JP2009161617A - Alkali-soluble resin obtained from low acid number intermediate and its application - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alkali-soluble resin having a radical polymerizable unsaturated group in a side chain, excellent in plate making properties, excellent also in storage stability, and suitably usable for a color filter. <P>SOLUTION: The alkali-soluble resin is obtained by modifying a side-chain double bond-containing polymer with a polybasic acid anhydride, wherein the alkali-soluble resin has a double bond equivalent of 400-2,000 by the polybasic acid anhydride modification of the side-chain double bond-containing polymer having an acid number of ≤25. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to an alkali-soluble resin obtained from a low acid value intermediate and its use. More specifically, the present invention relates to an alkali-soluble resin that is obtained from a low acid value intermediate and can be suitably used for the production of a color filter used for color liquid crystal display and the like and its use.

Photolithographic technology using an alkali developing type resist is a technology used in various industrial fields, and is indispensable particularly in the formation of electronic information field members such as display members and electronic circuit boards. Technology. One important member formed by this technique is a color filter. The color filter is an indispensable member for a color liquid crystal display device and a color image pickup tube element, and has a fine colored resin layer for separating colors. Various methods have been proposed as a method for producing a color filter, but the current mainstream is a method using an alkali developing resist (photosensitive resin composition) containing an alkali-soluble resin as an essential component. In recent years, in order to improve the plate-making characteristics and the reliability after curing, alkali-soluble resins to which not only alkali-soluble groups but also radical polymerizable unsaturated groups have been introduced to impart photosensitivity have come to be used. It is coming.

On the other hand, in order to improve the color characteristics of the color filter, the amount of the colorant contained in the photosensitive resin composition for the color filter tends to increase, and accordingly, the sensitivity, the edge shape of the fine pattern, and the surface state In addition, it has become difficult to achieve compatibility with plate making characteristics such as development residues.
In addition, due to the rapid spread of liquid crystal televisions and lower prices, demands for cost reduction of each member including color filters are becoming stricter year by year. However, the photosensitive resin composition for color filters and the resins used therefor are inevitably made up in a small amount and a wide variety because they are optimized for each color filter specification and production line. Therefore, in order to balance the cost with a variety of small quantities, it is desirable to mass-produce resins at once and store them for a long time in a warehouse without cooling equipment, and there is a demand for resins that are excellent in storage stability at high temperatures.

Conventionally, many photosensitive resin compositions for color filters using a (meth) acrylic acid copolymer added with glycidyl (meth) acrylate as an alkali-soluble resin imparted with photosensitivity have been proposed and used. (For example, refer to Patent Document 1). However, it has been found that a resin in which an epoxy group-containing monomer is added to such an acid group-containing polymer has room for improvement in plate-making characteristics and has insufficient storage stability at high temperatures.

Furthermore, as a method for improving the plate-making characteristics, an acrylic acid copolymer added with acrylic acid (3,4-epoxycyclohexyl) methyl, and further added with maleic anhydride or tetrahydrophthalic anhydride to the side chain hydroxyl group. A photosensitive resin composition for black matrix used has been proposed (see, for example, Patent Document 2). However, this resin also has room for improvement in terms of development residue.
JP 2003-192746 A JP-A-11-109616

The present invention has been made in view of the above situation, and is suitably used for a color filter having a radically polymerizable unsaturated group in a side chain, excellent in plate making characteristics and excellent in storage stability. An object of the present invention is to provide an alkali-soluble resin that can be used.

As a result of intensive studies to solve the above problems, the present inventors have added an epoxy group-containing monomer to an acid group-containing polymer to have a hydroxyl group and a radical polymerizable unsaturated group in the side chain. In an alkali-soluble resin which is a polymer and further modified with a polybasic acid anhydride to convert it to a carboxyl group, the acid value before modification with the polybasic acid anhydride is 25 mg KOH / g or less and is directly bonded to the main chain. When the number of acid groups is less than a specific value and the number of side chains having both a carboxyl group and a radical polymerizable unsaturated group generated by polybasic acid anhydride modification is greater than a specific value, the sensitivity, The present inventors have found that the fine plate edge shape, surface state, and development characteristics such as development residue are excellent, and that high temperature and long-term storage stability are improved, and that the above problems can be solved brilliantly.

That is, the present invention is an alkali-soluble resin obtained by polybasic acid anhydride modification of a side chain double bond-containing polymer, wherein the alkali-soluble resin has an acid value of 25 mgKOH / g or less. It is an alkali-soluble resin in which a polymer containing a heavy bond is polybasic acid anhydride modified and has a double bond equivalent of 400-2000.
The present invention is described in detail below.

The alkali-soluble resin of the present invention uses a polymer having an acid value of 25 mgKOH / g or less as a raw material, and further has a hydroxyl group reduced by polybasic acid anhydride modification, and is excellent in storage stability. become. Since there are few acid groups directly bonded to the main chain, and the carboxyl group and double bond are present at the tip of the side chain, it is cured with a small amount of exposure and is excellent in alkali solubility. Excellent plate making properties such as an edge pattern and reduced development residue are exhibited.

The acid value is more preferably 20 mgKOH / g or less, still more preferably 15 mgKOH / g or less, and particularly preferably 10 mgKOH / g or less.
When the acid value is such a preferable value, the plate making characteristics are more effectively exhibited. In addition, what is necessary is just to adjust suitably the acid value of the raw material polymer mentioned later and the quantity of the epoxy-group-containing monomer to add, for example to make the acid value of a side chain double bond containing polymer into the said range.

The double bond equivalent of the alkali-soluble resin of the present invention is 400 to 2000, but preferably 400 to 1800. More preferably, it is 400-1500. By setting the double bond equivalent within the above range, it can be expected that sufficient storage stability after modification with polybasic acid anhydride and good plate making characteristics such as sensitivity and pattern shape are compatible at a higher level. The double bond equivalent is the weight average molecular weight per double bond of the polymer. In order to make the double bond equivalent within the above range, for example, the amount of the epoxy group-containing monomer to be added to the raw material polymer described later may be appropriately adjusted.

The alkali-soluble resin of the present invention is obtained using a side chain double bond-containing polymer as a raw material. The side chain double bond-containing polymer is a polymer having a structure in which a side chain having a double bond is added to the main chain of the polymer. The main chain means the longest chain of a polymer formed by polymerizing monomer components, and a side chain is introduced by bonding a monomer having a double bond to the polymer. It is the part which becomes the origin. Moreover, a side chain means the part of the chain | strand branched from the main chain, The compound which forms a side chain may be 1 type, and 2 or more types may be sufficient as it.

The modification of the polybasic acid anhydride in the side chain double bond-containing polymer is an addition reaction of the acid anhydride group (—CO—O—CO—) of the polybasic acid anhydride to the hydroxyl group of the side chain. It is to modify the polymer. By the addition reaction, the hydroxyl group of the side chain is converted to a carboxyl group via an ester bond. Moreover, as the side chain double bond-containing polymer that is the basis of the alkali-soluble resin of the present invention, for example, a polymer having a side chain portion having a hydroxyl group and a double bond in the same side chain portion is used, or A polymer having a hydroxyl group and a double bond in separate side chains can be used.

The alkali-soluble resin is obtained by adding a side chain double bond site having a hydroxyl group by adding an epoxy group-containing monomer to a carboxyl group-containing polymer, and further adding a polybasic acid anhydride to the hydroxyl group. It is one of the preferred embodiments of the present invention to be a polymer.
The polymer obtained by such a production method is excellent in the above-mentioned plate making characteristics.
In the present specification, a polymer before introducing a side chain portion having a double bond is referred to as a raw material polymer. Further, a polymer after the introduction of a side chain portion having a double bond and before the modification with the polybasic acid anhydride is referred to as a side chain double bond-containing polymer before the modification, and the polybasic acid anhydride. The polymer after modification is referred to as a modified side chain double bond-containing polymer.

