the curing resin layer that becomes column spacer; preferably by aforementioned schemes (i), (iii), (iv), (vi), polymkeric substance (a) is to have the curable resin composition of the polymkeric substance occasion of acidic group to form.In addition; the curable resin composition that forms RGB picture element occasion contains each 3 natural colored pigment of red, green, blue; the curable resin composition that forms resin black egative film occasion contains the pigment of black, and the curable resin composition that forms protective membrane or column spacer occasion can not contain pigment.Moreover contain the occasion of pigment, preferably contain dispersion agent.

Colour filter of the present invention for example, can be made as follows.

1) uses known apparatus for coating such as spinner, wire bar spreader, curtain flow coater, pattern spreader, roller coating machine, spraying machine, the curable resin composition that contains pigment is coated on glass, on the transparency carrier of preferred non-alkali glass, transparent plastics etc., dry, make and film.As drying conditions preferably room temperature～120 ℃, preferred 60 ℃～100 ℃ temperature, under 10 seconds～60 minutes preferred 30 seconds～10 minutes, normal pressure or vacuum, carry out the method for heat drying.

2) then, the photomask that is provided with the peristome that meets desired diagram shape (drawing film) is stated from above-mentioned top one-tenth contact condition or contactless state of filming, irradiates light makes it to solidify.Here, so-called light, not only visible light, also mean ultraviolet ray, x ray, the radioactive rays of electron beam etc., but most preferably the ultraviolet ray.As ultraviolet source, general preferred use high voltage mercury lamp.

3) after the rayed, in solvent, water, alkali aqueous solution etc., develop.Among these, preferred because alkali aqueous solution can carry out highly sensitive development less to the load of environment.As the alkali composition, preferred potassium hydroxide, sodium hydroxide, yellow soda ash etc.As alkali concn, preferred 0.01-5 weight %, preferred again 0.05-3 weight %, most preferably 0.1-1 weight %.The solvability of aforementioned curable resin composition might be not enough when alkali concn was lower than above-mentioned scope, and when being higher than above-mentioned scope on the contrary, the too high development property sometimes of solvency power is poor.In addition, also can add tensio-active agent in the alkali aqueous solution.

At first, use the curable resin composition contain black pigment to carry out above-mentioned 1)～3) operation, on substrate, form the resin black egative film.

Then, change the pigment of curable resin composition, repeat above-mentioned 1 by red (R), green (G), blue (B) order)～3) operation, form the picture element of R, G, B, make the RGB picture element.

Next, for the RGB picture element that forms on the protective substrate or in order to improve surface smoothing, can form protective membrane as required.

In addition, aforementioned colour filter is the occasion of liquid crystal indicator with colour filter, is preferably formed column spacer.Column spacer can be coated on curable resin composition the thickness that makes it to become desired spacer height on the face of this formation spacer, can be through above-mentioned 1)～3) operation make.

During the making colour filter, when making each parts, heat (back baking) after preferred the development and be cured again, and the occasion of residual solvent is preferably fully except that desolvating.The preferred 120-300 of temperature ℃, preferred 150-150 ℃, most preferably 180-230 ℃ again of when baking back.When back storing temperature was higher than said temperature, picture element was painted, or because of thermolysis might destroy the smoothness of filming, otherwise when being lower than said temperature, solidifying and lack, and coating strength might reduce.Back baking can be carried out after the development during each parts forms, and also can carry out after forming whole parts.

Display unit of the present invention is to use substrate to be provided with the display unit of the colour filter of curing resin layer, and the resin combination that forms aforementioned curing resin layer is aforementioned curable resin composition of the present invention.As the concrete example of display unit of the present invention, preferably enumerate liquid crystal indicator, but be not limited thereto, for example, also can be to use the display unit of organic EL etc.Below, the occasion as liquid crystal indicator is described.

The foregoing liquid crystal display unit, be to pack into to utilize the liquid crystal spacer to make aforementioned colour filter and the filter substrate that sets ITO electrode, alignment films as required, and set as required between the counter substrate of alignment films, ITO electrode, driving element and be held in certain intervals, in this interval, enclose liquid crystal material, utilize the orientation of electrical signal change liquid crystal, carry out the liquid crystal indicator of the colored LCD panel that shows by the transmitance that changes tunable optical.Mode of operation, type of drive as liquid crystal can be used known method, consider preferred TFT mode from the aspect of display quality, response speed etc.

As the foregoing liquid crystal spacer, can use the column spacer of known micropartical spacer, usability photosensitiveness resin formation etc., but the column spacer that preferably uses curable resin composition of the present invention to form.

Be equipped with the alignment films that adapts to each liquid crystal mode of operation, type of drive orientation on aforementioned filter substrate and the counter substrate, also establish fine projection (rib) as required, but preferably use alignment film of polyimide.In addition, rib also can use curable resin composition of the present invention except polyimide.In addition, in the outside of filter substrate and counter substrate, must dispose the mode of operation that is adapted to each liquid crystal, the deflector plate of type of drive, optical compensation films.

