JP6381192B2 - Method for producing alkali-soluble resin - Google Patents

Description

The present invention relates to a method for producing an alkali-soluble resin. More specifically, the present invention relates to a method for producing an alkali-soluble resin and a resist composition containing the obtained alkali-soluble resin.

Alkali-soluble resins are materials used in various fields ranging from civil engineering and building materials to electronic information materials. One of the main uses is an alkali development type resist composition. The resist composition is a composition whose physical properties change by irradiating light or electron beam to the film on which it is applied, i.e., for example, the exposed part is cured and the other part is soluble, etc. It is a composition whose physical properties change. Utilizing these characteristics, various optical members such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, etc. used in liquid crystal display devices and solid-state imaging devices, electrical equipment and electronic devices, etc. With the development of so-called IT technology, the importance of resist compositions is increasing.

As a conventional resist composition, for example, a (meth) acrylate polymer, a polymerizable monomer, and photopolymerization start, which are composed of sufficient monomer components including a tertiary carbon-containing (meth) acrylate monomer A negative resist composition containing an agent is disclosed (see Patent Document 1), and a cured film with excellent physical properties and reduced film thickness is realized.

JP 2013-61599 A

As described above, Patent Document 1 discloses a resist composition that can realize a cured product (cured film) excellent in various physical properties. In this resist composition, the structural unit derived from the tertiary carbon-containing (meth) acrylate monomer contained in the (meth) acrylate polymer is decomposed by heating and partially volatilized. While the film thickness is reduced, the colorant concentration is increased, and various physical properties are improved. Therefore, this resist composition is extremely useful in the resist field. However, in order to further improve the performance, the polymer used in this resist composition has been studied repeatedly. When copolymerizing a (meth) acrylate monomer with an acid group-containing monomer, it was newly found that tertiary carbon is easily eliminated during the polymerization. When elimination occurs, an acid is generated and the polymer may not be obtained more easily. Even if a polymer is obtained, it may not be a desired polymer in terms of transparency and acid value. is there. Therefore, we found that there are challenges in these respects.

The present invention has been made in view of the above situation, has a structural unit derived from a tertiary carbon-containing (meth) acrylate monomer and an acid group-containing monomer, and is transparent and has a desired acid value. It is an object of the present invention to provide a production method capable of efficiently and easily obtaining an alkali-soluble resin, and a resist composition containing the alkali-soluble resin obtained by the production method.

As described above, the present inventors originated from the fact that when the tertiary carbon-containing (meth) acrylate monomer is copolymerized with the acid group-containing monomer, the tertiary carbon is easily detached during the polymerization. I found a new problem. Therefore, various studies have been made on the method for suppressing the elimination of tertiary carbon, and the polymerization process of the monomer component including the tertiary carbon-containing (meth) acrylate monomer and the acid group-containing monomer is changed to an alcohol type. When carried out in the presence of a solvent, the elimination of tertiary carbon during polymerization is sufficiently suppressed, and the generation of acid is sufficiently suppressed. Therefore, the polymer is transparent and has a desired acid value (alkali-soluble resin). ) Was found to be efficient and easy to obtain. Moreover, the resist composition containing an alkali-soluble resin obtained by such a production method is derived from a tertiary carbon-containing (meth) acrylate monomer by, for example, a heating step after development (also referred to as baking or post-baking step). As a result of the decomposition of the structural units of this product and partial volatilization, the thickness of the cured film is reduced, the colorant concentration is increased, and various physical properties are found to be superior, and the above problems are observed. The present inventors have reached the present invention by conceiving that the problem can be solved.

That is, the present invention is a method for producing an alkali-soluble resin, and the production method comprises a simple substance containing a tertiary carbon-containing (meth) acrylate monomer and an acid group-containing monomer in the presence of an alcohol solvent. It has a step of polymerizing a monomer component, and the amount of the alcohol solvent used is a method for producing an alkali-soluble resin, which is 10 to 80% by mass with respect to 100% by mass of the total amount of the polymerization solution.
The present invention is also a resist composition containing an alkali-soluble resin obtained by the above production method.
The present invention is described in detail below. In addition, the form which combined each preferable form of this invention described below 2 or 3 or more is also a preferable form of this invention.

[Method for producing alkali-soluble resin]
The production method of the present invention includes a step of polymerizing a monomer component including a tertiary carbon-containing (meth) acrylate monomer and an acid group-containing monomer (hereinafter also referred to as a polymerization step). Depending on the situation, one or more other steps may be included.

<Solvent>
The polymerization step is performed in the presence of an alcohol solvent.
The alcohol solvent means a saturated alcohol, that is, a compound having no unsaturated double bond and containing at least one hydroxyl group. Specifically, for example, monoalcohols such as methanol, ethanol, isopropanol, n-butanol and s-butanol; polyhydric alcohols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl 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 and other glycol monoethers are preferred; Or 2 or more types can be used.

The amount of the alcohol solvent used is suitably 10 to 80% by mass with respect to 100% by mass of the total amount of the polymerization solution. Thereby, the detachment of the tertiary carbon in the tertiary carbon-containing (meth) acrylate monomer can be sufficiently suppressed. More preferably 20% by mass or more, further preferably 30% by mass or more, particularly preferably 40% by mass or more, more preferably 70% by mass or less, still more preferably 60% by mass or less, and particularly preferably 50% by mass. It is as follows.