The introduction of a side chain double bond site having a hydroxyl group by addition reaction of the epoxy group-containing monomer with the acid group-containing polymer means that the epoxy group-containing monomer is added to the acid group of the starting polymer. An addition reaction of an epoxy group is performed to add a side chain double bond site having a hydroxyl group to the polymer (hereinafter referred to as an addition reaction step).
In addition, adding a polybasic acid anhydride to a hydroxyl group means converting the hydroxyl group into a carboxyl group via an ester bond by adding an acid anhydride group of the polybasic acid anhydride to the hydroxyl group of the side chain. Performing a process (hereinafter referred to as a denaturing process).
The alkali-soluble resin of the present invention is preferably obtained by performing the addition reaction step and the modification step in this order.
In the following, first, the raw material polymer will be described.

The said raw material polymer is a polymer which has acid groups and acid anhydride groups, such as a carboxyl group, a phenolic hydroxyl group, a phosphoric acid group, and a sulfonic acid group. Examples of the method for introducing an acid group include a method in which a monomer having an acid group is polymerized with another copolymerizable monomer, and a compound having an acid group is added to a polymer having no acid group. Examples thereof include a method and a method of ring-opening an acid anhydride group of a polymer having an acid anhydride group. Among these, a method of polymerizing a monomer having an acid group together with another copolymerizable monomer is preferable. Moreover, when making it superpose | polymerize, it can superpose | polymerize by a well-known method, for example, can superpose | polymerize in a solvent using a polymerization initiator and a chain transfer agent as needed. As the polymerization mechanism, known polymerization mechanisms such as radical polymerization, cationic polymerization, anionic polymerization, and coordination polymerization can be used, but radical polymerization is industrially simple and preferable.

Examples of the monomer having an acid group include monomers having an acid group such as a carboxyl group, a phenolic hydroxyl group, a phosphoric acid group, and a sulfonic acid group. Among these, a monomer having a carboxyl group is preferable. Examples of the monomer having a carboxyl group include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, and vinyl benzoic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and the like. Between unsaturated group and carboxyl group such as unsaturated polycarboxylic acid, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), ω-carboxypolycaprolactone mono (meth) acrylate And unsaturated monocarboxylic acids having a chain extended. Of these, (meth) acrylic acid is preferred. These monomers having a carboxyl group can be used alone or in combination of two or more.

The use amount of the monomer having an acid group is preferably 3 to 70% by weight of the monomer having an acid group when the total monomer component is 100% by weight. More preferably, it is 5 to 60% by weight. By setting it as the said range, sufficient double bond amount can be introduce | transduced into a polymer, and the storage stability when it is set as the photosensitive resin composition can be made more excellent.

Examples of the other copolymerizable monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, (meth) N-butyl acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, (meth) Tridecyl acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic Isobornyl acid, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, (meth) (Meth) acrylic acid esters such as 4-hydroxybutyl acrylate, allyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate; Aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene, and methoxystyrene; N-substituted maleimides listed in JP-A-2003-192746; Rings listed in JP-A-2004-300204 Tetrahydropyran structure is introduced into the main chain by chemical polymerization Α-hydroxymethyl acrylate ether dimers that can be treated; macromonomers having a (meth) acryloyl group at one end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, etc. Conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; (meth) acrylamide, N, N-dimethyl (meth) acrylate And unsaturated amides such as amide, N-vinylpyrrolidone, N-vinylcarbazole, N-vinylphthalimide, N-vinylimidazole, N-vinylmorpholine, and N- (meth) acryloylmorpholine.
Among these, it is easy to balance various plate-making characteristics such as pattern characteristics and development margins, so that methyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, and vinyltoluene are included. 1 type or 2 types or more are preferable. Moreover, in order to improve heat resistance, it is preferable to use maleimides. Furthermore, in order to improve low coloration, heat resistance, and pigment dispersibility, it is preferable to use ether dimers of α-hydroxymethyl acrylate.

The solvent used when the raw material polymer is produced is preferably inert to the polymerization reaction. Moreover, it is preferable to use the solvent used when setting it as the photosensitive resin composition. Thereby, the photosensitive resin composition can be efficiently prepared. In addition, it is suitable to set a solvent suitably according to superposition | polymerization conditions, such as superposition | polymerization mechanism, the kind and quantity of the monomer to be used, superposition | polymerization temperature, superposition | polymerization concentration.
Examples of the solvent include monoalcohols such as methanol, ethanol, isopropanol, n-butanol and sec-butanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl ether and ethylene Glycol monoethers such as glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 3-methoxybutanol; Ethylene glycol dimethyl ether , Glycol ethers such as ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate , Ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Esters of glycol monoethers such as chill ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate; methyl acetate, acetic acid Ethyl, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropion Alkyl esters such as methyl acetate, ethyl 3-ethoxypropionate, methyl acetoacetate and ethyl acetoacetate; acetone, methyl ester Ketones such as tilketone, methylisobutylketone and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; aliphatic hydrocarbons such as hexane, cyclohexane and octane; dimethylformamide, dimethylacetamide and N-methylpyrrolidone Amides and the like. These may be used alone or in combination of two or more. As a usage-amount of a solvent, 40 to 1000 weight% is preferable with respect to 100 weight% of all the monomer components. More preferably, it is 100 to 400% by weight.

The radical polymerization initiator used when producing the raw material polymer by radical polymerization may be any one that can initiate radical polymerization. The radical polymerization initiator is suitably selected according to the polymerization conditions such as the polymerization temperature, the solvent, and the type of monomer to be polymerized.
Examples of the radical polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-butylperoxy-2. -Ethylhexanoate, azobisisobutyronitrile, 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (2 -Methyl propionate) and the like, and known peroxides and azo compounds may be used. These may be used alone or in combination of two or more.

The amount of the radical polymerization initiator used is preferably 0.1 to 20% by weight with respect to 100% by weight of all monomer components, for example, in order to obtain a polymer having a weight average molecular weight of thousands to tens of thousands. . More preferably, it is 0.5 to 15% by weight. The amount of radical polymerization initiator used is suitably set according to the type and amount of monomer used, polymerization conditions such as polymerization temperature and polymerization concentration, and the molecular weight of the target polymer. .

When manufacturing the said raw material polymer by radical polymerization, a well-known chain transfer agent can be used with a radical polymerization initiator as needed. Examples of the chain transfer agent include n-dodecyl mercaptan, mercaptoacetic acid, methyl mercaptoacetate, 3-mercaptopropionic acid, methyl 3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis ( 3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), α-methylstyrene dimer, and the like. These may be used alone or in combination of two or more.

For example, in order to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, the chain transfer agent is preferably used in an amount of 0.1 to 20% by weight with respect to 100% by weight of all monomer components. More preferably, it is 0.5 to 15% by weight. The amount of chain transfer agent used is suitably set according to the type and amount of monomers used, the polymerization conditions such as the polymerization temperature and polymerization concentration, the molecular weight of the target polymer, and the like.

The polymerization temperature when producing the raw material polymer by radical polymerization is preferably, for example, 50 to 200 ° C. More preferably, it is 70-150 degreeC. In addition, it is suitable to set suitably according to the kind and quantity of a monomer to be used, the kind and quantity of a polymerization initiator, etc.

