JP2018178074A - Radically Polymerizable Polymer and Resin Composition Comprising the Radically Polymerizable Polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrially versatile radical polymerizable polymer having excellent heat resistance, alkali solubility and photocurability. SOLUTION: The carboxyl radical reacts with the carboxyl radical of a polymer having a maleimide-based monomer unit, an unsaturated carboxylic acid unit having no ester bond, and a monomer unit having a hydroxyl group as essential units. A radically polymerizable polymer obtained by reacting a monomer having a functional group to be obtained, and a resin composition containing the radically polymerizable polymer and a radically polymerizable compound are alkaline while having excellent heat resistance. It has been found that it exhibits solubility and photocurability. It can be used as a photosensitive resin composition, and a cured product having excellent heat resistance and adhesion can be obtained. [Selection diagram] None

Description

  The present invention relates to a radically polymerizable polymer soluble in an aqueous alkaline solution and a resin composition comprising the radically polymerizable polymer. More specifically, it relates to a cured product using it.

Since the photosensitive resin composition for image formation can be finely processed by applying the principle of photolithography (photolithography) and can give a cured product excellent in physical properties to form an image, the electronic component relationship It is widely used in applications such as various resist materials and printing plates. In recent years, an alkali developing type that can be developed with a dilute weak alkaline aqueous solution has become mainstream from the point of environmental protection.
When the negative photosensitive resin composition for image formation is used in the step of a photolithography method, first, the resin composition is coated on a substrate and then heat dried to form a coating film. After that, a series of steps of mounting a film for pattern formation on this coating film, exposing and developing it is adopted. In addition to developability, the coating film after photocuring is required to have properties relating to long-term reliability such as heat resistance, water resistance and moisture resistance.

  A carboxyl group-containing vinyl ester in which a carboxyl group is introduced by reacting an acid anhydride with a vinyl ester (epoxy acrylate) obtained by reacting an epoxy resin and (meth) acrylic acid is known as one that satisfies the above respective properties to a certain extent. It is done. This carboxyl group-containing vinyl ester is well-balanced and satisfied with conflicting properties such as tack-free property, photosensitivity, and developability, and important properties such as heat resistance and water resistance required for cured products are also relatively good. Although there is, there is a need for improvement and coexistence at a higher level.

  In keeping with this object, for example, unsaturated group-containing polycarboxylic acids obtained by reacting a (meth) acrylate compound having two carboxyl groups in the molecule with an epoxy resin having two epoxy groups in the molecule. A resin composition containing an acid resin is known to have good important properties such as developability, heat resistance, flexibility and the like (see Patent Document 1). However, with the progress of technology, higher level characteristics are required, for example, it is required to withstand high dimensional stability compatible with fine patterning and processing at higher temperature conditions. It has become so.

  By the way, polymers having an N-substituted maleimide group and an ethylenically unsaturated double bond have been studied as photosensitive resins capable of meeting high heat resistance requirements (for example, Patent Documents 2 and 3). However, even in these systems, too much emphasis on heat resistance may lower the alkali developability or cause the cured product to develop brittleness, and may develop alkali developability, curability, heat resistance, flexibility. There is room for improvement in terms of balance.

JP 2001-48945 A JP 10-139843 A Unexamined-Japanese-Patent No. 2002-62651

  Therefore, an object of the present invention is to provide a radically polymerizable polymer capable of giving a cured product having high thermal decomposition resistance and not exhibiting brittleness while having excellent alkali solubility and curability, and a resin composition containing the same. It is.

The inventors of the present invention, as a result of intensive studies, have found that a specific resin has alkali solubility and curability, and can give a cured product having high thermal decomposition resistance and not exhibiting brittleness.
That is, the object of the present invention is achieved by the following (1) to (8).
(1) In 100% by mass of the polymer, 10 to 60% by mass of a constituent unit derived from a maleimide-based monomer, 10 to 40% by mass of a constituent unit derived from an unsaturated carboxylic acid monomer having no ester bond, A structure in which a monomer having a functional group capable of reacting with the carboxyl group is reacted with a carboxyl group possessed by the polymer containing 10 to 40% by mass of the constituent unit derived from the monomer as an essential unit Radically polymerizable polymer having:
The above-mentioned radical polymerizable polymer has a relative value X / Y of 0.95 or more after heat treatment residual ratio X (mass%) obtained by the following formula and solid content concentration Y (mass%).
After heat treatment Residual ratio X (mass%) = {mass of dried mixture obtained by heating and drying a mixture of 0.3 g of radical polymerizable polymer (mass before heating and drying) and 2 ml of acetone at 200 ° C for 30 minutes ) / {Mass (0.3 (g) before heat drying of the radically polymerizable polymer)}
Solid content concentration Y (mass%) = {mass of solid content obtained by heating and drying radically polymerizable polymer 0.3 g (mass before heating and drying) at 160 ° C. for 1 hour and 30 minutes under a vacuum} / {Mass 0.3 (g) before drying by heating of radically polymerizable polymer}
(2) The radically polymerizable polymer according to (1), further comprising 1 to 35% by mass of a structural unit derived from an aromatic monomer having no ester bond in 100% by mass of the polymer.
(3) The radically polymerizable polymer as described in (1) or (2) whose structural unit derived from the unsaturated carboxylic acid monomer which does not have the said ester bond is a structural unit derived from (meth) acrylic acid.
(4) A resin composition comprising the radically polymerizable polymer according to any one of (1) to (3) and a radically polymerizable compound.
(5) A cured product obtained by curing the radically polymerizable polymer according to any one of (1) to (3) or the resin composition according to (4).
(6) the following formulas (1) and (2)
After heat treatment Residual ratio X (mass%) = {mass of dried mixture obtained by heating and drying a mixture of 0.3 g of radical polymerizable polymer (mass before heating and drying) and 2 ml of acetone at 200 ° C for 30 minutes ) / {Mass (0.3 (g) before heat drying of radically polymerizable polymer)} (1)
Solid content concentration Y (mass%) = {mass of solid content obtained by heating and drying radically polymerizable polymer 0.3 g (mass before heating and drying) at 160 ° C. for 1 hour and 30 minutes under a vacuum} / {Mass 0.3 (g) before drying by heating of radically polymerizable polymer} (2)
A method for producing a radically polymerizable polymer, wherein the relative value X / Y of the after-heat treatment residual ratio X (mass%) and the solid content concentration Y (mass%) obtained by
10 to 60 mass% of a maleimide-based monomer, 10 to 40 mass% of an unsaturated carboxylic acid monomer having no ester bond, and 10 to 40 mass of a monomer having a hydroxyl group in 100 mass% of the monomer component B. reacting the above-mentioned monomer component essentially containing C. to obtain a polymer,
Reacting a monomer having a functional group capable of reacting with the carboxyl group with a carboxyl group of the polymer to obtain a radically polymerizable polymer;
A method of producing a radically polymerizable polymer comprising:
(7) Furthermore, the manufacturing method of the radically polymerizable polymer as described in (6) which contains 1-35 mass% of aromatic monomers which do not have an ester bond in 100 mass% of said monomer components. .
(8) The method for producing a radically polymerizable polymer according to (6) or (7), wherein the polymer is obtained by polymerizing in a mixed solvent of an ester and an alcohol.