In the polymerization step, a solvent other than the alcohol solvent (also referred to as other solvent) may be used in combination. As another solvent, the following compounds etc. are mentioned, for example, These 1 type (s) or 2 or more types can be used. In addition, when using a solvent as a diluent etc. when using it as a resist composition later, it is also suitable to use the solvent containing this solvent for a superposition | polymerization process.
Cyclic ethers such as tetrahydrofuran and dioxane; glycol ethers such as ethylene glycol dimethyl 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, and 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 ether acetate), propylene glycol Monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl Esters of glycol monoethers such as cetate; methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxypropion Alkyl esters such as methyl acetate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl acetoacetate and ethyl acetoacetate; ketones such as acetone, 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-methylpyrrole Amides such as emissions; like.

The amount of the other solvent used is preferably 80% by mass or less with respect to 100% by mass of the total amount of the solvents used in the polymerization step. That is, the amount of the alcohol solvent used is preferably 20 to 100% by mass with respect to 100% by mass of the total amount of the solvent used in the polymerization step. Thereby, the effect by the alcohol solvent that suppresses the elimination of tertiary carbon is more sufficiently exhibited. The amount of the alcohol solvent used is more preferably 30% by mass or more, further preferably 40% by mass or more, and particularly preferably 50% by mass or more.

<Monomer component>
The monomer component used for the polymerization step includes a tertiary carbon-containing (meth) acrylate monomer and an acid group-containing monomer. These monomers can be used alone or in combination of two or more, and may further contain one or more other monomers as required.

(I) Tertiary carbon-containing (meth) acrylate monomer The tertiary carbon-containing (meth) acrylate monomer is a (meth) acryloyl group (CH ₂ = C (R) -C ( = O)-; R represents a hydrogen atom or a methyl group.) And a compound containing a tertiary carbon atom. Therefore, the alkali-soluble resin has a structural unit derived from such a tertiary carbon-containing (meth) acrylate monomer, that is, a polymerizable carbon-carbon double bond (C═C) in the monomer. It has a structural unit that is a single bond (C—C).
The tertiary carbon atom means a carbon atom having three other carbon atoms bonded to the carbon atom.

The tertiary carbon-containing (meth) acrylate monomer preferably has a structure in which an oxygen atom adjacent to a (meth) acryloyl group is bonded to a tertiary carbon atom. That is, the form in which the tertiary carbon-containing (meth) acrylate monomer has a structure in which an oxygen atom adjacent to the (meth) acryloyl group is bonded to a tertiary carbon atom is one of preferred forms of the present invention. One.

More preferably, the tertiary carbon-containing (meth) acrylate monomer is, for example, the following general formula (1):
_{CH 2 = C (R) -C} (= O) -O-A (1)
(R represents a hydrogen atom or a methyl group. A represents a monovalent organic group containing a structure having a tertiary carbon atom on the oxygen atom side).

In the general formula (1), the organic group represented by A can be represented by, for example, —C (R ¹ ) (R ² ) (R ³ ). In this case, R ¹ , R ² and R ³ are the same or different and are preferably a hydrocarbon group having 1 to 30 carbon atoms, and the hydrocarbon group may be a saturated hydrocarbon group. And may be an unsaturated hydrocarbon group. Moreover, it may have a cyclic structure and may further have a substituent. R ¹ , R ^2, and R ³ may be linked to each other at a terminal site to form a cyclic structure.

In the present invention, a new compound produced by cleavage of the O—C bond between the oxygen atom adjacent to the (meth) acryloyl group and the tertiary carbon atom in A adjacent thereto is likely to volatilize. The number of carbon atoms of the organic group represented by A is preferably 12 or less. Among them, the organic group represented by A is preferably a group derived from t-butyl (meth) acrylate and / or t-amyl (meth) acrylate. The organic group represented by A may have a branched structure.

In the tertiary carbon-containing (meth) acrylate-based monomer, the tertiary carbon atom bonded to the oxygen atom adjacent to the (meth) acryloyl group has at least one of the adjacent carbon atoms bonded to a hydrogen atom. It is preferable that For example, a tertiary carbon-containing (meth) acrylate monomer is a compound represented by the above general formula (1), and A is represented by -C (R ¹ ) (R ² ) (R ³ ). It is preferable that at least one of R ¹ , R ² and R ³ has one or more hydrogen atoms. In such a form, by heating, the O—C bond between the oxygen atom adjacent to the (meth) acryloyl group and the tertiary carbon atom adjacent thereto is cut, and (meth) acrylic acid is generated at the same time. Then, a double bond (C═C) is formed between the tertiary carbon atom and the carbon atom adjacent to the tertiary carbon atom, and a new compound is generated more stably.