It is preferable that the raw polymer solution is sufficiently reduced in moisture before the addition reaction step. Thereby, it is possible to prevent the epoxy group-containing monomer from being consumed due to the reaction of the epoxy group-containing monomer and moisture.
The amount of water in the raw polymer solution is preferably 1.0% by weight or less when the total mass of the raw polymer solution is 100% by weight. More preferably, the water content is 0.5% by weight or less, and still more preferably, the water content is 0.1% by weight or less. Examples of the method for reducing moisture include known methods such as a method of distilling together with a solvent contained in a solution, a method of blowing a dry inert gas, a method of using a dehydrating adsorbent such as a molecular sieve.
Then, the said addition reaction process is demonstrated.

The epoxy group-containing monomer used in the addition reaction step is a compound having an epoxy group and a double bond. Examples of the epoxy group include 1,2-epoxide group (oxirane group), 1,3-epoxide group (oxetanyl group), 1,4-epoxide group (tetrahydrofuranyl group), 1,5-epoxide group (tetrahydropyrani group). Group).
Examples of such compounds include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, allyl (meth) acrylate, vinylbenzyl glycidyl ether, allyl glycidyl ether, and the like. Monomer having an aliphatic 1,2-epoxide group, 3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryloxy Monomers having an aliphatic 1,3-epoxide group such as methyl oxetane, and alicyclic 1,2-epoxide groups such as (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, vinylcyclohexene oxide, etc. A monomer is mentioned. Among these, a monomer having an aliphatic 1,2-epoxide group is preferable from the viewpoints of reactivity to carboxyl groups and flow characteristics and coating characteristics when used as a coating solution. Particularly preferred is glycidyl (meth) acrylate. Most preferred is glycidyl methacrylate.

It is preferable to perform the said addition reaction process in the temperature range of 50-160 degreeC. In this case, usually, the raw material polymer, the epoxy group-containing monomer, the solvent, and the addition catalyst are mixed. More preferably, it is 70-140 degreeC as said temperature, More preferably, it carries out at 90-120 degreeC. If the temperature is lower than 50 ° C., the reaction may take a long time or the reaction rate may decrease. When the temperature exceeds 160 ° C., the polymer is easily gelled during the reaction. In order to prevent gelation, it is desirable to further mix a polymerization inhibitor and perform in the presence of a molecular oxygen-containing gas. As the molecular oxygen-containing gas, air or oxygen gas diluted with an inert gas such as nitrogen is usually used and blown into the reaction vessel.

The reaction time of the addition reaction step is preferably continued until the reaction rate of the epoxy group-containing monomer reaches 80% or more. More preferably, it is continued until it reaches 90% or more. As a result, effects such as introduction of a sufficient amount of double bonds in the side chain and sufficiently reduction of highly toxic epoxy group-containing monomers are exhibited. The reaction rate can be confirmed by quantifying the acid value of the reaction solution, quantifying the residual amount of the epoxy group-containing monomer using a gas or liquid chromatography method, and the like.

As the solvent used in the addition reaction step, those mentioned as the solvent used in obtaining the raw material polymer can be used, and one or more kinds may be used. It is efficient and preferable to synthesize the raw polymer using a solvent and use the solvent of the obtained raw polymer solution as it is as a solvent for the addition reaction step. The amount of the solvent used in the addition reaction step is preferably such that the concentration of the raw material polymer is 10 to 60% by weight when the total mass of the raw material polymer solution is 100% by weight. By carrying out within the above range, the reaction time can be shortened and it is economical, and since the viscosity of the system is relatively low, it is difficult to gel and temperature control can be expected. A more preferable concentration is 15 to 50% by weight, and further preferably 20 to 45% by weight.

As the addition catalyst used in the addition reaction step, known basic catalysts for esterification or transesterification and acidic catalysts can be used. Among these, it is preferable to use a basic catalyst because there are few side reactions.
Examples of the basic catalyst include tertiary amines such as dimethylbenzylamine, triethylamine, tri-n-octylamine and tetramethylethylenediamine, tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, and n-dodecyltrimethylammonium. Quaternary ammonium salts such as chloride, urea compounds such as tetramethylurea, alkylguanidines such as tetramethylguanidine, amide compounds such as dimethylformamide and dimethylacetamide, tertiary phosphines such as triphenylphosphine and tributylphosphine, tetraphenylphosphonium bromide And quaternary phosphonium salts such as benzyltriphenylphosphonium bromide. Among these, dimethylbenzylamine, triethylamine, tetramethylurea, and triphenylphosphine are preferable in terms of reactivity, handling properties, and halogen-free. These catalysts may be used alone or in combination of two or more.
The amount of the catalyst used in the addition reaction step is preferably 0.01 to 5.0% by weight when the total weight of the raw material polymer and the epoxy group-containing monomer is 100% by weight. More preferably, it is 0.1 to 3.0% by weight. By carrying out within the above range, the reaction time can be shortened and it is economical, and the storage stability of the resin after polybasic acid anhydride modification can be secured.

As the polymerization inhibitor used in the addition reaction step, a known polymerization inhibitor for radical polymerizable monomers can be used. Examples of the polymerization inhibitor for radical polymerizable monomers include hydroquinone, methylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, methoquinone, 6-t-butyl-2,4-xylenol, and 2,6-di-t-. Mention phenolic inhibitors such as butylphenol, 2,6-di-t-butyl-4-methoxyphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), organic acid copper salts and phenothiazines Can do. Among these, phenol-based inhibitors are preferable from the viewpoint of low coloring and ability to prevent polymerization. Among them, methoquinone, 6-t-butyl-2,4-xylenol, 2,6-di-t are particularly preferable in view of availability and economy. -Butylphenol is preferred. These polymerization inhibitors may be used alone or in combination of two or more.

The amount of the polymerization inhibitor used in the addition reaction step is preferably 0.001 to 1.0% by weight when the total weight of the raw material polymer and the epoxy group-containing monomer is 100% by weight. . More preferably, 0.005 to 0.5% by weight is used. By performing in the said range, coexistence with the gelatinization prevention in an addition reaction process and sufficient sclerosis | hardenability at the time of setting it as the photosensitive resin composition can be anticipated.
Subsequently, the modification step will be described.

The polybasic acid anhydride used in the modification step is a compound having an acid anhydride group. The polybasic acid anhydride is preferably a compound obtained by dehydration condensation of a carboxylic acid having two or more carboxyl groups in the molecule. More preferably, the following general formula (1);

(In the above formula, X represents a linking group which may form a 4- to 7-membered acid anhydride group and may have a substituent).
The compound represented by the general formula (1) has at least one 4- to 7-membered cyclic acid anhydride group, and the 4- to 7-membered cyclic acid anhydride group includes X and-(C A compound constituted by a structure in which a group represented by ═O) —O— (C═O) — is linked. In addition to the 4- to 7-membered cyclic acid anhydride group, X is constituted by a structure in which X and a group represented by — (C═O) —O— (C═O) — are linked. It may have an acid anhydride group. That is, the compound represented by the general formula (3) may have two or more 4- to 7-membered cyclic acid anhydride groups.

Examples of the compound represented by the general formula (1) include succinic anhydride, dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydro anhydride Phthalic acid, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, diphenic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, glutaric anhydride, phthalic anhydride, anhydrous Examples include trimellitic acid and pyromellitic anhydride. These 1 type (s) or 2 or more types can be used.

More preferably, among the polybasic acid anhydrides mentioned above, succinic anhydride type dibasic acid anhydrides such as succinic anhydride, dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, tetrahydro Hydrophilic phthalic anhydride type dibasic anhydrides such as phthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, etc. It is. Most preferred is succinic anhydride.
Ester bonds formed using these as polybasic acid anhydrides are stable and excellent in storage stability, and the distance between the double bond and the carboxyl group is optimal. As a result, it contributes to the display of further excellent plate-making characteristics.