[embodiment]

Below, be described more specifically the present invention by embodiment, but the present invention is not subjected to these any qualifications.In addition, below short of specified otherwise, then " part " expression " weight part ", " % " expression " weight % ".

Analysis in each synthesis example, the comparison synthesis example is carried out as described below.

(weight-average molecular weight)

Use gel permeation chromatography device (the clear and electrician's system of Shodex GPC System-21H), measure by polystyrene conversion.

(polymer concentration in the polymers soln)

In the 1g polymers soln, add 4g acetone, make the seasoning at normal temperatures of dissolved solution, carry out again drying under reduced pressure (160 ℃/5mmHg) after 5 hours, in moisture eliminator, put cold, gravimetry.Then, calculate the non-volatile content of polymers soln by the weight reduction, as polymer concentration.

(acid number)

In the polymers soln of 0.5-1g, add 80mL acetone and 10mL water, stir and make it uniform dissolution, as titrating solution, use automatic titration device (the flat natural pond of COM-555 industry system) to carry out titration, the acid number of mensuration solution the KOH aqueous solution of 0.1mol/L.Then, the acid number of calculating polymkeric substance by the acid number and the polymer concentration of solution.

(synthesis example 1)

The removable flask of preparing the band cooling tube is as reactive tank, in addition, preparation is with dimethyl-2,40 parts of 2 '-[hydroxyl two (methylene radical)] two-2-acrylate (to call " MD " in the following text), 40 parts of methacrylic acids (to call " MAA " in the following text), 120 parts of methyl methacrylates (to call " MMA " in the following text), the peroxidation caproic acid tertiary butyl-2-ethyl ester (4 parts of Japanese grease systems (Perbutyl O is to call " PBO " in the following text), 40 parts of grooves that fully mix of propylene glycol methyl ether acetate (to call " PGMEA " in the following text) are prepared 8 parts in n-dodecane mercaptan (to call " D-DM " in the following text) as the monomer dropping groove, the groove that PGMEA32 part fully mixes drips groove as chain-transfer agent.

Add PGMEA395 part in reactive tank, nitrogen replacement back, the temperature that heats reactive tank with oil bath while stirring are raised to 90 ℃.The temperature-stable of reactive tank is after 90 ℃, and beginning drips groove by monomer dropping groove and chain-transfer agent and drips.Drip the limit and make temperature remain on 90 ℃, carried out with 135 minutes respectively on the limit.Drip and finish to begin after back 60 minutes to heat up, make the reactive tank temperature reach 110 ℃.Keep 110 ℃ after 3 hours, on removable flask, set up gas introduction tube, begin logical oxygen/nitrogen=5/95 (V/V) gas mixture.Then, in reactive tank, add 70 parts in methyl propenoic acid glycidyl ether (to call " GMA " in the following text), 2,0.4 part of 2 '-methylene radical two (4-methyl-6-tert butyl phenol) (to call " MBMTB " in the following text), 0.8 part of triethylamine (to call " TEA " in the following text) directly reacted 12 hours down at 110 ℃.Add PGMEA150 part cool to room temperature then, make the polymers soln of concentration 30%.The weight-average molecular weight of polymkeric substance is 18000, and acid number is 2mg KOH/g.

(synthesis example 2)

The removable flask of preparing the band cooling tube is as reactive tank, in addition, the groove that preparation fully mixes MD40 part, GMA80 part, MMA80 part, PBO3 part, PGMEA40 part is as the monomer dropping groove, and the groove of preparing n-DM6 part, PGMEA24 part are fully mixed drips groove as chain-transfer agent.

Drip PGMEA403 part in reactive tank, after nitrogen replaced, the temperature that heats reactive tank with oil bath was raised to 90 ℃ while stirring.The temperature-stable of reactive tank is after 90 ℃, and beginning drips groove by monomer dropping groove and chain-transfer agent and drips.Drip the limit and make temperature remain on 90 ℃, carried out in 135 minutes respectively on the limit.Drip to finish that beginning after back 60 minutes heats up making the reactive tank temperature is 110 ℃.Keep 110 ℃ after 3 hours, cool to room temperature makes the polymers soln of concentration 30%.The weight-average molecular weight of polymkeric substance is 19000.

(synthesis example 3)

The removable flask of preparing the band cooling tube is as reactive tank, in addition, the groove that preparation fully mixes MD40 part, MAA32 part, MMA128 part, PBO3 part, PGMEA40 part is as the monomer dropping groove, and the groove of preparing n-DM6 part, PGMEA24 part are fully mixed drips groove as chain-transfer agent.