  The radically polymerizable polymer of the present invention and the resin composition containing the same have good alkali solubility and curability, and the resulting cured product has high thermal decomposition resistance and does not exhibit brittleness, and when it is used as a coating film It is excellent in adhesion to the material.

The radically polymerizable polymer of the present invention essentially comprises a constituent unit derived from a maleimide-based monomer, a constituent unit derived from an unsaturated carboxylic acid monomer having no ester bond, and a constituent unit derived from a monomer having a hydroxyl group. It has a structure in which a monomer having a functional group capable of reacting with a carboxyl group is reacted with a carboxyl group of a polymer (base polymer) having as a unit. The said carboxyl group is contained in the structural unit derived from the unsaturated carboxylic acid monomer which does not have the said ester bond in the said polymer (base polymer). In the radically polymerizable polymer of the present invention, a functional group capable of reacting with a carboxyl group is preferably included in part of the carboxyl group of the constituent unit derived from the unsaturated carboxylic acid monomer having no ester bond. It has a structure in which the monomer which it has is made to add.
In the radical polymerizable polymer, constituent units derived from the polymer (base polymer) constitute a main chain. The structural unit derived from the monomer having a functional group capable of reacting with the carboxyl group constitutes the side chain of the radically polymerizable polymer.
The monomer having a functional group capable of reacting with a carboxyl group preferably has a radically polymerizable carbon-carbon double bond (hereinafter sometimes simply referred to as a radically polymerizable double bond).
The radically polymerizable polymer of the present invention is preferably derived from 10 to 60% by mass of a structural unit derived from a maleimide-based monomer, and from an unsaturated carboxylic acid monomer having no ester bond in 100% by mass of the main chain. It contains 10 to 40% by mass of a constituent unit and 10 to 40% by mass of a constituent unit derived from a monomer having a hydroxyl group, and has a radically polymerizable carbon-carbon double bond in the side chain.
In addition, in the following, the description with a monomer unit shows the structural unit derived from a monomer, and the polymerizable carbon-carbon double bond (C = C) in the said monomer is single bond (C-). C) means the structural unit that became For example, the maleimide-based monomer unit means a structural unit derived from the maleimide-based monomer when the maleimide-based monomer is copolymerized or graft-polymerized.

  A polymer (base polymer) having a maleimide-based monomer unit, an unsaturated carboxylic acid (monomer) unit having no ester bond, and a monomer unit having a hydroxyl group as an essential unit is a maleimide-based monomer, It is preferably obtained by radical polymerization of an unsaturated carboxylic acid having no ester bond and a monomer having a hydroxyl group as an essential component. The monomers are described below.

As a maleimide-based monomer, N-phenyl maleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2, 6-diethylphenyl) maleimide, N- (2- Chlorophenyl) maleimide, N-methyl maleimide, N-ethyl maleimide, N-isopropyl maleimide, N-lauryl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-phenyl methyl maleimide, N- (2,4,6- tri Bromophenyl) maleimide, N- [3- (triethoxysilyl) propyl] maleimide, N-octadecenyl maleimide, N-dodecenyl maleimide, N- (2-methoxyphenyl) maleimide, N- (2, 2, 4,6-Trichlorophenyl) maleimide, N- (4-hydroxyphenyl) ) Maleimide, N- (1-hydroxyphenyl) include N- substituted maleimides or unsubstituted maleimides such as maleimide, may be used singly or in combination of two or more thereof. Among these, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (2,6-diethylphenyl) in that the heat resistance improving effect is large, the copolymerizability is good, and it is easy to obtain. Maleimide, N-lauryl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, etc. are preferred, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide is more preferred, N-phenyl maleimide, N-benzyl maleimide is most preferred .
Moreover, it is also preferable to use N-phenyl maleimide and N-benzyl maleimide in combination. When using together, the preferable ratio of N-phenyl maleimide and N- benzyl maleimide is 99: 1-1: 99 by mass ratio.

  Further, in the present invention, in order to introduce a carboxyl group which is essential for alkali development and to make the cured product excellent in addition, an unsaturated carboxylic acid having no ester bond as a monomer is used as an essential component . Specific examples thereof include (meth) acrylic acid, crotonic acid, cinnamic acid, sorbic acid, fumaric acid, and maleic acid. Among them, (meth) acrylic acid is preferable because of its excellent cured product properties. In another embodiment, another acid group may be introduced together with or in place of the carboxyl group. Examples of other acid groups include phenolic hydroxyl groups, carboxylic acid anhydride groups, phosphoric acid groups, sulfonic acid groups, and other functional groups that are neutralized with alkaline water, and have only one of these. Or you may have 2 or more types. In the following description, the statements for the carboxyl group also apply to the other acid groups mentioned above.

  In the present invention, a monomer having a hydroxyl group (hydroxyl group) is used as an essential component. Conventionally, as a polymer having a carboxyl group, one obtained by copolymerizing (meth) acrylic acid is known, but there is room for improvement in terms of alkali developability, and hydroxyl group is a method for improving alkali developability. And glycidyl in the glycidyl group-containing skeleton as described in Patent Document 3 and in which polybasic acid anhydride is reacted to the hydroxyl group in the hydroxyl group-containing skeleton by copolymerizing monomer units having It is known that an unsaturated monobasic acid such as (meth) acrylic acid is reacted with a group and a polybasic acid anhydride is reacted with a hydroxyl group formed by ring opening of a glycidyl group. However, there is room for improvement in terms of both alkali developability and heat resistance.

  On the other hand, in the present invention, good alkali developability can be expressed by copolymerizing the unsaturated carboxylic acid having no ester bond, the monomer having a hydroxyl group, and both as essential components. It can also be excellent in the properties of the cured product. As a monomer having a hydroxyl group in the molecule, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy (meth) acrylate (Di) hydroxyalkyl (meth) acrylates such as butyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-hydroxymethyl (Meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylamide, 3-hydroxypropyl (meth) acrylamide, 4-hydroxybutyl (meth) acrylamide, hydroxypivalyl (meth) acrylamide, 5 -Hydroxy-pliers (Meth) acrylamide, 6-hydroxyhexyl (meth) include hydroxyalkyl (meth) acrylamides such as acrylamide, one or more of these can be used. Among them, from the viewpoint of copolymerizability, hydroxyalkyl (meth) acrylate is preferable, and 2-hydroxyethyl (meth) acrylate is particularly preferable.