The modification step is preferably performed in the presence of a polymerization inhibitor and / or molecular oxygen gas. That is, the modification step is usually performed by mixing the side chain double bond-containing polymer, the polybasic acid anhydride, and the solvent before modification in the presence of an addition catalyst. Furthermore, it is preferable to carry out in the presence of a polymerization inhibitor and / or molecular oxygen gas.

As the solvent used in the modification step, those mentioned as the solvent used in obtaining the raw material polymer can be used. Moreover, in the said modification | denaturation process, since the solvent which has a primary or secondary hydroxyl group reacts with a polybasic acid anhydride, it is preferable not to use or to remove before a modification | denaturation process and to fully reduce. As the addition catalyst and the polymerization inhibitor, the same ones as in the addition step can be used. Subsequent to the addition step, it is efficient and preferable to add a polybasic acid anhydride.

The modified side chain double bond-containing polymer is a polymer obtained by adding a polybasic acid anhydride to 30 mol% or more of the hydroxyl groups of the side chain double bond-containing polymer before modification. preferable. More preferably, it is 50 mol% or more as said addition amount, More preferably, it is 60-100 mol%. By reducing the hydroxyl group, the crosslinking reaction caused by the reaction between the hydroxyl group and the carboxyl group or the ester group that proceeds gradually during storage can be suppressed without removing or deactivating the additional catalyst, even at relatively high temperatures. Long-term storage is possible, and storage stability is further improved.

The acid value of the modified side chain double bond-containing polymer is preferably 20 to 250 mgKOH / g. More preferably, it is 25-200 mgKOH / g, More preferably, it is 30-160 mgKOH / g. By setting it as the said range, pattern defect | deletion and a residue are hard to produce further and it can exhibit a further favorable plate-making characteristic.

The alkali-soluble resin of the present invention preferably has a weight average molecular weight of 40,000 or less. More preferably, it is 3000-40000, More preferably, it is 5000-30000. By setting it as the said range, it can be anticipated that sufficient storage stability after polybasic acid anhydride modification and plate-making characteristics such as development time and sensitivity are compatible at a higher level.

The present invention is also a photosensitive resin composition for a color filter which essentially contains the alkali-soluble resin.
The photosensitive resin composition for a color filter usually contains an alkali-soluble resin, a polyfunctional monomer, a photopolymerization initiator, and a solvent. However, the photosensitive resin composition for a color filter of the present invention contains an alkali. A side chain double bond-containing modified polymer obtained from the low acid value intermediate of the present invention is included as a soluble resin. The so-called resist is usually configured to include an alkali-soluble resin, a polyfunctional monomer, a photopolymerization initiator, and a solvent, and the color resist includes a colorant.

The side chain double bond-containing modified polymer of the present invention is an essential component constituting the photosensitive resin composition.
In addition, although the photosensitive resin composition of this invention is comprised with the side chain double bond containing modified polymer of this invention, it may contain the other polymer.
In this specification, when an essential component is included (contained), it can be said that it is a suitable form to include the essential component or to be a main component (main component) to the extent that the effects of the present invention are exhibited.

The preferred use mode of the above-mentioned photosensitive resin composition for a color filter includes a clear coat composition for a protective film, a composition for a photospacer, a coloring composition for a pixel, a coloring composition for a black matrix, and a liquid crystal alignment control structure. And the like. When used as a coloring composition for a pixel or a coloring composition for a black matrix, it usually contains a colorant in addition to the above components.
That is, it is one of the preferred embodiments of the present invention that the photosensitive resin composition for a color filter of the present invention contains a colorant.
Although the following description is given about the component which can be contained in the photosensitive resin composition, this invention is not limited to this.

<Alkali-soluble resin>
The alkali-soluble resin in the photosensitive resin composition of the present invention has a function enabling coating film formation and development with an alkali developer, that is, a function as a binder resin for controlling coating characteristics and plate-making characteristics. And an alkali-soluble group is essential. Furthermore, it is preferable to have a polymerizable unsaturated bond in order to improve sensitivity and pattern characteristics. In addition, the alkali-soluble resin contributes not only to coating properties and plate making properties, but also to mechanical properties and heat resistance of the cured coating film. When the photosensitive resin composition further contains a color component (pigment, dispersant, dispersion aid), a function as a dispersion resin for dispersing and stabilizing the color component is also required.
The alkali-soluble resin of the present invention is suitable as an alkali-soluble resin for a colored composition because it has an excellent dispersion stabilizing function for coloring components. In addition, the cured coating film is excellent in transparency and plate making characteristics, and is also useful as an alkali-soluble resin for protective films and photospacers.

In general, the photosensitive resin composition of the present invention preferably contains 10% by weight or more of an alkali-soluble resin when the total solid content of the photosensitive resin composition is 100% by weight. More preferably, it contains 20% by weight or more. As the alkali-soluble resin, in addition to the alkali-soluble resin of the present invention, other known alkali-soluble resins can be used in combination as long as the characteristics of the polymer and the photosensitive resin composition of the present invention are not impaired.
The amount of the alkali-soluble resin used in the present invention is preferably 20 to 100% by weight when the total solid content of the alkali-soluble resin is 100% by weight. More preferably, it is 30 to 100% by weight. The “total solid content” means all components other than the solvent.

<Multifunctional monomer>
The polyfunctional monomer in the photosensitive resin composition of the present invention is a monomer having two or more polymerizable unsaturated bonds. The polyfunctional monomer is a component that is polymerized and cured by radicals generated from the photopolymerization initiator to develop photosensitivity.
Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di ( Multivalents such as (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Esters of hydroxy compounds and unsaturated carboxylic acids; acid group-containing polymers obtained by reacting polybasic acid anhydrides with unreacted hydroxyl groups of esters of polyvalent hydroxy compounds and unsaturated carboxylic acids Urethane (meth) acrylates such as those obtained by reacting functional monomers, polyisocyanate compounds and hydroxyl-containing (meth) acrylic acid esters; such as addition reaction products of polyfunctional epoxy compounds and (meth) acrylic acid Epoxy (meth) acrylates; and allyl compounds such as diallyl phthalate and triallyl isocyanurate. These polyfunctional monomers may be used alone or in combination of two or more. The amount of the polyfunctional monomer used is preferably 5 to 80% by weight when the total solid content of the photosensitive resin composition is 100% by weight. More preferably, it is 10 to 70% by weight. As long as the performance of the photosensitive resin composition of the present invention is not impaired, a monofunctional monomer such as methyl (meth) acrylate is polyfunctional as a component that is polymerized and cured by radicals generated from a photopolymerization initiator. It may be used in combination with a functional monomer.

<Photopolymerization initiator>
The photopolymerization initiator in the photosensitive resin composition of the present invention is a compound that is excited by actinic rays to generate radicals and polymerizes polymerizable unsaturated bonds.
Examples of the photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one. 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl) Propionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 [4- (4-morpholinyl) phenyl] -1-alkyl phenone compounds such as butanone;
Benzophenone compounds such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 2-carboxybenzophenone;
Benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether;
Thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone;

2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 -Ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarboquinylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine, and other halomethylated triazine compounds ;
2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4-oxa Halomethylated oxadiazole compounds such as diazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole;
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1, Biimidazole compounds such as 2'-biimidazole;
1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 Oxime ester compounds such as -yl]-, 1- (O-acetyloxime);
Titanocene compounds such as bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium;
benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid;
Acridine compounds such as 9-phenylacridine;
These may be used alone or in combination of two or more. The amount of the photopolymerization initiator used is preferably 0.1 to 30.0% by weight when the total solid content of the photosensitive resin composition is 100% by weight. More preferably, it is 0.5-20.0 weight%.