The new compound produced as described above is preferably volatile. In this case, due to volatilization of the new compound from the cured product, the thickness of the cured product (cured film) is reduced, and at the same time, for example, a resist composition using an alkali-soluble resin in combination with a colorant. When used for objects, the colorant concentration increases after heating. Therefore, it is possible to realize a further thinner film, and to achieve higher color purity and higher light blocking ratio of the black matrix. In view of this point, R ¹ , R ² and R ³ are preferably the same or different and are each a saturated hydrocarbon group having 1 to 15 carbon atoms. More preferably, it is a C1-C10 saturated hydrocarbon group, More preferably, it is a C1-C5 saturated hydrocarbon group, Most preferably, it is a C1-C3 saturated hydrocarbon group.

The content ratio of the tertiary carbon-containing (meth) acrylate monomer is preferably 5% by mass or more with respect to 100% by mass of the total amount of the monomer components. Thereby, the effect resulting from the structural unit derived from a tertiary carbon containing (meth) acrylate type monomer will be expressed further. More preferably, it is 15 mass% or more, More preferably, it is 30 mass% or more. Further, the upper limit of the content ratio may be appropriately set in consideration of the content ratio of other monomers, for example, when used for color filter applications, from the viewpoint of further improving the pattern characteristics and developability, It is suitable that it is 90 mass% or less. More preferably, it is 80 mass% or less, More preferably, it is 75 mass% or less.

(Ii) Acid group-containing monomer The acid group-containing monomer is a compound containing an acid group and a polymerizable double bond in the molecule. Specifically, for example, unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, and vinyl benzoic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid Unsaturated carboxylic acids having a chain extended between an unsaturated group and a carboxyl group, such as mono (2-acryloyloxyethyl) succinate and mono (2-methacryloyloxyethyl) succinate; And unsaturated acid anhydrides such as acid and itaconic anhydride; phosphoric acid group-containing unsaturated compounds such as light ester P-1M (manufactured by Kyoeisha Chemical); and the like. Among these, it is preferable to use carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, unsaturated acid anhydrides) from the viewpoints of versatility and availability. More preferred are unsaturated monocarboxylic acids in terms of reactivity and alkali solubility, more preferred is (meth) acrylic acid, and particularly preferred is methacrylic acid.
In addition, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

The content ratio of the acid group-containing monomer is preferably set so that the acid value of the alkali-soluble resin falls within a preferable range described later. For example, the content ratio of the acid group-containing monomer is preferably 5% by mass or more, more preferably 7% by mass or more, and further preferably 9% by mass or more with respect to 100% by mass of the total amount of the monomer components. It is. Moreover, it is preferable that it is 85 mass% or less, More preferably, it is 80 mass% or less, More preferably, it is 70 mass% or less.

(Iii) Other monomer The above monomer component may also be a monomer other than a tertiary carbon-containing (meth) acrylate monomer and an acid group-containing monomer (other monomer if necessary). 1 type) or two or more types.

The other monomer is preferably N-substituted maleimide, acrylic ether dimer, and / or α- (allyloxymethyl) acrylate. By using these, in a cured product (cured film) using the obtained alkali-soluble resin, various physical properties such as heat resistance, hardness, transparency, colorant dispersibility, and plate-making property can be further improved. Thus, the embodiment in which the monomer component further contains at least one compound selected from the group consisting of N-substituted maleimide, acrylic ether dimer, and α- (allyloxymethyl) acrylate is also included in the present invention. One preferred form. In this case, the content of at least one compound selected from the group consisting of N-substituted maleimide, acrylic ether dimer, and α- (allyloxymethyl) acrylate (the total amount when two or more are included) It is suitable that it is 2-60 mass% with respect to 100 mass% of monomer components. More preferably, it is 5-50 mass%, More preferably, it is 5-40 mass%.

(Iii-1) N-substituted maleimide When the monomer component further contains an N-substituted maleimide, a cured film having particularly improved heat resistance, colorant dispersibility, hardness and the like can be obtained. Examples of the N-substituted maleimide include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, Nt-butylmaleimide, N-dodecylmaleimide, N-benzylmaleimide, N-naphthylmaleimide etc. are mentioned, These 1 type (s) or 2 or more types can be used. Among these, N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide are preferable, and N-benzylmaleimide is particularly preferable because it is less colored and excellent in colorant dispersibility.

Examples of the N-benzylmaleimide include benzylmaleimide; alkyl-substituted benzylmaleimide such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl group-substituted benzylmaleimide such as p-hydroxybenzylmaleimide; o-chlorobenzylmaleimide , Halogen-substituted benzylmaleimides such as o-dichlorobenzylmaleimide and p-dichlorobenzylmaleimide.

The content ratio of the N-substituted maleimide is, for example, preferably 2 to 60% by mass with respect to 100% by mass of the monomer component. Within this range, it is possible to obtain a cured film having further improved heat resistance, colorant dispersibility, hardness, and the like. In addition, when there is too much content rate of N substituted maleimide, a developing speed may not become a more appropriate thing and transparency of a cured film may not become more enough. More preferably, it is 5-50 mass%, More preferably, it is 5-40 mass%.