Add PGMEA403 part in reactive tank, after nitrogen replaced, the temperature that heats reactive tank with oil bath was raised to 90 ℃ while stirring.The temperature-stable of reactive tank begins to drip the groove dropping from monomer dropping groove and chain-transfer agent after 90 ℃.Dripping the limit makes temperature remain on 90 ℃, limit to carry out in 135 minutes respectively.Drip to finish that beginning after back 60 minutes heats up making the reactive tank temperature is 110 ℃.Keep 110 ℃ of 3 hours postcooling to room temperature, make the polymers soln of concentration 30%.The weight-average molecular weight of polymkeric substance is 17000, and acid number is 104mg KOH/g.

(synthesis example 4)

The removable flask of preparing the band cooling tube is as reactive tank, in addition, preparation is with MD40 part, MAA32 part, the groove that 80 parts of benzyl methacrylates (to call " BzMA " in the following text), MMA48 part, PBO3 part, PGMEA40 part fully mix is as the monomer dropping groove, preparation is with n-DM6 part, and the groove that PGMEA24 part fully mixes drips groove as chain-transfer agent.

Add PGMEA403 part in reactive tank, after nitrogen replaced, the temperature that heats reactive tank with oil bath was raised to 90 ℃ while stirring.The temperature-stable of reactive tank begins to drip the groove dropping from monomer dropping groove and chain-transfer agent after 90 ℃.Drip the limit and make temperature remain on 90 ℃, carried out in 135 minutes respectively on the limit.Drip to finish that beginning after 60 minutes heats up making the reactive tank temperature is 110 ℃.Keep 110 ℃ after 3 hours, cool to room temperature makes the polymers soln of concentration 30%.The weight-average molecular weight of polymkeric substance is 17000, and acid number is 104mg KOH/g.

(synthesis example 5)

The removable flask of preparing the band cooling tube is as reactive tank, in addition, preparation is with MD40 part, MAA32 part, the groove that 60 parts of cyclohexyl methacrylates (to call " CHMA " in the following text), MMA68 part, PBO3 part, PGMEA40 part fully mix is as the monomer dropping groove, preparation is with n-DM6 part, and the groove that PGMEA24 part fully mixes drips groove as chain-transfer agent.

Add PGMEA403 part in reactive tank, after nitrogen replaced, the temperature that heats reactive tank with oil bath was raised to 90 ℃ while stirring.The temperature-stable of reactive tank begins to drip the groove dropping from monomer dropping groove and chain-transfer agent after 90 ℃.Drip the limit and make temperature remain on 90 ℃, carried out in 135 minutes respectively on the limit.Drip to finish that beginning after 60 minutes heats up making the reactive tank temperature is 110 ℃.Keep 110 ℃ after 3 hours, cool to room temperature makes the polymers soln of concentration 30%.The weight-average molecular weight of polymkeric substance is 18000, and acid number is 104mg KOH/g.

(synthesis example 6)

The removable flask of preparing the band cooling tube is as reactive tank, in addition, the groove that preparation fully mixes MD40 part, MAA32 part, 50 parts of vinylbenzene (to call " St " in the following text), MMA78 part, PBO3 part, PGMEA40 part is as the monomer dropping groove, preparation is with n-DM6 part, and the groove that PGMEA24 part fully mixes drips groove as chain-transfer agent.

Add PGMEA403 part in reactive tank, after nitrogen replaced, the temperature that heats reactive tank with oil bath was raised to 90 ℃.The temperature-stable of reactive tank begins to drip the groove dropping from monomer dropping groove and chain-transfer agent after 90 ℃.Drip the limit and make temperature remain on 90 ℃, carried out in 135 minutes respectively on the limit.Drip to finish that beginning after 60 minutes heats up making the reactive tank temperature is 110 ℃.Keep 110 ℃ after 3 hours, cool to room temperature makes the polymers soln of concentration 30%.The weight-average molecular weight of polymkeric substance is 18000, and acid number is 104mg KOH/g.

(synthesis example 7)

The removable flask of preparing the band cooling tube is as reactive tank, in addition, preparation is with MD40 part, MAA60 part, BzMA80 part, MMA20 part, PBO4 part, 40 parts of grooves that fully mix of diethylene glycol dimethyl ether (to call " DMDG " in the following text) are as the monomer dropping groove, preparation is with n-DM8 part, and the groove that DMDG32 part fully mixes drips groove as chain-transfer agent.

Add DMDG395 part in reactive tank, after nitrogen replaced, the temperature that heats reactive tank with oil bath was raised to 90 ℃ while stirring.The temperature-stable of reactive tank begins to drip the groove dropping from monomer dropping groove and chain-transfer agent after 90 ℃.Drip the limit and make temperature remain on 90 ℃, carried out in 135 minutes respectively on the limit.Drip to finish that beginning after 60 minutes heats up making the reactive tank temperature is 110 ℃.Keep 110 ℃ after 3 hours, on removable flask, set up gas introduction tube, begin logical oxygen/nitrogen=5/95 (v/v) gas mixture.Then, in reactive tank, add GMA56 part, MBMTB0.4 part, TEA0.8 part, directly 110 ℃ of reactions 9 hours.Add DMDG128 part cool to room temperature then, make the polymers soln of concentration 30%.The weight-average molecular weight of polymkeric substance is 16000, and acid number is 70mg KOH/g.