The said photosensitive resin composition can also use a hydrogen donor together with a photoinitiator as needed. Thereby, sensitivity and curability can be improved.
Examples of the hydrogen donor include amine hydrogen donors such as ethyl 4-dimethylaminobenzoate and 2-ethylhexyl 4-dimethylaminobenzoate, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole. And mercaptan-based hydrogen donors. These hydrogen donors may be used alone or in combination of two or more.
The amount of the hydrogen donor used is usually preferably 0 to 20% by weight when the total solid content of the photosensitive resin composition is 100% by weight. More preferably, it is 0.1 to 10% by weight.

The said photosensitive resin composition can also use a sensitizing dye together with a photoinitiator as needed. Thereby, sensitivity and curability can be improved.
Examples of sensitizing dyes include xanthene dyes, coumarin dyes, 3-ketocoumarin compounds, pyromethene dyes, dialkylaminobenzene compounds, and the like. These sensitizing dyes may be used alone or in combination of two or more.
The amount of the sensitizing dye used is usually preferably 0 to 20% by weight when the total solid content of the photosensitive resin composition is 100% by weight. More preferably, it is 0.1 to 10% by weight.

<Solvent>
As the solvent in the photosensitive resin composition of the present invention, an alkali-soluble resin, a polyfunctional monomer, a photopolymerization initiator, and, if necessary, a colorant, a dispersant, and other additives are dissolved or dispersed, and viscosity or Any device having a function of adjusting the drying characteristics and the like may be used.
Examples of such solvents include monoalcohols such as methanol, ethanol, isopropanol, n-butanol and sec-butanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl Glycol monomers such as ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 3-methoxybutanol Ethers; ethylene glycol dimethyl ether Glycol ethers such as ether ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol Methyl monoacetate acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, esters of glycol monoether such as 3-methoxybutyl acetate; methyl acetate , Ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Alkyl esters such as methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl acetoacetate and ethyl acetoacetate; acetone , Ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; aliphatic hydrocarbons such as hexane, cyclohexane and octane; dimethylformamide, dimethylacetamide and N-methyl Examples include amides such as pyrrolidone. These may be used alone or in combination of two or more.

As the usage-amount of the said solvent, when the total mass of the photosensitive resin composition is 100 weight%, it is preferable that a total solid is 5 to 50 weight%. More preferably, the total solid content is 10 to 40% by weight. Note that the amount of solvent used is suitably set according to the type and amount of components other than the solvent.

<Colorant>
When the photosensitive resin composition of the present invention is used as a coloring composition, dyes and pigments can be used alone or in admixture of two or more as a coloring agent. From the viewpoint of heat resistance and light resistance, organic or inorganic pigments are preferred.
Examples of organic pigments include azo, anthraquinone, quinophthalone, phthalocyanine, quinacridone, benzimidazolone, isoindoline, dioxazine, indanthrene, perylene, diketopyrrolopyrrole, and the like. For example,
C. I. Pigment Red 81, 105, 122, 149, 150, 177, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265, 272;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment Yellow 11, 24, 31, 53, 83, 128, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 168, 175, 185, 199;
C. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55;
C. I. Pigment blue 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64;
C. I. Pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50;
C. I. Pigment brown 1, 6, 11, 25, 28, 30, 43;
C. I. Pigment black 1, 6, 7, 12, 20, 31, 32;
Carbon black, graphite, aniline black;
Etc. “CI” means a color index.
Inorganic pigments include titanium oxide, titanium black, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red pepper, cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, synthetic iron black, etc. Examples include oxides and complex salts.
Examples of the dye include azo, anthraquinone, phthalocyanine, quinoneimine, quinoline, nitro, carbonyl, and methine.
The amount of the colorant used is preferably 10 to 60% by weight when the total solid content of the colored composition is 100% by weight. More preferably, it is 20 to 50% by weight.

<Dispersant>
When making the photosensitive resin composition of this invention into a coloring composition with a pigment, a dispersing agent and a dispersing aid can be used. Thereby, the dispersibility of the pigment can be improved.
As the dispersant, a known one can be used, and a compound having both a hydrophilic part and a lipophilic part is usually used. In particular, a polymer chain having an affinity for a solvent or an alkali-soluble resin, amino A polymer dispersant having a pigment adsorbing group such as a group, a carboxyl group or a phosphoric acid group is preferably used. Examples include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, aliphatic modified polyester dispersants, and the like. Specifically, Disperbik series (manufactured by Big Chemie Japan Co., Ltd.), SOLPERSE series (manufactured by Nippon Lubrizol Co., Ltd.), EFKA series (manufactured by EFKA ADDITIVES), Ajisper series (manufactured by Ajinomoto Fine Techno Co., Ltd.), Dispalon series (manufactured by Enomoto Kasei Co., Ltd.), KP series (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.) and the like are commercially available. These dispersants can be used alone or in admixture of two or more, and the amount used is 0 to 50% by weight, preferably 0 to 30% by weight, based on the total solid content.
Examples of the dispersion aid include a dye derivative having a functional group introduced therein. The base dye structure includes azo, anthraquinone, quinophthalone, phthalocyanine, quinacridone, benzimidazolone, isoindoline, dioxazine, indanthrene, perylene, and diketopyrrolopyrrole. Examples of the functional group of the derivative include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a dialkylamino group, a hydroxyl group, a carboxyl group, and an amide group. These dispersing aids can be used alone or in admixture of two or more.
The amount of the dispersion aid used is preferably 0 to 20% by weight when the total solid content of the coloring composition is 100% by weight. More preferably, it is 0 to 10% by weight.

<Surfactant>
A surfactant can be added to the photosensitive resin composition of the present invention as necessary. Thereby, the leveling property can be improved. Examples of the surfactant include nonionic, fluorine, and silicone. Of these, fluorine-based and silicone-based surfactants are particularly preferable.

<Silane coupling agent>
A silane coupling agent can be added to the photosensitive resin composition of the present invention as necessary. Thereby, adhesiveness can be improved.
Examples of the silane coupling agent include epoxy, methacrylic, amino and the like. Among these, an epoxy-based silane coupling agent is particularly preferable.

<Heat resistance improver>
If necessary, the photosensitive resin composition of the present invention may contain an N- (alkoxymethyl) melamine compound and a compound having two or more epoxy groups. Thereby, heat resistance and strength can be improved.

<Other ingredients>
The photosensitive resin composition of the present invention comprises various additives as required, for example, development improvers such as low molecular carboxylic acids and low molecular carboxylic acid anhydrides, thermal polymerization inhibitors such as p-methoxyphenol, glass, Fillers such as alumina; polymer compounds such as polyvinyl alcohol and polyvinyl pyrrolidone; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole; polyacrylic acid An aggregation inhibitor such as sodium, a thermal polymerization initiator, a plasticizer, and the like can be blended.

The photosensitive resin composition of the present invention comprises the alkali-soluble resin of the present invention and other alkali-soluble resins, polyfunctional monomers, photopolymerization initiators, solvents, if necessary, colorants, dispersants, and other components. Can be prepared by mixing and dispersing using various mixers and dispersers.
When the photosensitive resin composition of the present invention contains a pigment as a colorant, it is produced through a pigment dispersion treatment step. For example, first, a predetermined amount of each of the pigment, solvent, and dispersant is weighed, and the pigment is finely dispersed using a disperser such as a paint conditioner, bead mill, roll mill, ball mill, jet mill, homogenizer, kneader, blender, etc. A dispersion is obtained. Preferably, after kneading and dispersing with a roll mill, kneader, blender or the like, fine dispersion with a media mill such as a bead mill filled with 0.01 to 1 mm zirconia beads. In addition to the pigment, solvent, and dispersant, it is preferable to use an alkali-soluble resin as a dispersion resin in combination or a dispersion aid. To the obtained pigment dispersion, additives such as a solvent, an alkali-soluble resin as a binder resin, a polyfunctional monomer, a photopolymerization initiator, and other surfactants are added and mixed to obtain a uniform dispersion solution. A functional resin composition is obtained. The obtained photosensitive resin composition is desirably filtered through a filter or the like to remove fine dust.