  The maleimide-based monomer (maleimide-based monomer unit) is 10 to 60% by mass in all the monomer components (100% by mass of all the monomer units constituting the base polymer) constituting the base polymer. By making content of a maleimide-type monomer 10 mass% or more, sufficient heat resistance can be provided to hardened | cured material. On the other hand, by setting the content to 60% by mass or less, the alkali developability and the cured product characteristics attributed to the unsaturated carboxylic acid and the monomer having a hydroxyl group can be sufficiently imparted. The lower limit of the maleimide monomer is preferably 15% by mass, and more preferably 20% by mass. The upper limit is preferably 55% by mass, and more preferably 50% by mass.

  The unsaturated carboxylic acid having no ester bond (unsaturated carboxylic acid unit having no ester bond) comprises all monomer components constituting the base polymer (100% by mass of all monomer units constituting the base polymer) The content is 10 to 40% by mass. By setting the content of unsaturated carboxylic acid to 10% by mass or more, good alkali developability can be exhibited. On the other hand, by setting the content to 40% by mass or less, cured product properties such as heat resistance attributed to the maleimide-based monomer can be sufficiently imparted. The lower limit of the unsaturated carboxylic acid is preferably 15% by mass, and more preferably 20% by mass. The upper limit is preferably 35% by mass, and more preferably 30% by mass.

  The monomer having a hydroxyl group (monomer unit having a hydroxyl group) is 10 to 40% by mass in all the monomer components constituting the base polymer (100% by mass of all monomer units constituting the base polymer) . By setting the content of the monomer having a hydroxyl group to 10% by mass or more, good alkali developability can be exhibited. On the other hand, by setting the content to 40% by mass or less, cured product properties such as heat resistance attributed to the maleimide-based monomer can be sufficiently imparted. The lower limit of the monomer having a hydroxyl group is preferably 12% by mass, and more preferably 15% by mass. The upper limit is preferably 35% by mass, and more preferably 30% by mass.

In the present invention, other copolymerizable monomer components may be used in obtaining a polymer (base polymer) as long as the properties are not adversely affected.
Specific examples of such monomer components include aromatic monomers having no ester bond; vinyl ester monomers such as vinyl acetate and vinyl adipate; methyl (meth) acrylate, ethyl (meth) acrylate, (Meth) acrylic monomers such as butyl (meth) acrylate; n-propyl vinyl ethers, isopropyl vinyl ethers, n-butyl vinyl ethers, isobutyl vinyl ethers, n-hexyl vinyl ethers, alkyl vinyl ethers such as cyclohexyl vinyl ethers, 2-ethylhexyl vinyl ethers and the like Alkyl vinyl (thio) ethers; acid anhydride group-containing monomers such as maleic anhydride or monomers obtained by ring-opening modification of acid anhydride groups with alcohols etc. and unsaturated basic acids other than those mentioned above N-vinylpyrrolidone N- vinyl monomers such as N- vinyl oxazolidone; acrylonitrile, cyano group-containing monomers such as methacrylonitrile, and the like.

  Among these, an aromatic monomer having no ester bond is preferable because the copolymerizability with a maleimide monomer is good and the characteristics of the cured product are also excellent. Specific examples thereof include styrene, α-methylstyrene, α-chlorostyrene, vinyl toluene and the like, and styrene is most preferable in terms of excellent electric characteristics and inexpensiveness.

The total content of the other copolymerizable monomer components is preferably 0 to 100% by mass of all monomer components constituting the base polymer (100% by mass of all monomer units constituting the base polymer). It is 70% by mass, more preferably 0 to 55% by mass, and still more preferably 0 to 20% by mass.
In addition, an aromatic monomer having no ester bond (aromatic monomer unit having no ester bond) is an entire monomer component constituting the base polymer (an entire unit amount constituting the base polymer) It is preferable to be contained in an amount of 1 to 35% by mass in 100% by mass of the body unit. By setting the content of the aromatic monomer having no ester bond to 1% by mass or more, cured product properties can be more sufficiently imparted. On the other hand, by setting the content to 35% by mass or less, the heat resistance and the alkali developability resulting from the maleimide-based monomer, the unsaturated carboxylic acid, and the monomer having a hydroxyl group can be sufficiently imparted. A more preferable lower limit of the aromatic monomer having no ester bond is 5% by mass, a further preferable lower limit is 7% by mass, and a particularly preferable lower limit is 8% by mass. Moreover, a more preferable upper limit is 33 mass%, and a still more preferable upper limit is 30 mass%.

The method for producing a radically polymerizable polymer of the present invention is represented by the following formulas (1) and (2)
After heat treatment Residual ratio X (mass%) = {mass of dried mixture obtained by heating and drying a mixture of 0.3 g of radical polymerizable polymer (mass before heating and drying) and 2 ml of acetone at 200 ° C for 30 minutes ) / {Mass (0.3 (g) before heat drying of radically polymerizable polymer)} (1)
Solid content concentration Y (mass%) = {mass of solid content obtained by heating and drying radically polymerizable polymer 0.3 g (mass before heating and drying) at 160 ° C. for 1 hour and 30 minutes under a vacuum} / {Mass 0.3 (g) before drying by heating of radically polymerizable polymer} (2)
A method for producing a radically polymerizable polymer, wherein the relative value X / Y of the after-heat treatment residual ratio X (mass%) and the solid content concentration Y (mass%) obtained by
10 to 60 mass% of a maleimide-based monomer, 10 to 40 mass% of an unsaturated carboxylic acid monomer having no ester bond, and 10 to 40 mass of a monomer having a hydroxyl group in 100 mass% of the monomer component B. reacting the above-mentioned monomer component essentially containing C. to obtain a polymer (base polymer);
Reacting a monomer having a functional group capable of reacting with the carboxyl group with a carboxyl group of the polymer to obtain a radically polymerizable polymer;
Contains.

In the step of obtaining the polymer (base polymer) by reacting the monomer components, the method of obtaining the polymer is not particularly limited, and it is possible to adopt conventionally known polymerization methods such as solution polymerization method and bulk polymerization method. is there. Among them, a solution polymerization method in which temperature control during the polymerization reaction is easy is preferable.
The solvent in the solution polymerization is not particularly limited as long as it is a solvent which does not have the possibility of inhibiting the polymerization or deteriorating the components of the raw material monomers. Specific examples of usable solvents include hydrocarbons such as toluene and xylene; cellosolve acetate, carbitol acetate, (di) propylene glycol monomethyl ether acetate, glutaric acid (di) methyl, succinic acid (di) methyl, adipine Esters such as acid (di) methyl, methyl acetate, ethyl acetate, butyl acetate, methyl propionate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, Examples thereof include ethers such as methyl-t-butyl ether and (di) ethylene glycol dimethyl ether; amides such as N, N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide and the like; Others can be used in combination of two or more. In particular, when the amount of use of the maleimide monomer exceeds 30% by mass, or when the amount of use of the unsaturated carboxylic acid such as (meth) acrylic acid exceeds 30% by mass, the monomer or polymer In order to improve the solubility of the solvent, a mixed solvent of an ester such as propylene glycol monomethyl ether acetate or carbitol acetate and an alcohol such as propylene glycol monomethyl ether or isopropanol is preferable.