(synthesis example 8)

The removable flask of preparing the band cooling tube is as reactive tank, in addition, preparation is with MD60 part, MAA62 part, BzMA78 part, PBO3 part, PGMEA30 part, 30 parts of grooves that fully mix of Virahol (to call " IPA " in the following text) are as the monomer dropping groove, and the groove of preparing 4.4 parts of 3-thiohydracrylic acids, PGMEA15 part, IPA15 part are fully mixed drips groove as chain-transfer agent.

Add PGMEA189 part and IPA189 part in reactive tank, nitrogen heats to IPA with oil bath while stirring and refluxes after replacing.After refluxing, IPA begins to drip the groove dropping from monomer dropping groove and chain-transfer agent.Drip the limit and keep making IPA to reflux, carried out with 135 minutes respectively on the limit.Drip to finish that beginning after 60 minutes heats up heats up in a steamer IPA, reactive tank stops to heat up in a steamer IPA to 110 ℃ the moment, and IPA was refluxed 90 minutes.On removable flask, set up gas introduction tube then, begin logical oxygen/nitrogen=5/95 (v/v) gas mixture.Then, in reactive tank, add GMA68 part, MBMTB0.4 part, TEA0.8 part, directly under IPA refluxes, reacted 9 hours.Then, add PGMEA210 part, after IPA was heated up in a steamer in decompression, cool to room temperature made the polymers soln of concentration 37%.The weight-average molecular weight of polymkeric substance is 13500, and acid number is 72mg KOH/g.

(synthesis example 9)

The removable flask of preparing the band cooling tube is as reactive tank, in addition, the groove that preparation fully mixes MD40 part, MAA60 part, CHMA60 part, MMA40 part, PBO4 part, DMDG40 part is as the monomer dropping groove, and the groove of preparing n-DM8 part, DMDG32 part are fully mixed drips groove as chain-transfer agent.

Add DMDG395 part in reactive tank, after nitrogen replaced, the temperature that heats reactive tank with oil bath was raised to 90 ℃ while stirring.The temperature-stable of reactive tank begins to drip the groove dropping from monomer dropping groove and chain-transfer agent after 90 ℃.Drip the limit and make temperature remain on 90 ℃, carried out at 135 minutes respectively on the limit.Drip to finish that beginning after 60 minutes heats up making the reactive tank temperature is 110 ℃.Keep 110 ℃ after 3 hours, on removable flask, set up gas introduction tube, begin logical oxygen/nitrogen=5/95 (v/v) gas mixture.Then, add GMA56 part, MBMTB0.4 part, TEA0.8 part,, then, add DMDG128 part cool to room temperature, make the polymers soln of concentration 30% directly 110 ℃ of reactions 9 hours.The weight-average molecular weight of polymkeric substance is 17000, and acid number is 70mg KOH/g.

(synthesis example 10)

The removable flask of preparing the band cooling tube is as reactive tank, in this reactive tank, add PGMEA467 part, MD40 part, GMA80 part, MAA32 part, St30 part, MMA18 part, dimethyl 2, (pure pharmaceutical worker already makes V-65 to 2 '-azo two (2, the 4-methyl pentane nitrile) with light; To call " V-65 " in the following text) 20 parts, nitrogen fully mixes after replacing, and then, with the oil bath heating temperature of reactive tank is raised to 70 ℃ while stirring.After this temperature kept 3 hours, cool to room temperature made the polymers soln of concentration 30%.The weight-average molecular weight of polymkeric substance is 21000, and acid number is 104mgKOH/g.

(relatively synthesis example 1)

Except MD being made into N-phenylmaleimide (to call " PMI " in the following text), other and synthesis example 1 similarly make the polymers soln of concentration 30%.The weight-average molecular weight of polymkeric substance is 13000, and acid number is 2mg KOH/g.

(relatively synthesis example 2)

Except changing MD into PMI respectively, the amount of PBO changes 2 parts, the amount of n-DM into and changes 4 into especially, and other and synthesis example 2 similarly make the polymers soln of concentration 30%.The weight-average molecular weight of polymkeric substance is 18000.

(relatively synthesis example 3)

Except changing MD into PMI respectively, the amount of PBO makes 2 parts, the amount of n-DM into and makes 4 into especially, and other and synthesis example 3 similarly make the polymers soln of concentration 30%.The weight-average molecular weight of polymkeric substance is 18000, and acid number is 104mg KOH/g.