The present invention is also a color filter having a segment formed using the photosensitive resin composition. The segment is a black matrix, each color pixel, a photo spacer, a protective film, or the like.
Examples of the method for forming the color filter segment include a photolithography method, a printing method, an electrodeposition method, and an ink jet method. Photolithographic methods include mainstream negative acrylic photosensitive resin composition (photosensitive acrylic method) and non-photosensitive polyimide resin composition and positive resist (nonphotosensitive polyimide method). There is. Specifically, in the photosensitive acrylic method, a negative photosensitive resin composition is applied onto a support substrate and dried, and then a photomask is overlaid on the formed coating film, and exposure is performed through this photomask. In this method, the exposed portions are photocured, the unexposed portions are developed, washed as necessary, and further heat-cured or photocured to form each color filter segment.

As a form of the color filter, it is a necessary requirement that a pixel is formed on a transparent substrate in the case of a liquid crystal display device, and a photoelectric conversion element substrate in the case of an image pickup tube element. Forming a black matrix that isolates each pixel, forming a protective film on the pixel, forming a photo spacer on the black matrix region, or forming a transparent electrode such as ITO on the pixel or protective film In some cases, an alignment film and an alignment control structure are formed. In some cases, a black matrix and pixels, and a protective film, a photospacer, and the like are formed on a transparent substrate on which TFTs (thin film transistors) are formed.

The color filter of the present invention may be any color filter as long as it has at least one segment formed using the photosensitive resin composition of the present invention. Preferably, the color of all pixels is more preferably black. A matrix and a pixel are formed by using the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention is particularly suitable for a pixel and a black matrix that need to be colored, but is also suitable for forming a segment that does not require coloring, such as a photo spacer or a protective film.

As the transparent substrate constituting the color filter, in addition to a glass plate, a thermoplastic sheet such as polyester, polycarbonate, polyolefin, polysulfone, cyclic olefin ring-opening polymer or hydrogenated product thereof, epoxy resin, unsaturated polyester resin And other thermosetting plastic sheets. Among these, a glass plate or a heat resistant plastic sheet is preferable from the viewpoint of heat resistance. The transparent substrate may be subjected to chemical treatment with a corona discharge treatment, an ozone treatment, a silane coupling agent, or the like, if necessary.

The black matrix constituting the color filter is preferably formed on a support substrate using a metal thin film or a photosensitive colored resin composition for black matrix. The black matrix using the metal thin film is preferably formed of, for example, a single layer of chromium or two layers of chromium and chromium oxide. In this case, first, the metal or metal / metal oxide thin film is formed on the support substrate by vapor deposition, sputtering, or the like. Next, after forming a positive photosensitive film thereon, the photomask is exposed and developed using the photomask to form a black matrix image. Thereafter, the thin film is etched to form a black matrix. When using the photosensitive coloring resin composition for black matrix, a black matrix is formed according to segment formation by said photosensitive acrylic method.

In the case of a liquid crystal display device, the pixels constituting the color filter are usually three colors of red, green, and blue. For example, first, segment formation by the above photosensitive acrylic method using a green photosensitive coloring composition. To form a green pixel. This operation is performed for the remaining two colors to form pixels of three colors. The order of forming the pixels of each color is not particularly limited.
The protective film is formed on the pixels according to the above-described segment formation by the photosensitive acrylic method using the transparent photosensitive resin composition for the protective film after forming the pixels as necessary. In some cases, a protective film is not formed in order to reduce costs and simplify processes. In some cases, such as when a TFT or a photoelectric conversion element is formed on a supporting substrate, a pixel is formed on the protective film after the protective film is formed on the supporting substrate.
When forming a transparent electrode on a pixel or a protective film, using indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), or an alloy thereof, sputtering method, vacuum deposition method, A thin film is formed by a CVD method or the like, and if necessary, a predetermined pattern can be obtained by etching using a positive resist or using a jig. In some liquid crystal driving methods such as a planar alignment driving method (IPS mode), a transparent electrode may not be formed.

The photo spacer constituting the color filter may be formed directly on the black matrix according to the segment formation by the photosensitive acrylic method using the photosensitive resin composition for the photo spacer, if necessary, or in the black matrix region. They are also formed on a protective film or a transparent electrode. In some cases, the cell gap is maintained by a particulate spacer without forming a photospacer.
Examples of the method of applying the photosensitive resin composition to the substrate include spin coating, slit coating, roll coating, and cast coating. When the substrate is large, a method by slit coating is preferable. The thickness of the coating film is usually 0.3 to 3.5 μm in the case of a black matrix, a pixel and a protective film, and is usually 1 to 10 μm in the case of a photospacer.
The coating film after being applied to the substrate is dried using a hot plate, IR oven, convection oven or the like. The drying conditions are appropriately selected according to the boiling point of the solvent component contained, the type of the curing component, the film thickness, the performance of the dryer, etc., but are usually performed at a temperature of 50 to 160 ° C. for 10 seconds to 300 seconds.

The exposure for curing the photosensitive resin composition includes a step of irradiating the coating film with an actinic ray through a predetermined mask pattern. Examples of active light sources include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, fluorescent lamps, argon ion lasers, YAG Laser light sources such as laser, excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser are used. Examples of the exposure system include a proximity system, a mirror projection system, and a stepper system, but the proximity system is preferably used.
After the exposure, the film is developed with a developer to remove unexposed portions and form a pattern. Any developer can be used as long as it dissolves the photosensitive resin composition of the present invention. Usually, an organic solvent or an alkaline aqueous solution is used. When an alkaline aqueous solution is used as the developer, it is preferable to wash with water after development. In addition to the alkaline agent, the alkaline aqueous solution may contain a surfactant, an organic solvent, a buffering agent, a dye, a pigment, and the like as necessary. Alkaline agents include inorganic alkali agents such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate, and sodium bicarbonate. ; Amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc., and these may be used alone or in combination of two or more; Also good.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan acid alkyl esters, monoglyceride alkyl esters; alkylbenzene sulfonates, alkylnaphthalene sulfonic acids, and the like. Anionic surfactants such as salts, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; amphoteric surfactants such as alkyl betaines and amino acids, and the like. These may be used alone or in combination of two or more. Also good.
Examples of the organic solvent include alcohols such as isopropanol, benzyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene glycol, and these may be used alone or in combination of two or more. The development treatment is usually performed at a development temperature of 10 to 50 ° C. by a method such as immersion development, spray development, brush development, or ultrasonic development.
After the development, it is usually heated at a temperature of 150 to 250 ° C. for 5 to 60 minutes using a heating device such as a hot plate, a convection oven, a high-frequency heater, etc., and subjected to a thermosetting treatment.

The present invention comprises the above-described configuration, has a radically polymerizable unsaturated group in the side chain, is excellent in plate making characteristics, and is excellent in storage stability, and can be suitably used for a color filter. Resin.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.

In the following Examples and Comparative Examples, various physical properties of resins or resin solutions were measured as follows.
<Analysis of photosensitive resin>
[Weight average molecular weight]
It measured with the following gel permeation chromatography (GPC) apparatus and conditions.
Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation)
Elution solvent: Tetrahydrofuran standard substance: Tosoh standard polystyrene separation column: TSKgel SuperHZM-M

[Non-volatile content]
About 1 g of the polymer solution was weighed into an aluminum cup, dissolved by adding about 3 g of acetone, and then naturally dried at room temperature. After drying at 120 ° C. for 3 hours using a hot air dryer (manufactured by ESPEC Co., Ltd., PHH-101), the mixture was allowed to cool in a desiccator and the weight was measured. From the weight loss, the nonvolatile content of the polymer solution was calculated.