  As a polymerization initiator which can be used at the time of polymerization reaction, a usual radical polymerization initiator is mentioned. Specifically, 2,2'-azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) Azo compounds such as 2,2′-azobis (2-methylisobutyronitrile); lauroyl peroxide, benzoyl peroxide, t-butylperoxy neodecanate, t-butylperoxypivalate, t- Examples include organic peroxides such as amyl peroxy octoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy benzoate, methyl ethyl ketone peroxide, dicumyl peroxide, etc. It may be appropriately selected and used according to the conditions and the required characteristics for the obtained polymer.

  The amount of the polymerization initiator used is preferably 0.001 to 15% by mass, and more preferably 0.01 to 10% by mass, with respect to 100% by mass of the monomer component used in the polymerization reaction. is there.

  A specific method for obtaining a polymer (base polymer) is not particularly limited. However, a method in which all components are charged at once into a solvent and polymerized, and the remaining components in a reaction vessel in which a part of the solvent and components are charged in advance. A method of continuously adding or sequentially adding and polymerizing can be adopted.

In the production of a polymer (base polymer), 10 to 60% by mass of a maleimide-based monomer and 10 to 40% of an unsaturated carboxylic acid monomer having no ester bond in all the monomer components constituting the base polymer It is preferable to radically polymerize a monomer having 10% to 40% by mass of a monomer having a hydroxyl group as an essential component using the above-mentioned polymerization initiator.
It is preferable to further contain 1 to 35% by mass of an aromatic monomer having no ester bond in the above-mentioned all monomer components.

  There is no particular limitation on the pressure at the time of reaction, and the reaction may be performed under any conditions of normal pressure and pressure. The temperature at the time of polymerization reaction depends on the type and composition ratio of the raw material monomers used and the type of solvent used, but usually it is preferably in the range of 20 to 150 ° C., more preferably 30 to 120 ° C. .

  During the polymerization reaction, it is preferable to set the amount of the solvent and each monomer component such that the final solid concentration of the polymer solution is 10 to 70% by mass. If this final solid content concentration is less than 10% by mass, productivity is unfavorably low. On the other hand, when the final solid content concentration exceeds 70% by mass, the viscosity of the polymerization solution may increase and the polymerization conversion may not increase even in the case of solution polymerization. The more preferable final solid concentration is 20 to 65% by mass, and more preferably 25 to 60% by mass.

Considering the characteristics as the radically polymerizable polymer of the present invention and the resin composition comprising the radically polymerizable polymer, the alkali developability, the cured film physical properties, the heat resistance, etc., the weight average molecular weight Mw of the polymer As a value when it measures by gel permeation chromatography (GPC), 1,000-100,000 are preferable at a polystyrene conversion value. By setting Mw to 1,000 or more, sufficient heat resistance can be imparted to the cured product. On the other hand, sufficient alkali developability can be provided by setting Mw to 100,000 or less. A more preferable lower limit of Mw is 2,000, and a further preferable lower limit is 3,000. Moreover, a more preferable upper limit is 50,000, and a still more preferable upper limit is 30,000.
A chain transfer agent may be used during the polymerization reaction, if necessary, in order to adjust the molecular weight within this range, but by not using it, a resin composition free of mercaptan odor can be obtained.

  As a chain transfer agent which can be used when it is used, any one which does not adversely affect each monomer component used for polymerization, a thiol compound is usually used. Specifically, alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan and t-dodecyl mercaptan; aryl mercaptans such as thiophenol; mercapto group-containing aliphatic carboxylic acids such as mercapto propionic acid and methyl mercapto propionate; Ester etc. are mentioned as a preferable thing. The use amount of the chain transfer agent is not particularly limited and may be appropriately adjusted so as to obtain a polymer having a desired molecular weight, but generally, it is 0 based on the total amount of monomers used for polymerization. The content is preferably in the range of 1 to 15% by mass, and more preferably 0.5 to 10% by mass.

  Next, in the step of obtaining a radically polymerizable polymer, a monomer having a functional group capable of reacting with the carboxyl group is reacted with a carboxyl group possessed by the polymer (base polymer) to impart radical polymerization property. , To obtain a radically polymerizable polymer. In order to impart radical polymerizability, preferably, a radical polymerizable carbon-carbon double bond introduction reaction is carried out. The radically polymerizable group (preferably carbon-carbon double bond) introduction reaction comprises the carboxyl group of the above polymer, a functional group capable of reacting with the carboxyl group, and a radically polymerizable group (preferably carbon-carbon double bond) And a polymerization inhibitor such as methyl hydroquinone and oxygen, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzyl ammonium chloride, and 2-ethyl-4-methyl. The reaction can be performed at about 80 to 130 ° C. in the coexistence of a reaction catalyst such as imidazoles such as imidazole, phosphorus compounds such as triphenylphosphine, organic acid salts and inorganic acid salts of metals, and chelate compounds. In another embodiment, it may be reacted with the above-mentioned other acid group together with or in place of the carboxyl group.

  The functional group capable of reacting with an acid group such as a carboxyl group is preferably selected from the group consisting of glycidyl group, oxazolinyl group, isocyanate group and oxetanyl group. The radically polymerizable carbon-carbon double bond is preferably a (meth) acryloyl group.

  Specific examples of the monomer having a glycidyl group include glycidyl (meth) acrylate, allyl glycidyl ether, α-ethyl glycidyl (meth) acrylate, 3,4-epoxycyclohexyl methyl acrylate (eg, “manufactured by Daicel Chemical Industries, Ltd. Cyclomer A400 "and the like), 3,4-epoxycyclohexylmethyl methacrylate (for example," Cyclomer M100 "and the like manufactured by Daicel Chemical Industries, Ltd.), and the like.

  As a specific example of the monomer which has an oxazolinyl group, N-vinyl oxazoline, 2-isopropenyl 2-oxazoline, etc. are mentioned.

  Specific examples of the monomer having an isocyanate group include (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxyethoxyethyl isocyanate, bis (acryloxymethyl) ethyl isocyanate, and modified products thereof. More specifically, "Kalen MOI" (methacryloyloxyethyl isocyanate), "Kalen AOI" (acryloyloxy ethoxyethyl isocyanate), "Kalen MOI-EG" (methacryloyloxy ethoxyethyl isocyanate), "Kalen MOI-BM" ( Isocyanate block of Karenz MOI), "Kalens MOIBP" (isocyanate block of Karenz MOI), and "Karenz BEI" (bis (acryloxymethyl) ethyl isocyanate) are commercially available from Showa Denko. All of these product names are registered trademarks.

  Specific examples of the monomer having an oxetanyl group include 3- (meth) acryloyloxymethyl oxetane and 3-ethyl-3- (meth) acryloyloxymethyl oxetane.