(Iii-2) Acrylic ether dimer As the acrylic ether dimer, the following general formula (2):

(In the formula, R ⁴ represents a hydrogen atom or an organic group having 1 to 25 carbon atoms which may have a substituent. R ⁵ may have a hydrogen atom or a substituent. A compound represented by a good organic group having 1 to 25 carbon atoms is preferred. When the monomer component contains such an acrylic ether dimer, a cured film that is further excellent in transparency and heat resistance can be realized.
This is presumably due to the cyclization reaction of the acrylic ether dimer during polymerization to form a tetrahydropyran ring structure in the structural unit derived from the dimer.

In the general formula (2), R ⁴ and R ⁵ are the same or different and represent a hydrogen atom or an organic group having 1 to 25 carbon atoms which may have a substituent. Is preferably a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. For example, linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl An alicyclic group such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; alkoxy such as 1-methoxyethyl, 1-ethoxyethyl; A substituted alkyl group; an alkyl group substituted with an aryl group such as benzyl; and the like. Of these, primary or secondary carbon hydrocarbon groups that are difficult to be removed by acid or heat, such as methyl, ethyl, cyclohexyl, benzyl, etc., are preferable in terms of heat resistance.
R ⁴ and R ⁵ may be the same organic group or different organic groups.

Specific examples of the acrylic ether dimer include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate and diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate. Di (n-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n -Butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butyl)- 2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2 ′-[oxybis (methylene)] bis-2 Propenoate, di (stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2- Ethylhexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxy) Ethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis (methylene) )] Bis-2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate Di (t-butylcyclohexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate , Di (tricyclodecanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, and the like. These 1 type (s) or 2 or more types can be used. Among them, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2 ′-[oxybis ( Methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred.

The content ratio of the acrylic ether dimer is preferably 2 to 60% by mass with respect to 100% by mass of the monomer component, for example. When it is in this range, it becomes possible to obtain a cured film having further improved heat resistance, transparency, and the like. In addition, when there is too much content rate of an acrylic ether dimer, it may gelatinize and it may be unable to superpose | polymerize more efficiently. More preferably, it is 5-50 mass%, More preferably, it is 5-40 mass%.

(Iii-3) α- (allyloxymethyl) acrylate As the α- (allyloxymethyl) acrylate, the following general formula (3):

(Wherein R ⁶ represents a hydrogen atom or an organic group having 1 to 30 carbon atoms which may have a substituent). When the above monomer component contains such α- (allyloxymethyl) acrylate, in particular, performance that contributes to plate making properties such as adhesion, curability, and dry redissolvability, colorant dispersibility, and heat resistance. Property, transparency, etc. are further improved.
This is because, when α- (allyloxymethyl) acrylate is incorporated into the structure of the alkali-soluble resin, a cyclization reaction forms a tetrahydrofuran ring structure. It is considered that since the methylene group is present, the flexibility is high, and each performance derived from the tetrahydrofuran ring such as dispersibility, adhesion, curability, compatibility, and dry resolubility is effectively expressed.

In the general formula (3), R ⁶ represents a hydrogen atom or an organic group having 1 to 30 carbon atoms which may have a substituent, and as described above, α- (allyloxymethyl) Since the expression of each performance derived from acrylate is considered to be caused by the tetrahydrofuran ring in the main chain of the (meth) acrylate polymer and the methylene group on both sides of the tetrahydrofuran ring, R ⁶ is used for purposes and applications. In addition, it may be selected as appropriate.

As said C1-C30 organic group, it is suitable that it is a C1-C30 hydrocarbon group which may have a substituent. Specifically, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-amyl, s-amyl, t-amyl, n-hexyl, s-hexyl , N-heptyl, n-octyl, s-octyl, t-octyl, 2-ethylhexyl, capryl, nonyl, decyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, stearyl, nonadecyl, eicosyl, ceryl, melyl Chain saturated hydrocarbon groups such as methoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, ethoxyethyl, ethoxyethoxyethyl, phenoxyethyl, phenoxyethoxyethyl, etc. Al is replaced with an alkoxy group A hydroxy-substituted chain saturated hydrocarbon group; a hydroxy-substituted chain saturated hydrocarbon group in which part of the hydrogen atoms of a chain saturated hydrocarbon group such as hydroxyethyl, hydroxypropyl, hydroxybutyl, etc. is replaced by a hydroxy group; fluoroethyl, difluoro Halogen-substituted chain saturated hydrocarbon groups in which part of the hydrogen atoms of chain saturated hydrocarbon groups such as ethyl, chloroethyl, dichloroethyl, bromoethyl, dibromoethyl are replaced with halogens; vinyl, allyl, methallyl, crotyl, propargyl, etc. A chain unsaturated hydrocarbon group, and a chain unsaturated hydrocarbon group in which part of the hydrogen atom is replaced by an alkoxy group, a hydroxy group or a halogen; cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-t-butylcyclohexyl, Tricyclodecanyl, isobornyl, adamantyl An alicyclic hydrocarbon group such as dicyclopentadienyl and an alicyclic hydrocarbon group in which a part of the hydrogen atom is replaced with an alkoxy group, a hydroxy group or a halogen; phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, 4 -Aromatic hydrocarbon groups such as t-butylphenyl, benzyl, diphenylmethyl, diphenylethyl, triphenylmethyl, cinnamyl, naphthyl, anthranyl, etc. and aromatics in which some of the hydrogen atoms are replaced with alkoxy groups, hydroxy groups or halogens Hydrocarbon group; and the like. Moreover, arbitrary substituents may be further bonded to these organic groups.