(relatively synthesis example 4)

Make into 4 parts except the amount that respectively MD is made into α-(hydroxymethyl) methyl acrylate (to call " MHMA " in the following text), PBO makes 2 parts, the amount of n-DM into, other and synthesis example 3 similarly make polymers soln.But produce water and methyl alcohol during owing to the lactone cyclisation, and residual monomer is many, so the concentration of resulting polymers solution is 25%.The weight-average molecular weight of polymkeric substance is 17000, acid number is 85mg KOH/g.

(relatively synthesis example 5)

Except making MD40 part into BzMA80 part respectively, the amount of MMA makes 88 parts, the amount of PBO into and makes 2 parts, n-DM amount into and make 4 into especially, and other and synthesis example 3 similarly make the polymers soln of concentration 30%.The weight-average molecular weight of polymkeric substance is 20000, acid number is 105mg KOH/g.

＜embodiment 1-1 (scheme (i)) 〉

10 parts of polymers solns, 3 parts of five vinylformic acid dipentaerythritol ester (to call " DPPA " in the following text), optical free radical propellant " Irgacure " 907 Ciba-Geigy corporate systems that synthesis example 1 is made; To call " Irg 907 " in the following text) 0.09 part, PGMEA5 part mix equably, makes curable resin composition.

Use spinner the curable resin composition that makes to be coated on to make dried thickness on the non-alkali glass plate be 2 μ m,, use the ultrahigh pressure mercury lamp irradiation ultraviolet radiation to make irradiation dose be 200mJ/cm on the hot plate 80 ℃ down after dry 5 minutes ², making test film A, use-testing sheet A adopts following method to estimate light solidified.In addition, the reusable heat plate made test film B with afore-mentioned test sheet A in 1 hour 200 ℃ of heating, used the test film B that makes to adopt following method to estimate the transparency and thermotolerance.The results are shown in table 1.

The state that (light solidified) visual observation test film A films when flooding 1 minute in the tetrahydrofuran (THF) of room temperature is judged by following benchmark.

Zero: film do not peel off, *: film and peel off

(transparency) uses spectrophotometer (" UV-3100 " island Tianjin system) to measure the transmitance (%) of wavelength 380-800nm.

(thermotolerance) uses the film degree of contact pin type surfaceness meter (Dektak IIA Japan vacuum technique system) determination test sheet B.Use hot plate that this test film was heated 1 hour at 250 ℃ then, measure thickness behind the cool to room temperature again.Calculate and heat the decrement (%) that causes thickness.

＜embodiment 1-2 (scheme (iv)) 〉

10 parts of the polymers solns that synthesis example 2 is made, light acid propellant (" SP-170 " rising sun electrification system; To call " SP-170 " in the following text) 0.09 part, trimellitic acid 1,2-anhydride mix for 0.6 part, makes curable resin composition.

The curable resin composition that use makes is similarly estimated light solidified, the transparency and thermotolerance with embodiment 1-1.Show the result in table 1.

＜embodiment 1-3 (scheme (vi)) 〉

10 parts of the polymers solns that synthesis example 3 is made, cresols lacquer resins type Resins, epoxy (EOCN-103S Japan chemical drug system; To call " EOCN-103S " in the following text) 3 parts, 0.3 part of trimellitic acid 1,2-anhydride, PGMEA5 part mix, and make curable resin composition.

Use spinner the curable resin composition that makes to be coated on to make dried thickness on the non-alkali glass plate be 2 μ m, use hot plate 80 ℃ of dryings after 5 minutes, the reusable heat plate made test film B in 1 hour 200 ℃ of heating.The test film B that use makes similarly estimates the transparency and thermotolerance with embodiment 1-1.The results are shown in table 1.

＜comparative example 1-1 (scheme (i)) 〉

0.09 part of 10 parts of polymers solns, DPPA3 part, Irg907, PGMEA5 part that comparison synthesis example 1 is made mix, and make curable resin composition.

The curable resin composition that use makes is similarly estimated light solidified, the transparency and thermotolerance with embodiment 1-1.The results are shown in table 1.

＜comparative example 1-2 (scheme (iv)) 〉

0.09 part of 10 parts of polymers solns, SP-170, trimellitic acid 1,2-anhydride that comparison synthesis example 2 is made mix for 0.6 part, make curable resin composition.

The curable resin composition that use makes, with embodiment 1-1 similarly estimate light solidified, the transparency and thermotolerance.The results are shown in table 1.

＜comparative example 1-3 (scheme (vi)) 〉

0.3 part of 3 parts of 10 parts of polymers solns, EOCN-103S, trimellitic acid 1,2-anhydride, PGMEA5 part that comparison synthesis example 3 is made mix, and make curable resin composition.

The curable resin composition that use makes is similarly estimated the transparency and thermotolerance with embodiment 1-3.The results are shown in table 1.

Table 1

＜embodiment 2-1～2-2, comparative example 2-1～2-2 〉

Each composition of proportioning shown in the table 2 (numerical value adopts weight part to represent) is mixed, make curable resin composition.