  One or more of these monomers can be used. Among these, glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl methacrylate are preferable from the viewpoint of reactivity and industrial availability. Particularly preferred are glycidyl methacrylate and 3,4-epoxycyclohexylmethyl methacrylate.

  In the radically polymerizable polymer of the present invention, it is preferable to carry out a radically polymerizable carbon-carbon double bond introducing reaction so that the double bond equivalent is 600 to 4000 g / equivalent. The double bond equivalent is related to the photo-curing property and the physical properties of the cured product, and by setting it in the above range, a cured product excellent in physical properties such as heat resistance, strength and flexibility can be obtained. In addition, a photosensitive resin can be obtained in which a balance between photocurability and alkali developability is obtained. A more preferable range of the double bond equivalent is 700 to 3000 g / equivalent, more preferably 800 to 2500 g / equivalent.

  The acid value of the radically polymerizable polymer obtained as described above is preferably 30 mg KOH / g or more, more preferably 40 mg KOH / g or more, further preferably 50 mg KOH / g or more, and preferably 160 mg KOH / g or less, 155 mg KOH / g. g or less is more preferable, and 150 mg KOH / g or less is more preferable. By setting the acid value of the radically polymerizable polymer to 30 mg KOH / g or more, it becomes easy to develop good alkali developability. When the acid value of the radically polymerizable polymer is 160 mg KOH / g or less, the exposed portion is less likely to be corroded by the alkali developer, and the water resistance and moisture resistance of the cured product are improved.

  The amount of the monomer having a functional group capable of reacting with a carboxyl group is 0.01 to 0.99 per equivalent of the carboxyl group possessed by the polymer prior to the radical polymerizable carbon-carbon double bond introducing reaction. It is preferable to determine so that the double bond equivalent and the acid value of the radically polymerizable polymer to be obtained fall within the above-mentioned preferable range within the range of the equivalent. In addition, the suitable range of Mw of the radically polymerizable polymer of this invention is the same as the suitable range of Mw of the polymer before the said radically polymerizable carbon-carbon double bond introduction reaction.

The radical polymerizable polymer of the present invention has a relative value X / Y of 0.95 or more after heat treatment residual ratio X (mass%) obtained by the following formula and solid content concentration Y (mass%).
After heat treatment Residual ratio X (mass%) = {mass of dried mixture obtained by heating and drying a mixture of 0.3 g of radical polymerizable polymer (mass before heating and drying) and 2 ml of acetone at 200 ° C for 30 minutes ) / {Mass (0.3 (g) before heat drying of the radically polymerizable polymer)}
Solid content concentration Y (mass%) = {mass of solid content obtained by heating and drying radically polymerizable polymer 0.3 g (mass before heating and drying) at 160 ° C. for 1 hour and 30 minutes under a vacuum} / {Mass 0.3 (g) before drying by heating of radically polymerizable polymer}

  In the above formula, the radical polymerizable polymer may contain the above solvent. The heating and drying of the radically polymerizable polymer is preferably performed in a container with high thermal conductivity such as an aluminum cup. With regard to the mass 0.3 g of the radically polymerizable polymer before heating and drying, the precisely weighed mass may be known, and may be around 0.3 g (for example, 0.28 to 0.32 g).

  In the radically polymerizable polymer of the present invention, 10 to 60% by mass of a constitutional unit derived from a maleimide-based monomer in 100% by mass of constitutional units derived from all the monomers of the polymer before radically polymerizable group introduction reaction, ester Since it has 10 to 40 mass% of structural units derived from unsaturated carboxylic acid monomer having no bond and 10 to 40 mass% of structural units derived from monomers having a hydroxyl group as an essential unit, the ester bond content is It can be kept low and excellent thermal decomposition resistance can be obtained.

  The relative value X / Y is 1 when no thermal decomposition occurs, and the closer the relative value X / Y is to 1, the better the heat decomposition resistance. The relative value X / Y is preferably 0.96 or more, more preferably 0.97 or more, and still more preferably 0.98 or more.

  Since the radically polymerizable polymer of the present invention has both a carboxyl group and a radically polymerizable group (preferably a radically polymerizable carbon-carbon double bond), it should be an alkali-soluble photosensitive resin alone. You can also. In particular, it can be suitably used as a negative type alkali-soluble photosensitive resin.

  In the present invention, by using a resin composition containing a radically polymerizable polymer and a known radically polymerizable compound, a coating film having a crosslinked structure can be obtained through heat or light reaction. Such radically polymerizable compounds include radically polymerizable resins and radically polymerizable monomers.

  Unsaturated polyester, epoxy acrylate, urethane acrylate, polyester acrylate etc. can be used as radically polymerizable resin. When using these radically polymerizable resin, it is preferable to use a radically polymerizable resin in 80 mass parts or less with respect to 100 mass parts of radically polymerizable polymers of this invention. A more preferable upper limit is 70 parts by mass, and a further preferable upper limit is 60 parts by mass.

As a radically polymerizable monomer, any of a monofunctional monomer (one radically polymerizable double bond) and a polyfunctional monomer (two or more radically polymerizable double bonds) can be used. Since the radically polymerizable monomer participates in polymerization, the viscosity of the resin composition can also be adjusted in addition to improving the properties of the resulting cured product. The preferable amount used in the case of using a radically polymerizable monomer is 300 parts by mass or less, more preferably 100 parts by mass or less, with respect to 100 parts by mass of the radically polymerizable polymer of the present invention. The preferable lower limit value is 1 part by mass, more preferably 5 parts by mass with respect to 100 parts by mass of the radically polymerizable polymer.
Specific examples of the radically polymerizable monomer include N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- ( 2-Chlorophenyl) maleimide, N-methyl maleimide, N-ethyl maleimide, N-isopropyl maleimide, N-lauryl maleimide, N-cyclohexyl maleimide, N-phenylmethyl maleimide, N- (2,4,6-tribromophenyl) Maleimide, N- [3- (triethoxysilyl) propyl] maleimide, N-octadecenyl maleimide, N-dodecenyl maleimide, N- (2-methoxyphenyl) maleimide, N- (2,4,6 -Trichlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide N-substituted maleimide group-containing monomers such as N- (1-hydroxyphenyl) maleimide; styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, p-hydroxystyrene, divinylbenzene, diallyl phthalate, diallylbenzene Aromatic vinyl monomers such as phosphonates; vinyl ester monomers such as vinyl acetate and vinyl adipate; (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxy Ethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxymethyl (meth) acrylamide, pentaerythritol mono (meth) Acrylate, dipentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, glycerol mono (meth) acrylate, (di) ethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris [2- (meth) acrylate Acryloyloxyethyl] triazine, (meth) acrylic monomers such as dendritic acrylate; n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl (Hydroxy) alkylvinyl (thio) ethers such as dithioether, isobutylvinylether, n-hexylvinylether, cyclohexylvinylether, 2-ethylhexylvinylether, 4-hydroxybutylvinylether etc; 2- (vinyloxyethoxy) ethyl (meth) acrylate ( (Meth) acrylic acid 2- (isopropenoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropenoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropenoxyethoxyethoxyethoxy) ethyl etc. (Thio) ethers having a radically polymerizable double bond; acid anhydride group-containing monomers such as maleic anhydride or monomers obtained by ring-opening modification of acid anhydride groups with alcohols, amines, water, etc. Mer; N- N-vinyl monomers such as vinyl pyrrolidone and N-vinyl oxazolidone; compounds having one or more radically polymerizable double bonds such as allyl alcohol and triallyl cyanurate.
These are suitably selected according to a use or a required characteristic, and 1 type or 2 or more types can be mixed and used.