Specific examples of the α- (allyloxymethyl) acrylate include the following compounds.
α-allyloxymethyl acrylic acid, methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, n-propyl α-allyloxymethyl acrylate, i-propyl α-allyloxymethyl acrylate, α- N-butyl allyloxymethyl acrylate, s-butyl α-allyloxymethyl acrylate, t-butyl α-allyloxymethyl acrylate, n-amyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate s -Amyl, α-allyloxymethyl acrylate t-amyl, α-allyloxymethyl acrylate n-hexyl, α-allyloxymethyl acrylate s-hexyl, α-allyloxymethyl acrylate n-heptyl, α-allyl N-octyl oxymethyl acrylate, α-allyloxymethyl S-octyl crylate, t-octyl α-allyloxymethyl acrylate, 2-ethylhexyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate capryl, α-allyloxymethyl acrylate nonyl, α-allyloxy Decyl methyl acrylate, undecyl α-allyloxymethyl acrylate, lauryl α-allyloxymethyl acrylate, tridecyl α-allyloxymethyl acrylate, myristyl α-allyloxymethyl acrylate, pentadecyl α-allyloxymethyl acrylate, Cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, stearyl α-allyloxymethyl acrylate, nonadecyl α-allyloxymethyl acrylate, eicosi α-allyloxymethyl acrylate , Ceryl α-allyloxymethyl acrylate, melyl α-allyloxymethyl acrylate,

methoxyethyl α-allyloxymethyl acrylate, methoxyethoxyethyl α-allyloxymethyl acrylate, methoxyethoxyethoxyethyl α-allyloxymethyl acrylate, 3-methoxybutyl α-allyloxymethyl acrylate, α-allyloxymethyl Ethoxyethyl acrylate, ethoxyethoxyethyl α-allyloxymethyl acrylate, phenoxyethyl α-allyloxymethyl acrylate, phenoxyethoxyethyl α-allyloxymethyl acrylate, hydroxyethyl α-allyloxymethyl acrylate, α-allyl Hydroxypropyl oxymethyl acrylate, hydroxybutyl α-allyloxymethyl acrylate, fluoroethyl α-allyloxymethyl acrylate, difluoro α-allyloxymethyl acrylate Chill, chloroethyl α-allyloxymethyl acrylate, dichloroethyl α-allyloxymethyl acrylate, bromoethyl α-allyloxymethyl acrylate, dibromoethyl α-allyloxymethyl acrylate, vinyl α-allyloxymethyl acrylate, α -Allyloxymethyl acrylate, α-allyloxymethyl methacrylic acid, crotyl α-allyloxymethyl acrylate, propargyl α-allyloxymethyl acrylate, cyclopentyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic Acid cyclohexyl, α-allyloxymethyl acrylate 4-methylcyclohexyl, α-allyloxymethyl acrylate 4-t-butylcyclohexyl, α-allyloxymethyl acrylate tricyclodecanyl, α-a Isobornyl ryloxymethyl acrylate, adamantyl α-allyloxymethyl acrylate, dicyclopentadienyl α-allyloxymethyl acrylate, phenyl α-allyloxymethyl acrylate, methyl phenyl α-allyloxymethyl acrylate, α- Dimethylphenyl allyloxymethyl acrylate, trimethylphenyl α-allyloxymethyl acrylate, 4-t-butylphenyl α-allyloxymethyl acrylate, benzyl α-allyloxymethyl acrylate, diphenylmethyl α-allyloxymethyl acrylate , Α-allyloxymethyl acrylate diphenylethyl, α-allyloxymethyl acrylate triphenylmethyl, α-allyloxymethyl acrylate cinnamyl, α-allyloxymethyl naphthyl, α-a Examples include anthranyl ryloxymethyl acrylate, and one or more of these can be used.

The α- (allyloxymethyl) acrylate is preferably 2 to 60% by mass with respect to 100% by mass of the monomer component, for example. When it is within this range, it becomes possible to obtain a cured film having further improved plate-making properties, colorant dispersibility, heat resistance, transparency and the like. More preferably, it is 5-50 mass%, More preferably, it is 5-40 mass%.

(Iii-4) Monomers other than the above As the other monomers, for example, one or more of the following compounds can be used.
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, N-amyl (meth) acrylate, s-amyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, Cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, Isobornyl (meth) acrylate, adamantyl (meth) acrylate, (meth) acrylic acid Cyclodecanyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxy (meth) acrylate Butyl, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ( (Meth) acrylic acid glycidyl, (meth) acrylic acid β-methylglycidyl, (meth) acrylic acid β-ethylglycidyl, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, (meth) acrylic acid N, N— Dimethylaminoethyl, α-hydroxymethyl acrylate methyl , (Meth) acrylic acid esters such as α- hydroxymethyl acrylate;

(Meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene and methoxystyrene; polystyrene and polymethyl (meth) Macromonomers having a (meth) acryloyl group at one end of a polymer molecular chain such as acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, polycaprolactam; conjugated dienes such as 1,3-butadiene, isoprene and chloroprene Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ester Ter, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether and other vinyl ethers; N-vinyl N-vinyl compounds such as pyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine, N-vinylacetamide; unsaturated isocyanates such as isocyanatoethyl (meth) acrylate and allyl isocyanate.