After the strainer that uses 1 μ m filtered the curable resin composition that makes, using spinner to be coated on and making dried thickness on the non-alkali glass plate was 2 μ m, used hot plate 80 ℃ of dryings 5 minutes.Then, by have 10 μ m at interval line and the mask of compartment, use the ultrahigh pressure mercury lamp irradiation ultraviolet radiation, making irradiation dose is 100mJ/cm ², then, use the dissolving of 0.05% potassium hydroxide aqueous solution to remove not illuminated portion, made test film A in 1 minute with pure water rinsing, use this test piece to adopt following method to estimate figure.In addition, use hot plate that afore-mentioned test sheet A was made test film B in 1 hour 200 ℃ of heating, use gained test film B to adopt following method evaluate cure to be coated with the transparency and the thermotolerance of membrane portions.The results are shown in table 2.

(figure) uses observation by light microscope test film A, judges by following benchmark.

Zero: the shapeliness of uviolizing part (residual figure) and not illuminated portion do not have residue

*: uviolizing part (residual figure) is damaged or peel off, illuminated portion does not have residue

(transparency) uses spectrophotometer (UV-3100 island Tianjin system) to measure the transmitance (%) of wavelength 380-800nm.

(thermotolerance) uses the thickness of contact pin type surfaceness meter (Dektak IIA Japan vacuum technique system) determination test sheet B.Then, use hot plate that test film B was heated 1 hour at 250 ℃, measure thickness behind the cool to room temperature again.Calculate the decrement (%) that heats the thickness that causes.

[table 2]

＜embodiment 3-1～3-3, comparative example 3-1～3-2 〉

Table 3 each composition with proportioning (numerical value is represented with weight part) shown in the table 4 is mixed, make the colored curable resin composition of red (R), green (G), blue (B), black (K).In addition, the dispersion liquid that uses " Pigment red 254 " respectively is as red dispersion liquid, use " pigment green 36 ": the dispersion liquid of " pigment yellow 13 8 "=6: 4 (weight ratio) as the dispersion liquid of phthalocyanine dispersion liquid, use " Pigment blue-15:6 " as blue dispersible pigment dispersion.

[table 3]

[table 4]

After using the colored curable resin composition of the red, green, blue that makes the strainer of 1 μ m to filter, using spinner to be coated on and making dried thickness on the non-alkali glass plate is 2 μ m, uses hot plate 80 ℃ of dryings 5 minutes.Then by have 20 μ m at interval line and the mask of compartment, use the ultrahigh pressure mercury lamp irradiation ultraviolet radiation to make irradiation dose be 100mJ/cm ²Use the dissolving of 0.05% potassium hydroxide aqueous solution to remove not illuminated portion, use pure water rinsing 1 minute, make test film A, use this test film A to adopt following method to estimate figure.In addition, use hot plate that afore-mentioned test sheet A was made test film B in 1 hour 200 ℃ of heating, use the test film B that makes to adopt following method to measure the colourity of cured coating film part.The results are shown in table 5.

(figure) judged by following benchmark with observation by light microscope test film A.

Zero: the shape of uviolizing part (residual figure) good and not illuminated portion do not have residue.

*: uviolizing part (residual figure) has damaged or peels off, and illuminated portion does not have residue.

(colourity) uses spectral photometric colour measuring instrumentation fixation degree (Y value, x value, y value)

In addition, use the strainer of 1 μ m to filter the black colored curable resin composition that makes after, using spinner to be coated on and making dried thickness on the non-alkali glass plate is 1 μ m, uses hot plate 80 ℃ of dryings 5 minutes.Then, by have 10 μ m at interval line and the mask of compartment, making irradiation dose with the ultrahigh pressure mercury lamp irradiation ultraviolet radiation is 300mJ/cm ²Use the dissolving of 0.05% potassium hydroxide aqueous solution to remove not illuminated portion, use pure water rinsing 1 minute, make test film C, use this test film C to adopt following method to estimate figure.In addition, use afore-mentioned test sheet C hot plate to make test film D in 1 hour, use the test film D that makes to adopt following method to measure the OD value of cured coating film part 200 ℃ of heating.The results are shown in table 5.

(figure) judged by following benchmark with observation by light microscope test film C.

Zero: the shape of uviolizing part (residual figure) is good, and illuminated portion does not have residue

*: uviolizing part (residual figure) have damaged or peel off or not illuminated portion residue is arranged

(OD value) uses the OD value under the spectrophotometric determination 550nm.

[table 5]

＜embodiment 4-1～4-6, comparative example 4-1～4-2 〉

Each composition of proportioning shown in the table 6 (numerical value is represented with weight part) is mixed, make curable resin composition.