  The resin composition comprising the radically polymerizable polymer of the present invention and the radically polymerizable compound can also be thermally polymerized by using a known thermal polymerization initiator such as benzoyl peroxide or cumene hydroperoxide. However, radical polymerization by light becomes possible by setting it as the photosensitive resin composition which mix | blended the photoinitiator. In particular, it can be set as a negative photosensitive resin composition.

  As the photopolymerization initiator, known ones can be used, and benzoins such as benzoin, benzoin methyl ether and benzoin ethyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone Acetophenones such as 4- (1-t-butyldioxy-1-methylethyl) acetophenone; 2-methylanthraquinone, 2-amyl anthraquinone, 2-t-butyl anthraquinone, anthraquinones such as 1-chloroanthraquinone; 2,4 Thioxanthones such as dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4- (1- (1-) Benzophenones such as -butyldioxy-1-methylethyl) benzophenone and 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone; 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; acyl phosphine oxides and xanthones.

  These photopolymerization initiators are used as one or a mixture of two or more, and are contained in an amount of 0.5 to 30 parts by mass with respect to 100 parts by mass of the radically polymerizable polymer of the present invention and the radically polymerizable compound. Is preferred. When the amount of the photopolymerization initiator is less than 0.5 parts by mass, it is necessary to increase the light irradiation time, or polymerization is difficult to occur even when the light irradiation is performed, so that an appropriate surface hardness is obtained. It disappears. In addition, even if it mix | blends a photoinitiator with more than 30 mass parts, the merit used in large quantities is small.

  In the resin composition of the present invention, if necessary, fillers such as talc, clay and barium sulfate, pigments for coloring, antifoaming agents, coupling agents, leveling agents, sensitizers, mold release agents and lubricants You may add well-known additives, such as a plasticizer, antioxidant, a ultraviolet absorber, a flame retardant, a polymerization inhibitor, a thickener. In addition, various reinforcing fibers can be used as reinforcing fibers to make a fiber reinforced composite material.

  When the resin composition comprising the radically polymerizable polymer of the present invention and the radically polymerizable compound is used for image formation, it is usually coated on a substrate by a known method, dried, exposed and cured. After obtaining the coating film, the unexposed area is dissolved in an aqueous alkali solution to carry out alkali development.

  Specific examples of the alkali usable for development include, for example, alkali metal compounds such as sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide; alkaline earth metal compounds such as calcium hydroxide; ammonia; monomethylamine, dimethylamine , Trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, triethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, dimethyl And water soluble organic amines such as aminoethyl methacrylate and polyethylene imine. It can be used one or more.

The resin composition of the present invention can also be used in the form of a dry film which is previously applied to a film such as polyethylene terephthalate and dried, in addition to a method of directly applying a liquid one to a substrate. In this case, a dry film may be laminated on a substrate, and the film may be peeled off before or after exposure.
In addition, CTP (Computer To Plate) system, which is widely used recently in the field of printing and plate making, that is, without exposure to a film for pattern formation during exposure, laser light is directly scanned and exposed onto a coating film by digitized data. The method of drawing can be adopted.

  Hereinafter, the present invention will be described in more detail by way of examples, but the following examples do not limit the present invention, and all modifications and variations within the scope of the present invention are included in the technical scope of the present invention. Be done. In each example, parts and percentages are by weight unless otherwise stated. In the following examples, physical properties were evaluated as follows.

In the following examples, various physical properties and the like were measured as follows.
<Acid number>
About 0.3 g of each solution was precisely weighed, dissolved in an acetone / water mixed solvent, and an aqueous solution of 0.1 N KOH was used as a titration solution, and the acid value was measured by an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd.).

<Weight average molecular weight (Mw)>
The weight average molecular weight was measured by GPC (gel permeation chromatography) method using HLC-8220GPC (manufactured by Tosoh Corporation) using polystyrene as a standard substance and tetrahydrofuran as an eluent.

<Heat resistant decomposition resistance>
About 0.3 g of each solution was accurately weighed in an aluminum cup, approximately 2 ml of acetone was added, mixed well, and then placed in a hot-air dryer at 200 ° C. The mass after drying by heating for 30 minutes was measured, and the mass after drying by heating at 200 ° C. was divided by the mass before drying by heating to determine the residual ratio after heat treatment X (%). It evaluated by the relative value (X / Y) with solid content concentration Y (%) obtained by making this X (%) heat-dry at 160 degreeC under vacuum for 1 hour 30 minutes, and obtain it. The larger the value, the higher the heat decomposition resistance.

<Alkali solubility>
The solution obtained by the formulation shown in the table is applied on a copper plate by spin coating, dried at 80 ° C. for 30 minutes, cooled to room temperature, and immersed in a 30 ° C. 1 mass% aqueous solution of sodium carbonate to coat It evaluated by solubility.

<Photo-curing property>
After irradiating the light of ² J / cm < ² > to the test board for alkali solubility evaluations obtained above, it immersed in 30 degreeC 1 mass% sodium carbonate aqueous solution, and evaluated.

<Cold cycle test resistance (TCT resistance)>
The dry film formation and light irradiation were performed similarly to the time of photocurability evaluation, and the hardened | cured material was obtained. This was heated at 150 ° C. for 1 hour to prepare a test substrate. Using this test substrate, a thermal cycle test was carried out with 15 minutes at -65 ° C and 15 minutes at 150 ° C, and the appearance after 200 cycles was observed and visually evaluated.