Of these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and (meth) acrylic acid are easy to balance heat resistance, colorant dispersibility, and solvent resolubility. (Meth) acrylic esters such as isobornyl, tricyclodecanyl (meth) acrylate, phenoxyethyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate; aromatic vinyls such as styrene and vinyltoluene; cyclohexyl It is also preferable to use N-substituted maleimides such as maleimide, phenylmaleimide and benzylmaleimide; macromonomers having a (meth) acryloyl group at one end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate and polycaprolactone. . More preferred are (meth) acrylic acid esters. Thus, the form in which the monomer component further contains (meth) acrylic acid esters is also a preferred form of the present invention.

Among the other monomers described above, the content of monomers other than N-substituted maleimide, acrylic ether dimer, and α- (allyloxymethyl) acrylate is 0 to 100% by mass of the total monomer components. It is suitable that it is 30 mass%. More preferably, it is 0-20 mass%, More preferably, it is 0-10 mass%.

<Polymerization method>
The polymerization method employed in the polymerization step is preferably a solution polymerization method. In addition, as a polymerization mechanism, for example, a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization can be used, but the polymerization method based on the radical polymerization mechanism is industrially advantageous. This is preferable.

The polymerization initiating method in the above-mentioned polymerization step may be performed by supplying energy necessary for initiating polymerization from an active energy source such as heat, electromagnetic waves (infrared rays, ultraviolet rays, X-rays, etc.), electron beams, etc. If an agent is used in combination, the energy required for initiation of polymerization can be greatly reduced, and reaction control is facilitated, which is preferable. Further, the molecular weight of the polymer obtained by polymerizing the monomer component can be controlled by adjusting the amount and type of the polymerization initiator, the polymerization temperature, the type and amount of the chain transfer agent, and the like.

When the monomer component is polymerized by a radical polymerization mechanism, it is industrially advantageous and preferable to use a polymerization initiator that generates radicals by heat. Such a polymerization initiator is not particularly limited as long as it generates radicals by supplying heat energy, and may be appropriately selected depending on the polymerization temperature, solvent, type of monomer to be polymerized, and the like. Good. Moreover, you may use together reducing agents, such as transition metal salt and amines, with a polymerization initiator.

Examples of the 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-methylpropionate), hydrogen peroxide, persulfate, etc., which are usually used as polymerization initiators, such as peroxides and azo compounds, may be used alone or in combination of two or more. May be.

The amount of the polymerization initiator used may be appropriately set according to the type and amount of the monomer used, the polymerization conditions such as the polymerization temperature and the polymerization concentration, the molecular weight of the target polymer, etc., and is particularly limited. It is not a thing. For example, in order to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, the content is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the monomer component. More preferably, it is 0.5-15 mass parts.

In the polymerization step, a chain transfer agent that is usually used may be used as necessary. Preferably, a polymerization initiator and a chain transfer agent are used in combination. In addition, when a chain transfer agent is used at the time of superposition | polymerization, it exists in the tendency which can suppress the increase in molecular weight distribution or gelatinization.

Examples of the chain transfer agent include mercaptocarboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, and n-mercaptopropionic acid n- Octyl, methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3- Mercaptocarboxylic esters such as mercaptopropionate); alkyl mercapts such as ethyl mercaptan, t-butyl mercaptan, n-dodecyl mercaptan, 1,2-dimercaptoethane Mercapto alcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; Aromatic mercaptans such as benzenethiol, m-toluenethiol, p-toluenethiol and 2-naphthalenethiol; Tris [(3- Mercaptopropionyloxy) -ethyl] isocyanurate and other mercaptoisocyanurates; 2-hydroxyethyl disulfide and diethyl sulfides such as tetraethyl thiuram disulfide; dithiocarbamates such as benzyldiethyldithiocarbamate; α-methylstyrene dimer and the like Body dimers; alkyl halides such as carbon tetrabromide. These may be used alone or in combination of two or more.

Among these, mercaptocarboxylic acids, mercaptocarboxylic esters, alkyl mercaptans, mercapto alcohols, aromatic mercaptans, mercaptoisocyanurates, in terms of availability, ability to prevent crosslinking, and low degree of polymerization rate reduction. It is preferable to use a compound having a mercapto group such as More preferred are alkyl mercaptans, mercaptocarboxylic acids, mercaptocarboxylic acid esters, and still more preferred are n-dodecyl mercaptan and mercaptopropionic acid.

The amount of the chain transfer agent used is not particularly limited as long as it is appropriately set according to the type and amount of the monomer used, the polymerization temperature, the polymerization conditions such as the polymerization concentration, the molecular weight of the target polymer, etc. In order to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, the content is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the monomer component. More preferably, it is 0.5-15 mass%.