[Acid value]
The acid value of the polymer solution was measured with an automatic titrator (COM-555, manufactured by Hiranuma Sangyo Co., Ltd.) using a 0.1 N aqueous KOH solution as the titrant. The non-volatile acid value was calculated from the acid value and non-volatile content of the solution.

[Double bond equivalent]
As a simple method, calculation was performed according to the following formula.
Double bond equivalent = (Mw + Cw + Ew + Aw) / Em
Mw: weight of monomer used for polymerization Cw: weight of chain transfer agent used for polymerization Ew: weight of GMA used for monomer addition Aw: weight of acid anhydride used for acid addition Em: used for monomer addition Number of moles of GMA

[Acid anhydride addition amount]
As a simple method, calculation was performed according to the following formula.
Acid anhydride addition amount = number of moles of acid anhydride used for acid anhydride addition / number of moles of GMA used for monomer addition × 100

<Calculation of intermediate acid value>
As a simple method, calculation was performed according to the following formula.
Intermediate acid value = (Ma + Ca−Ea) / (Mw + Cw + Ew) × 1000 × 56.11
Ma: Total number of moles of acid contained in monomer used for polymerization Ca: Total number of moles of acid contained in chain transfer agent used for polymerization Ea: Number of moles of GMA used for monomer addition Mw: Monomer used for polymerization Weight Cw: Weight of chain transfer agent used for polymerization Ew: Weight of GMA used for monomer addition

<Synthesis of photosensitive resin>
[Example 1-1]
As a reaction tank, a four-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was purged with nitrogen. Under a nitrogen stream, 881.6 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was charged into the reaction vessel, and the temperature was raised to 90 ° C. On the other hand, the dropping tank A contains 250.0 parts by weight of benzyl methacrylate (BzMA), 135.0 parts by weight of methyl methacrylate (MMA), 115.0 parts by weight of methacrylic acid (MAA), t-butylperoxy-2- A mixture obtained by thoroughly stirring and mixing 10.0 parts by weight of ethylhexanoate (PBO) was mixed well in the dropping tank B with 25.0 parts by weight of n-dodecyl mercaptan (n-DM) and 47.0 parts by weight of PGMEA. I prepared something.
After confirming that the internal temperature of the reaction tank was stabilized, the dropwise addition of each mixture was started simultaneously from the dropping tanks A and B, and the internal temperature was adjusted to 90 ° C., and dripped over 3 hours from either tank. Then, a polymerization reaction was performed. 30 minutes after the completion of dropping, 2.5 parts by weight of PBO was charged into the reaction vessel, and after 30 minutes, the temperature was raised and the temperature was raised to 115 ° C. 115 ° C. was maintained for 1 hour and then cooled to room temperature.
The gas to be introduced is switched from nitrogen to a nitrogen / oxygen mixed gas (oxygen 7%), 0.2 part by weight of 6-t-butyl-2,4-xylenol (TBXL), 165.1 parts by weight of glycidyl methacrylate (GMA) After adding each substance to the reaction vessel in the order of 2.1 parts by weight of dimethylbenzylamine (DMBA), the monomer addition reaction was performed while stirring and heating were started and the internal temperature was adjusted to 110 ° C. . After maintaining at 110 ° C. for 13 hours, it was cooled to room temperature.
Under a stream of nitrogen / oxygen mixed gas, 58.1 parts by weight of succinic anhydride (SA) was charged into the reaction vessel, and then stirring and heating were started, and while adjusting the internal temperature to 110 ° C., acid anhydride was adjusted. A product addition reaction was carried out. After maintaining at 110 ° C. for 3 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of a photosensitive resin. The analysis results of the solution are shown in Table 1 below.

[Examples 1-2 to 1-6 and Comparative Examples 1-2 to 1-4]
The same procedure as in Example 1-1 was performed except that the type and amount of the charged substance were changed as described in Table 1 below. These results are shown in Table 1 below.

[Comparative Example 1-1]
The procedure was performed in the same manner as in Example 1-1 except that the types and amounts of the charged substances were changed as shown in Table 1 below and the acid anhydride addition reaction was not performed. The results are shown in Table 1 below.

In Table 1 above, all the numerical values for the preparation represent parts by weight.
Moreover, the abbreviations described in Table 1 above represent the following.
PGMEA: propylene glycol monomethyl ether acetate DMDG: diethylene glycol dimethyl ether BzMI: benzyl maleimide BzMA: benzyl methacrylate CHMA: methacrylic acid cyclohexyl MMA: methyl methacrylate MAA: methacrylic acid AA: acrylic acid PBO: t-butylperoxy-2-ethylhexa Noate
n-DM: n-dodecyl mercaptan GMA: glycidyl methacrylate A400: acrylic acid (3,4-epoxycyclohexyl) methyl TBXL: 6-tert-butyl-2,4-xylenol DMBA: dimethylbenzylamine SA: succinic anhydride THPA : Tetrahydrophthalic anhydride

[Example 1-7]
As a reaction tank, a four-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was purged with nitrogen. Under a nitrogen stream, 381.0 parts by weight of PGMEA and 381.0 parts by weight of 2-propanol (IPA) were charged in the reaction vessel, and the temperature was raised until IPA was refluxed. On the other hand, in the dropping tank A, 391.3 parts by weight of MD solution, 300.0 parts by weight of BzMA, 78.0 parts by weight of MMA, 132.0 parts by weight of MAA, and 12.0 parts by weight of PBO were mixed well. Prepared 21.0 parts by weight of 3-mercaptopropionic acid (β-MPA), 25.5 parts by weight of PGMEA, and 25.5 parts by weight of IPA with sufficient stirring and mixing.
After confirming that the reflux state of the reaction tank and the internal temperature were stable, the dropping of each mixture was started simultaneously from the dropping tanks A and B, and the polymerization reaction was carried out by dropping from both tanks over 2.5 hours. went. 30 minutes after the completion of dropping, 3.0 parts by weight of PBO was put into the reaction vessel, and the reflux was further continued for 30 minutes. The temperature of the cooling tube was changed to that for distillation, and then the temperature was raised. While IPA was distilled away, the same amount of PGMEA as that of the distillate was dropped, and the temperature was raised to 115 ° C. After reaching 115 ° C., the cooling tube was replaced with one for refluxing again, and refluxing was maintained for 1 hour, and then cooled to room temperature.
The gas to be introduced was switched from nitrogen to a nitrogen / oxygen mixed gas (oxygen 7%), and after charging each substance in the order of 0.3 parts by weight of TBXL, 198.2 parts by weight of GMA, and 2.5 parts by weight of DMBA, stirring, The monomer addition reaction was performed while starting the temperature increase and adjusting the internal temperature to 110 ° C. After maintaining at 110 ° C. for 13 hours, the cooling tube was replaced with one for distillation, and the temperature was raised to 113 ° C. while reducing the pressure to 37.3 kPa, and IPA was completely distilled off. During the distillation of IPA, the same amount of PGMEA as the distillate was added dropwise. After the system pressure reached 37.3 kPa and the internal temperature reached 113 ° C., the pressure was released to normal pressure and cooled to room temperature.
Under a nitrogen / oxygen mixed gas stream, 69.7 parts by weight of SA was charged into the reaction vessel, and then stirring and heating were started, and an acid anhydride addition reaction was performed while adjusting the internal temperature to 110 ° C. . After maintaining at 110 ° C. for 3 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of an alkali-soluble resin. The analysis results of the solution are shown in Table 2 below.

[Examples 1-8 to 1-12]
The same procedure as in Example 1-7 was conducted, except that the type and amount of the charged substance were changed as shown in Table 2 below. The results are shown in Table 2 below.