Synthesis example 1
Synthesis of Radical Polymerizable Polymer 81.5 parts of carbitol acetate was charged into a separable flask equipped with a cooling pipe as a reaction vessel, and after nitrogen substitution, the temperature was raised to 80 ° C. On the other hand, 30 parts of N-phenylmaleimide and 120 parts of carbitol acetate were mixed in the dropping tank 1, 29 parts of styrene and 20 parts of 2-hydroxyethyl methacrylate in the dropping tank 2, and the dropping tank 3 A mixture of 21 parts of acrylic acid and 10.6 parts of carbitol acetate, and Luperox 11 (trade name; manufactured by Arkema Yoshitomi Co., Ltd., 70% of t-butyl peroxypivalate as a polymerization initiator in the dropping tank 4) A mixture of 10 parts of a hydrocarbon solution and 21.2 parts of carbitol acetate was charged. While maintaining the reaction temperature at 80 ° C., dropping was performed over the dropping tank 1, 2, 4 to 3 hours, and from the dropping tank 3 over 2.5 hours. After completion of the dropwise addition, the reaction was further continued at 80 ° C. for 30 minutes. Thereafter, the reaction temperature was raised to 95 ° C., and the reaction was continued for 1.5 hours to obtain a polymer solution before the radical polymerizable double bond introduction reaction.
Next, 9.9 parts of glycidyl methacrylate, 7.4 parts of carbitol acetate, 0.7 parts of triphenylphosphine as a reaction catalyst, 0.7 parts of triphenylphosphine as a reaction catalyst, and Anthey W-400 (manufactured by Kawaguchi Chemical Industry Co., Ltd. as a polymerization inhibitor) 0.2 part) was added, and mixed gas (oxygen concentration 7%) of nitrogen and oxygen was bubbled to react at 115 ° C. to obtain a radically polymerizable polymer solution A-1 of the present invention.
The physical properties of the obtained radical polymerizable polymer solution A-1 were measured. The weight average molecular weight was 19,800, and the solid content concentration obtained by heating and drying at 160 ° C. under vacuum was 32.0%, solid content The acid value per unit was 121 mg KOH / g. The heat decomposition resistance was X / Y = 0.972.

Synthesis example 2
Synthesis of Radical Polymerizable Polymer 81.5 parts of propylene glycol monomethyl ether acetate was charged into a separable flask equipped with a cooling pipe as a reaction vessel, and after nitrogen substitution, the temperature was raised to 80 ° C. On the other hand, 30 parts of N-phenylmaleimide and 120 parts of propylene glycol monomethyl ether acetate were mixed in the dropping tank 1, and 28.5 parts of styrene and 20 parts of 2-hydroxyethyl methacrylate were mixed in the dropping tank 2. A mixture of 21.5 parts of acrylic acid and 10.6 parts of propylene glycol monomethyl ether acetate in the dropping tank 3, 10 parts of Luperox 11 as a polymerization initiator, 21.2 parts of propylene glycol monomethyl ether acetate in the dropping tank 4 Each mixture was charged separately. While maintaining the reaction temperature at 80 ° C., dropping was performed over the dropping tank 3 over 2.5 hours from the dropping tank 3 over a period of 3 to 4 hours. After completion of the dropwise addition, the reaction was further continued at 80 ° C. for 30 minutes. Thereafter, the reaction temperature was raised to 95 ° C., and the reaction was continued for 1.5 hours to obtain a polymer solution before the radical polymerizable double bond introduction reaction.
Next, 13.6 parts of Cyclomer M100 (manufactured by Daicel Chemical Industries, Ltd.), 7.4 parts of propylene glycol monomethyl ether acetate, 0.7 parts of triphenylphosphine as a reaction catalyst, and a polymerization inhibitor were added to this polymer solution. 0.2 parts of Ange W-400 was added and reacted at 115 ° C. while bubbling a mixed gas of nitrogen and oxygen (oxygen concentration 7%) to obtain a radically polymerizable polymer solution A-2 of the present invention.
The physical properties of the obtained radical polymerizable polymer solution A-2 were measured, and the weight average molecular weight was 16,900, and the solid content concentration obtained by heating and drying at 160 ° C. under vacuum was 31.9%, solid content The acid value per unit was 123 mg KOH / g. The heat decomposition resistance was X / Y = 0.997.

Synthesis example 3
Synthesis of Radical Polymerizable Polymer 82.4 parts of propylene glycol monomethyl ether acetate and 35.3 parts of isopropanol were charged into a separable flask equipped with a cooling pipe as a reaction vessel, and after nitrogen substitution, the temperature was raised to 100 ° C. On the other hand, 40 parts of N-phenylmaleimide, 128 parts of propylene glycol monomethyl ether acetate, and 32 parts of isopropanol were mixed in the dropping tank 1, 13 parts of styrene and 20 parts of 2-hydroxyethyl methacrylate in the dropping tank 2. A mixture of 27 parts of methacrylic acid and 22.2 parts of isopropanol, Perbutyl O as a polymerization initiator in a dropping tank 3 (trade name; t-butylperoxy-2-ethylhexanoate, manufactured by NOF Corporation) I prepared 10 parts each. While maintaining the reaction temperature at 100 ° C., dropping was performed over 3 hours from the dropping tanks 1 to 3. After completion of the dropwise addition, the reaction was further continued at 100 ° C. for 30 minutes. Thereafter, the reaction temperature was raised to 115 ° C., and the reaction was continued for 1.5 hours to obtain a polymer solution before the radical polymerizable double bond introduction reaction.
Then, 13.7 parts of cyclomer M100, 31.2 parts of propylene glycol monomethyl ether acetate, 0.7 parts of triphenylphosphine as a reaction catalyst, 0.7 parts of triphenylphosphine as a reaction catalyst, and 0. Two parts were added, and a mixed gas of nitrogen and oxygen (oxygen concentration 7%) was bubbled to react at 115 ° C. to obtain a radically polymerizable polymer solution A-3 of the present invention.
The physical properties of the obtained radical polymerizable polymer solution A-3 were measured. The weight average molecular weight was 7,400, and the solid content concentration obtained by heating and drying at 160 ° C. under vacuum was 32.0%, solid content The acid value per unit was 124 mg KOH / g. The heat decomposition resistance was X / Y = 0.982.

Synthesis example 4
Synthesis of Radically Polymerizable Polymer A radically polymerizable polymer solution of the present invention was prepared in the same manner as in Synthesis Example 3 except that 40 parts of N-phenylmaleimide was used instead of 40 parts of N-phenylmaleimide. A-4 was obtained.
The physical properties of the obtained radical polymerizable polymer solution A-4 were measured. The weight average molecular weight was 6,200, and the solid content concentration obtained by heating and drying at 160 ° C. under vacuum was 32.0%, solid content The acid value per unit was 125 mg KOH / g. The heat decomposition resistance was X / Y = 0.980.

Synthesis example 5
Synthesis of Radical Polymerizable Polymer In Synthesis Example 3, except that 40 parts of N-phenylmaleimide were replaced with 20 parts of N-phenylmaleimide and 20 parts of N-benzylmaleimide, and the preparation amount of perbutyl O was 8 parts. In the same manner as in Synthesis Example 3, a radically polymerizable polymer solution A-5 of the present invention was obtained.
The physical properties of the obtained radical polymerizable polymer solution A-5 were measured. The weight average molecular weight was 7600, and the solid content concentration obtained by heating and drying at 160 ° C. under vacuum was 32.0%, solid content The acid value per unit was 126 mg KOH / g. The heat decomposition resistance was X / Y = 0.985.