<Polymerization conditions>
In the above polymerization step, the polymerization temperature may be appropriately set according to the type and amount of the monomer to be used, the type and amount of the polymerization initiator, and is preferably 50 to 150 ° C, for example. More preferably, it is 70-120 degreeC. The polymerization time can be appropriately set similarly, but for example, 1 to 5 hours is preferable. More preferably, it is 2 to 4 hours.

The production method of the present invention also comprises a step of reacting a polymer (also referred to as a base polymer) obtained in the above polymerization step with a compound having a functional group capable of bonding to an acid group and a polymerizable double bond (double bond addition). It is also preferable to include a process). As a result, an alkali-soluble resin as a polymer having a double bond in the side chain (also referred to as a side chain double bond-containing polymer) can be obtained, and a cured product excellent in adhesion to the substrate and the surface hardness. It becomes possible to give. Thus, the production method of the present invention is preferably in a form including the polymerization step and the double bond addition step, and the alkali-soluble resin obtained by the production method of the present invention is obtained in the polymerization step. A polymer having no double bond in the side chain (base polymer); a polymer having a double bond in the side chain obtained by performing a double bond addition step after the above polymerization step. May be.

In the compound having a functional group capable of binding to the acid group and a polymerizable double bond, examples of the polymerizable double bond include (meth) acryloyl group, vinyl group, allyl group, methallyl group, and the like. A compound having one or more of these compounds is suitable. Of these, a (meth) acryloyl group is preferable in terms of reactivity. In addition, examples of the functional group capable of binding to an acid group include a hydroxy group, an epoxy group, an oxetanyl group, an isocyanate group, and the like, and those having one or more of these as the compound are suitable. . Of these, epoxy groups (including glycidyl groups) are preferred from the viewpoint of the speed of the modification treatment reaction, heat resistance, and dispersibility.

Examples of the compound having a functional group capable of binding to the acid group and a polymerizable double bond include glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and (meth) acrylate β-methylglycidyl. , (Meth) acrylic acid β-ethyl glycidyl, vinyl benzyl glycidyl ether, allyl glycidyl ether, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, vinyl cyclohexene oxide, etc., one or two of these The above can be used. Among these, it is preferable to use a compound (monomer) having an epoxy group and a (meth) acryloyl group.

The amount of the compound having a functional group capable of binding to the acid group and a polymerizable double bond is, for example, 1 to 100 parts by mass of the base polymer component (total amount of monomer components constituting the base polymer). It is preferable to set it as 170 mass parts. More preferably, it is 3-150 mass parts, More preferably, it is 5-120 mass parts.

In the step of reacting the base polymer with a compound having a functional group capable of bonding to an acid group and a polymerizable double bond, for example, the amount of the acid group (preferably a carboxyl group) of the base polymer component is changed to the acid group. A method in which the amount exceeds the amount of the compound having a functional group capable of binding to and a polymerizable double bond; and reacting the base polymer component with a compound having a functional group capable of binding to an acid group and a compound having a polymerizable double bond. Thereafter, it is preferable to employ a method of reacting a compound having a polybasic acid anhydride group. Thereby, a side chain double bond containing polymer can be obtained suitably.

The step of reacting the base polymer (preferably a polymer having a carboxyl group) with a compound having a functional group capable of binding to an acid group and a polymerizable double bond ensures a good reaction rate and gels. In order to prevent this, it is preferable to carry out in the temperature range of 50-160 degreeC. More preferably, it is 70-140 degreeC, More preferably, it is 90-130 degreeC. Moreover, in order to improve reaction rate, the basic catalyst and acidic catalyst for esterification or transesterification normally used can be used as a catalyst. Among them, it is preferable to use a basic catalyst because side reactions are reduced.

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-dodecyltrimethyl. Quaternary ammonium salts such as ammonium 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 Quaternary phosphonium salts such as bromide and benzyltriphenylphosphonium bromide; It is possible to have. Of these, dimethylbenzylamine, triethylamine, tetramethylurea, and triphenylphosphine are preferable in terms of reactivity, handling properties, and halogen-free properties.

The catalyst is used in a total amount of 100 parts by mass of the base polymer component (monomer component constituting the base polymer) and the compound having a functional group capable of binding to an acid group and a polymerizable double bond group. It is preferable to set it as 0.01-5 mass parts with respect to. More preferably, it is 0.1-3 mass parts.

The step of reacting the above base polymer with a compound having a functional group capable of bonding to an acid group and a polymerizable double bond is also possible to add a polymerization inhibitor and prevent the presence of a molecular oxygen-containing gas in order to prevent gelation. It is preferable to carry out below. 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.

As the polymerization inhibitor, a commonly used polymerization inhibitor for radically polymerizable monomers can be used. For example, hydroquinone, methylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, methoquinone, 6-t-butyl. -2,4-xylenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methoxyphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), etc. Phenolic inhibitors, organic acid copper salts, phenothiazines and the like, and one or more of these can be used. Among them, a phenol-based inhibitor is preferable in terms of low coloration and ability to prevent polymerization, and 2,2′-methylenebis (4-methyl-6-tert-butylphenol), methoquinone, 6-t- Butyl-2,4-xylenol and 2,6-di-t-butylphenol are more preferable.