After the curable resin composition that makes filtered with the strainer of 1 μ m, using spinner to be coated on and making dried thickness on the non-alkali glass plate was 2 μ m, with hot plate 80 ℃ of dryings 5 minutes.Then, by have 10 μ m at interval line and the mask of compartment, making irradiation dose with the ultrahigh pressure mercury lamp irradiation ultraviolet radiation is 100mJ/cm ²Use the dissolving of 0.05% potassium hydroxide aqueous solution to remove not illuminated portion, use pure water rinsing 1 minute, make test film A, use this test film A to adopt following method to estimate figure.

In addition, afore-mentioned test sheet A is made test film B with hot plate in 1 hour 200 ℃ of heating, use the test film B that makes to adopt following method evaluate cure to be coated with the transparency, surface hardness, resistance to chemical reagents, heat-resisting discolouration and the heat-resisting flatness of membrane portions.The results are shown in table 6.

In addition, embodiment 4-6, do not carry out the evaluation of uviolizing and figure, and 80 ℃ of dryings after 5 minutes, continue to make test film B in 1 hour 200 ℃ of heating, use the test film B that makes to adopt following method evaluate cure to be coated with the transparency, surface hardness, resistance to chemical reagents, heat-resisting discolouration and the heat-resisting flatness of membrane portions with hot plate.

(figure) judged by following benchmark with observation by light microscope test film A.

Zero: the shape of uviolizing part (residual figure) is good, and illuminated portion does not have residue

*: uviolizing part (residual figure) is damaged or peel off, or illuminated portion does not have residue

(transparency) uses the transmitance (%) under spectrophotometer (UV-3100 island Tianjin system) the mensuration wavelength 380-800nm.

(surface hardness) measures surface hardness according to JIS K-5400 pencil test.

(resistance to chemical reagents) is immersed in test film B in 30 ℃ the N-Methyl pyrrolidone, after 30 minutes, draws lattice Continuous pressing device for stereo-pattern method according to JIS K-5400 checkerboard type and carries out the tack test 200 ℃ of dryings with hot plate, adopts remaining number of squares/100 to estimate.

(heat-resisting discolouration) after 1 hour, uses the transmitance (%) under spectrophotometer (UV-3100 island Tianjin system) the mensuration wavelength 400-800nm to test film B 250 ℃ of heat treated with hot plate.Like this, the transmitance by measure gained after transmitance before the heat treated (transmitance of measuring) and the heat treated in the transparency is estimated adopts following formula to calculate the decrement of transmitance, estimates by following benchmark.

The decrement of transmitance (%)=[transmitance before (transmitance after the transmitance-heat treated before the heat treated)/heat treated] * 100

Zero: decrement less than 1%

*: decrement is more than 1%

(heat-resisting flatness) after 1 hour, uses test film B contact pin type surfaceness meter (Dektak IIA Japan vacuum technique system) to measure the Ra value () as the cured coating film surfaceness 250 ℃ of heating with hot plate.

Table [6]

＜embodiment 5, comparative example 5 〉

Each composition of proportioning shown in the table 7 (numerical value is represented with weight part) is mixed, make curable resin composition.

After the curable resin composition that makes filtered with the strainer of 1 μ m, using spinner to be coated on and making dried thickness on the non-alkali glass plate was 5 μ m, used hot plate 80 ℃ of dryings 5 minutes.Then, by the mask of 15 μ m square opening portions is arranged, use the ultrahigh pressure mercury lamp irradiation ultraviolet radiation to make irradiation dose be 100mJ/cm ², use the dissolving of 0.05% potassium hydroxide aqueous solution to remove not illuminated portion, after 1 minute, use hot plate with pure water rinsing 200 ℃ of heating 1 hour, form figure at interval.Use the slight compression trier that the plane pressure head is housed then, in load loading 0.27gf/sec, the failing load of measuring interval portion (gf) under the room temperature.The results are shown in table 7.

[table 7]

＜embodiment 6 〉

Make colour filter and liquid-crystal display as described below, estimate.In addition, employed each curable resin composition of making colour filter is as shown in table 8.

[table 8]

	Embodiment 6	Comparative example 6
			Black-colored resin composition	Embodiment 3-3	Comparative example 3-2
The red resin composition	Embodiment 3-3	Comparative example 3-2
			The green resin composition	Embodiment 3-3	Comparative example 3-2
The blue resins composition	Embodiment 3-3	Comparative example 3-2
			The protective membrane resin combination	Embodiment 4-3	Comparative example 4-2
The spacer resin combination	Embodiment 5	Comparative example 5

(making of colour filter, evaluation)

At first, adopt spin-coating method that the black curable resin composition is coated on to form on the alkali-free glass substrate of 300mm * 400mm, thick 1.1mm and film, carried out prebake conditions 5 minutes at 80 ℃.Then, use ultrahigh pressure mercury lamp to press 500mJ/cm as the proximity exposure machine of light source ²Exposure, aim at exposure by the black matrix sheet of setting with photomask, in alkaline developer, develop, after cleaning with pure water, carry out back baking 30 minutes at 230 ℃, formation black matrix sheet (thickness 1.2 μ m).