Synthesis example 6
Synthesis of Radical Polymerizable Polymer for Comparison 81.5 parts of carbitol acetate was charged into a separable flask equipped with a cooling pipe as a reaction vessel, and after nitrogen substitution, the temperature was raised to 80 ° C. On the other hand, 30 parts of N-phenylmaleimide and 120 parts of carbitol acetate were mixed in the dropping tank 1, 39 parts of styrene and 10 parts of 2-hydroxyethyl methacrylate in the dropping tank 2, and the dropping tank 3 A mixture of 21 parts of acrylic acid and 10.6 parts of carbitol acetate was charged, and a mixture of 10 parts of Luperox 11 as a polymerization initiator and 21.2 parts of carbitol acetate was charged in the dropping tank 4 respectively. While maintaining the reaction temperature at 80 ° C., dropping was performed over the dropping tank 1, 2, 4 to 3 hours, and from the dropping tank 3 over 2.5 hours. After completion of the dropwise addition, the reaction was further continued at 80 ° C. for 30 minutes. Thereafter, the reaction temperature was raised to 95 ° C., and the reaction was continued for 1.5 hours to obtain a polymer solution before the radical polymerizable double bond introduction reaction.
Next, 9.9 parts of glycidyl methacrylate, 7.4 parts of carbitol acetate, 0.7 parts of triphenylphosphine as a reaction catalyst, and 0.2 parts of Ange W-400 as a polymerization inhibitor are added to the polymer solution. A mixed gas of nitrogen and oxygen (oxygen concentration 7%) was bubbled to react at 115 ° C. to obtain a radically polymerizable polymer solution B-1 for comparison.
The physical properties of the obtained radical polymerizable polymer solution B-1 were measured. The weight average molecular weight was 15600, and the solid content concentration obtained by heating and drying at 160 ° C. under vacuum was 31.6%, solid content The acid value per unit was 121 mg KOH / g. The heat decomposition resistance was X / Y = 0.959.

  The formulations shown in Table 1 were prepared using each solution, and evaluated for alkali solubility, photocurability, and TCT resistance by the method described above. The results are shown in Table 1 together.

The terms in Table 1 are as follows.
Monomer: dipentaerythritol hexaacrylate polymerization initiator: Irgacure 907 (photopolymerization initiator manufactured by BASF Japan Ltd.)

As for the thermal decomposition resistance, the radically polymerizable polymer solutions A-1 to A-5 are better than the comparative radically polymerizable polymer solution B-1, and among them, A-2 obtained by reacting the cyclomer M100 among others. The result of ~ A-5 was high. In addition, as shown in Examples 1 to 5, the resin compositions obtained using the radically polymerizable polymer solutions A-1 to A-5 are all good in alkali solubility, photocurability, TCT resistance, there were.
On the other hand, as shown in Comparative Example 1, in the resin composition using the radical polymerizable polymer solution for comparison B-1, the result was inferior in alkali solubility.

  Since the radically polymerizable polymer of the present invention, and the resin composition comprising the radically polymerizable polymer and the radically polymerizable compound have alkali solubility which is essential for fine processing, a photosensitive resin can be obtained. It can be used as a composition.

The radically polymerizable polymer of the present invention, and a resin composition comprising the radically polymerizable polymer and a radically polymerizable compound have alkali solubility and photocurability while having excellent heat resistance, Furthermore, in the case of a cured coating film, the adhesion to a substrate is good, and thus, as a component of a photosensitive resin composition for image formation capable of alkali development, for example, a printing plate, a protective film of a color filter It can use suitably for various uses, such as for liquid crystal display board manufacture of color filters, a black matrix, a photo spacer, a black column spacer, etc.

Claims (8)

In 100% by mass of the polymer, 10 to 60% by mass of a constitutional unit derived from a maleimide-based monomer, 10 to 40% by mass of a constitutional unit derived from an unsaturated carboxylic acid monomer not having an ester bond, and a unit having a hydroxyl group Radical having a structure in which a monomer having a functional group capable of reacting with the carboxyl group is reacted with a carboxyl group possessed by the polymer containing 10 to 40% by mass of a structural unit derived from a body as an essential unit A polymerizable polymer, and
The radically polymerizable polymer whose relative value X / Y of residual ratio X (mass%) and solid content concentration Y (mass%) after heat processing obtained by a following formula is 0.95 or more.
After heat treatment Residual ratio X (mass%) = {mass of dried mixture obtained by heating and drying a mixture of 0.3 g of radical polymerizable polymer (mass before heating and drying) and 2 ml of acetone at 200 ° C for 30 minutes ) / {Mass (0.3 (g) before heat drying of the radically polymerizable polymer)}
Solid content concentration Y (mass%) = {mass of solid content obtained by heating and drying radically polymerizable polymer 0.3 g (mass before heating and drying) at 160 ° C. for 1 hour and 30 minutes under a vacuum} / {Mass 0.3 (g) before drying by heating of radically polymerizable polymer}   The radically polymerizable polymer according to claim 1, containing 1 to 35% by mass of a constituent unit derived from an aromatic monomer having no ester bond in 100% by mass of the polymer.   The radically polymerizable polymer according to claim 1 or 2, wherein the structural unit derived from the unsaturated carboxylic acid monomer having no ester bond is a structural unit derived from (meth) acrylic acid.   A resin composition comprising the radically polymerizable polymer according to any one of claims 1 to 3 and a radically polymerizable compound.   A cured product obtained by curing the radically polymerizable polymer according to any one of claims 1 to 3 or the resin composition according to claim 4. The following formulas (1) and (2)
After heat treatment Residual ratio X (mass%) = {mass of dried mixture obtained by heating and drying a mixture of 0.3 g of radical polymerizable polymer (mass before heating and drying) and 2 ml of acetone at 200 ° C for 30 minutes ) / {Mass (0.3 (g) before heat drying of radically polymerizable polymer)} (1)
Solid content concentration Y (mass%) = {mass of solid content obtained by heating and drying radically polymerizable polymer 0.3 g (mass before heating and drying) at 160 ° C. for 1 hour and 30 minutes under a vacuum} / {Mass 0.3 (g) before drying by heating of radically polymerizable polymer} (2)
A method for producing a radically polymerizable polymer, wherein the relative value X / Y of the after-heat treatment residual ratio X (mass%) and the solid content concentration Y (mass%) obtained by
10 to 60 mass% of a maleimide-based monomer, 10 to 40 mass% of an unsaturated carboxylic acid monomer having no ester bond, and 10 to 40 mass of a monomer having a hydroxyl group in 100 mass% of the monomer component B. reacting the above-mentioned monomer component essentially containing C. to obtain a polymer,
Reacting a monomer having a functional group capable of reacting with the carboxyl group with a carboxyl group of the polymer to obtain a radically polymerizable polymer;
A method of producing a radically polymerizable polymer comprising:   The manufacturing method of the radically polymerizable polymer of Claim 6 which contains 1-35 mass% of aromatic monomers which do not have an ester bond in 100 mass% of said monomer components. The polymer is obtained by polymerization in a mixed solvent of an ester and an alcohol,
The manufacturing method of the radically polymerizable polymer of Claim 6 or 7.