[Comparative Example 1-5]
It carried out like Example 1-7 except having changed the kind and quantity of the substance which were prepared as shown in following Table 2, and not having performed acid anhydride addition reaction. The results are shown in Table 2 below.

In Table 2 above, all the numerical values for the preparation represent parts by weight.
The abbreviations described in Table 2 above represent the following.
IPA: 2-propanol MD solution: Dimethyl-2,2 ′-[oxybis (methylene)] bisacrylate dissolved in PGMEA / IPA = 1/1 (weight ratio) mixed solvent to 23% β-MPA : 3-mercaptopropionic acid

[Example 1-13]
As a reaction tank, a four-neck separable flask equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirring device was prepared, and the inside of the reaction tank was purged with nitrogen. Under a nitrogen stream, 801.4 parts by weight of PGMEA was charged into the reaction vessel and heated to 90 ° C. On the other hand, in the dropping tank A, 319.0 parts by weight of styrene (St) and 121.0 parts by weight of MAA were well stirred and mixed. In the dropping tank B, 110.0 parts by weight of BzMI, 220.0 parts by weight of PGMEA, and 14.9 parts of PBO. What mixed the weight part well with stirring was prepared.
After confirming that the internal temperature of the reaction tank was stabilized, the dropping of each mixture was started simultaneously from the dropping tanks A and B, and dropped from the dropping tank A over 5 hours and from the dropping tank B over 7 hours. A polymerization reaction was performed. After completion of dropping, the temperature was maintained at 90 ° C. for 1 hour, and then heated to 115 ° C. Further, 115 ° C. was maintained for 1 hour, and then cooled to room temperature.
The gas to be introduced was changed from nitrogen to a nitrogen / oxygen mixed gas (oxygen 7%), and each substance was charged in the order of 0.2 parts by weight of TBXL, 181.6 parts by weight of GMA, and 2.2 parts by weight of DMBA, and then stirred. The monomer addition reaction was performed while starting the temperature increase and adjusting the internal temperature to 110 ° C. After maintaining at 110 ° C. for 16 hours, it was cooled to room temperature.
Under a nitrogen / oxygen mixed gas stream, 95.9 parts by weight of SA was charged into the reaction vessel, and then stirring and heating were started, and an acid anhydride addition reaction was performed while adjusting the internal temperature to 110 ° C. . After maintaining at 110 ° C. for 3 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of alkali-soluble fat. The analysis results of the solution are shown in Table 3 below.

[Examples 1-14 to 1-17]
The same procedure as in Example 1-13 was carried out except that the kind and amount of the charged substance were changed as shown in Table 3 below. The results are shown in Table 3 below.

[Comparative Example 1-6]
It carried out like Example 1-13 except having changed the kind and quantity of the substance which were prepared as shown in following Table 3, and not having performed acid anhydride addition reaction. The results are shown in Table 3 below.

In Table 3 above, all the numerical values of preparation represent parts by weight.
Abbreviations described in Table 3 above represent the following.
St: Styrene VTl: Vinyl toluene

[Example 2-1]
<Storage stability promotion test>
After the resin solution obtained in Example 1-1 was diluted to 40.0% with PGMEA, the temperature was controlled in a thermostatic bath at 25 ° C., and the viscosity was measured with a B-type viscometer. Then, it put into the resin-made airtight container and preserve | saved with the 85 degreeC dryer.
After storing for one week, it was taken out from the dryer, temperature-controlled in a thermostatic bath at 25 ° C., and the viscosity was measured with a B-type viscometer. The degree of increase compared with the initial viscosity was evaluated according to the following criteria, and then returned to the 85 ° C. dryer after the evaluation.
A: Increase is less than 30% B: Increase is 30% or more and less than 60% Δ: Increase is 60% or more and no gelation ×: Gelation This was performed every 2 weeks up to 8 weeks. The results are shown in Table 4 below.

<Developability test>
(Preparation of pigment dispersion)
As a coloring agent, C.I. I. Pigment Green 36, 10.0 parts by weight, C.I. I. Pigment Yellow 150 is 5.0 parts by weight, Disperbyk-161 (manufactured by Big Chemie) as a dispersant is 1.8 parts by weight (in terms of solid content), and the resin solution obtained in Example 1-1 is used as the dispersion resin solution. 12.0 parts by weight of PGMEA diluted to 0.0%, 71.2 parts by weight of PGMEA as a solvent, 300 parts by weight of zirconia beads having a diameter of 0.5 mm are filled in a stainless steel container and dispersed for 6 hours in a paint shaker To prepare a green pigment dispersion.
(Preparation of colored resin composition)
53.0 parts by weight of the obtained green pigment dispersion, 3.5 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and 40 of the resin solution obtained in Example 1-1 as a binder resin solution 8.5 parts by weight diluted with PGMEA to 0.0%, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1, as a photopolymerization initiator system component 0.9 parts by weight of 2′-biimidazole, 0.3 parts by weight of 2-mercaptobenzothiazole, 0.6 parts by weight of 4,4′-bis (dimethylamino) benzophenone, and 33.2 parts by weight of PGMEA as a solvent After stirring and mixing so as to be uniform, the mixture was filtered through a 1 μm filter to obtain a green colored composition.
(Evaluation of developability)
Using a spin coater, adjust the number of rotations of the green coloring composition on a 100 mm × 100 mm glass substrate on which a chrome black matrix is formed so that the film thickness after drying is 1.5 μm. After coating, it was pre-baked at 90 ° C. for 2 minutes. Next, it exposed at 100 mJ / cm < ² > with the proximity type exposure machine and the pattern mask which has a 10 micrometer width line and space. Then, it developed with 0.1% sodium carbonate aqueous solution using the spray developing device. The development time was 10 to 100 seconds, and was the time for obtaining the best developability. Subsequently, it was washed with water and air-dried. The obtained glass substrate with a green pattern was observed with a laser microscope, and the development residue and the pattern shape were evaluated according to the following criteria.
(1) Development residue ◎: There is no residue in the space portion ○: There is a very thin residue in a part of the space portion △: There is a thin residue in the space portion ×: There is a dark residue in the space portion
(2) Pattern shape ◎: Line edge is straight and sharp ○: Line edge is blurred △: Line edge is totally blurred ×: Line edge is clearly rattled

[Examples 2-2 to 2-17 and Comparative Examples 2-1 to 2-6]
The storage stability and heat resistance were evaluated in the same manner as in Example 1 except that the resin solution used was changed as shown in Table 4. The results are shown in Table 4.

Claims (6)

An alkali-soluble resin obtained by modifying a polymer containing a side chain double bond with a polybasic acid anhydride,
The alkali-soluble resin is an alkali characterized in that a side chain double bond-containing polymer having an acid value of 25 mgKOH / g or less is polybasic acid anhydride-modified and has a double bond equivalent of 400 to 2000. Soluble resin. The alkali-soluble resin is obtained by adding a side chain double bond site having a hydroxyl group by adding an epoxy group-containing monomer to a carboxyl group-containing polymer, and further adding a polybasic acid anhydride to the hydroxyl group. The alkali-soluble resin according to claim 1, which is a polymer obtained. The alkali-soluble resin is a polymer obtained by adding a polybasic acid anhydride to 30 mol% or more of the hydroxyl groups of the side chain double bond sites introduced into the carboxyl group-containing polymer. Item 3. The alkali-soluble resin according to Item 1 or 2. The alkali-soluble resin according to any one of claims 1 to 3, wherein the alkali-soluble resin has a weight average molecular weight of 40000 or less. A photosensitive resin composition for a color filter, comprising the alkali-soluble resin according to claim 1. A color filter comprising the photosensitive resin composition according to claim 5.