Then, the employing spin-coating method is coated on red curable resin composition to form on the substrate that forms the black matrix sheet and films, and carries out prebake conditions 5 minutes at 80 ℃.Then, use the proximity exposure machine of ultrahigh pressure mercury lamp, press 100mJ/cm as light source ²Exposure, aim at exposure by the picture element of setting with photomask, in alkaline developer, develop, after cleaning with pure water, carry out back at 200 ℃ and toasted 30 minutes, form red picture element figure (thickness 2.0 μ m).Similarly, use green curable resin composition to form green picture element figure, use blue curable resin composition to form blue picture element figure.

Then, adopt spin-coating method that protective membrane is coated on resin combination to form on the substrate that forms black matrix sheet and picture element of all kinds and film, carried out prebake conditions 5 minutes at 80 ℃.After this, use the proximity exposure machine of ultrahigh pressure mercury lamp, press 100mJ/cm as light source ²Exposure, aim at exposure by the protective membrane of setting with photomask, in alkaline developer, develop, after the pure water washing, carry out back baking 30 minutes at 200 ℃, formation protective membrane (thickness 1.5 μ m).

Then, adopt spin-coating method to film, carried out prebake conditions 5 minutes at 80 ℃ being coated on to form on the substrate that forms protective membrane with resin combination at interval.Then, use the proximity exposure machine of ultrahigh pressure mercury lamp, press 100mJ/cm as light source ²Exposure, aim at exposure by the interval of setting with photomask, in alkaline developer, develop, after cleaning with pure water, carry out back baking 30 minutes at 220 ℃, formation spacer (high 4.8 μ m, bottom 12 μ m * 12 μ m squares).

The colour filter that uses light microscopy to make, the result does not have the damaged of figure or development residue, and the smoothness on protective membrane surface is also good.

(making of liquid crystal indicator, evaluation)

As above-mentioned, on the colour filter of made, adopt sputtering method to form the transparency conducting layer (thickness 0.15 μ m) that Indium sesquioxide constitutes, establish again after polyimide alignment layers carries out orientation process (friction), use epoxy resin sealing agent applying tft array substrate, from the inlet that is located at sealing after injecting TN type liquid crystal between colour filter and the tft array substrate, the shutoff inlet, fit the again optical thin film of Polarizer etc. is made the liquid crystal indicator of TN mode.

The liquid crystal indicator that makes can obtain brightness and purity of color height, does not produce good display qualities such as color spot.

＜comparative example 6 〉

Except the curable resin composition that the making colour filter is used made the composition of table 8 expression into, other made colour filter and liquid-crystal display similarly to Example 6, evaluation result, and colour filter has the damaged of figure or development residue.Liquid crystal indicator brightness and purity of color are low, also produce color spot.

Curable resin composition of the present invention is applicable to for example purposes of erosion resistant, various coating agent, coating etc.

Claims (7)

1. curable resin composition, it is characterized in that, it is the curable resin composition that contains component of polymer (A) and be selected from compound (b1) with free-radical polymerised pair of key and at least a kind of cure component of being formed (B) of compound (b2) with epoxy group(ing)

Aforementioned polymer composition (A) is that the compound of following general expression (1) expression is the polymkeric substance (a) that necessary monomer component polymerization forms, and the ratio of the compound of the expression of the aforementioned general expression (1) in the aforementioned polymer (a) is the 2-60 weight % in the total monomer composition

In the formula (1), R ¹With R ²Represent separately that respectively hydrogen atom maybe can have substituent C ₁-C ₂₅Alkyl.

2. the described curable resin composition of claim 1 is characterized in that, aforementioned polymer (a) is the polymkeric substance with acidic group.

3. the described curable resin composition of claim 1, it is characterized in that, aforementioned polymer (a) also is from the compound (b1) with free-radical polymerised pair of key and has at least a kind the compound of selecting the compound (b2) of epoxy group(ing), and double as cure component (B).

4. the described curable resin composition of claim 1, it is characterized in that, aforementioned cure component (B) is the compound (b1) with free-radical polymerised pair of key, contains be selected from optical free radical propellant (c1) and the hot radical propellant (c2) at least a kind in addition as polymerization starter (C).

5. the described curable resin composition of claim 1, it is characterized in that, aforementioned cure component (B) is the compound (b2) with epoxy group(ing), contains be selected from light acid propellant (c3) and the hot acid propellant (c4) at least a kind in addition as polymerization starter (C).

6. colour filter is the colour filter that substrate is provided with curing resin layer, it is characterized in that, the resin combination that forms aforementioned curing resin layer is each the described curable resin composition among the claim 1-5.

7. display unit is to use substrate to be provided with the display unit of the colour filter of curing resin layer, it is characterized in that, the resin combination that forms aforementioned curing resin layer is each the described curable resin composition among the claim 1-5.