The amount of the polymerization inhibitor used is a functional group capable of bonding with the base polymer component and the acid group from the viewpoint of ensuring sufficient polymerization prevention effect and curability when the curable resin composition is used. And it is preferable that it is 0.001-1 mass part with respect to 100 mass parts of total amounts with the compound which has a polymerizable double bond. More preferably, it is 0.01-0.5 mass part.

Examples of the compound having a polybasic acid anhydride group include succinic anhydride, dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride. Acid, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, glutaric anhydride, phthalic anhydride, trimellitic anhydride, anhydrous Examples include pyromellitic acid, and one or more of these can be used.

[Alkali-soluble resin]
The alkali-soluble resin obtained by the production method of the present invention preferably has an acid value of 30 to 230 mgKOH / g. When the acid value is in this range, sufficient alkali solubility is exhibited. For example, when a resist composition containing this alkali-soluble resin is used as an alkali development resist, it exhibits particularly good plate-making properties. Can do. Further, by employing the production method of the present invention, an alkali-soluble resin having an acid value in such a range can be obtained efficiently and easily. Thus, the form in which the production method is a method for obtaining an alkali-soluble resin having an acid value of 30 to 230 mgKOH / g is one of the preferred forms of the present invention. The acid value of the alkali-soluble resin is more preferably 40 mgKOH / g or more, more preferably 220 mgKOH / g or less, still more preferably 210 mgKOH / g or less, particularly preferably 200 mgKOH / g or less, more preferably 190 mgKOH / g or less. Most preferably, it is 180 mgKOH / g or less.

The acid value of the polymer is determined by, for example, an automatic titration apparatus (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.) using 0.1 N (N) KOH aqueous solution as the titrant. And the acid value per 1 g of polymer (mgKOH / g) can be calculated from the acid value of the polymer solution and the solid content concentration of the polymer solution.
Here, the solid content of the polymer solution can be determined as follows.
About 0.3 g of the polymer solution is weighed into an aluminum cup, and about 1 g of acetone is added and dissolved, followed by natural drying at room temperature. Then, after drying at 140 degreeC for 3 hours using a hot air dryer (brand name: PHH-101, Espec Co., Ltd.), it cools in a desiccator and measures a weight. From the weight reduction amount, the weight of the solid content (resin) of the polymer solution is calculated.

The alkali-soluble resin preferably has a weight average molecular weight of 2000 to 250,000. When the molecular weight is within this range, it is possible to obtain better platemaking properties. More preferably, it is 3000-100,000, More preferably, it is 4000-50000, Especially preferably, it is 4000-40000, Most preferably, it is 4000-30000. When the alkali-soluble resin has a high molecular weight, the higher the acid value, the better plate-making property is obtained. When the alkali-soluble resin has a low molecular weight, the good plate-making property tends to be obtained even when the acid value is low. There is.

For example, GPC (gel permeation chromatography; HLC-8220 GPC, manufactured by Tosoh Corporation) is used as the weight average molecular weight of the polymer, THF is used as an eluent, and TSKgel SuperHZM-N (manufactured by Tosoh Corporation) is used as a column. It can be determined in terms of polystyrene.

[Resist composition]
The alkali-soluble resin obtained by the production method of the present invention has a structural unit derived from a tertiary carbon-containing (meth) acrylate monomer, resulting in photosensitivity, adhesion to a substrate, developability, and heat resistance. Cured product (cured film) with excellent physical properties such as transparency and transparency, image formation and surface smoothness, no residue of unexposed areas, background stains, etc., and sufficiently reduced film thickness Can be given. Therefore, the alkali-soluble resin is, for example, various optical members such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, and photoresists used in liquid crystal display devices and solid-state imaging devices, and electrical / electronic devices. It is preferably used for such applications. Especially, it is suitable to use as a component of the resist composition used for these uses. Thus, the form in which the alkali-soluble resin is used in the resist composition is also one of the preferred forms of the present invention. A resist composition containing an alkali-soluble resin obtained by the above production method is also one aspect of the present invention.

The resist composition preferably contains a polymerizable compound and a photopolymerization initiator in addition to the alkali-soluble resin described above.

<Polymerizable compound>
The polymerizable compound is also called a polymerizable monomer, and can be polymerized by irradiation with active radicals such as free radicals, electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays), electron beams, etc. It is a low molecular compound having (also referred to as a polymerizable unsaturated group). For example, the monofunctional compound which has one polymerizable unsaturated group in a molecule | numerator, and the polyfunctional compound which has 2 or more are mentioned.

Examples of the monofunctional polymerizable monomer include, for example, N-substituted maleimide and (meta) among the compounds exemplified as other monomers preferably contained in the monomer component of the (meth) acrylate polymer. ) Acrylic esters; (Meth) acrylamides; Unsaturated monocarboxylic acids; Unsaturated polycarboxylic acids; Unsaturated monocarboxylic acids in which the chain between the unsaturated group and the carboxyl group is extended; Unsaturated acid anhydride Aromatic vinyls, conjugated dienes, vinyl esters, vinyl ethers, N-vinyl compounds, unsaturated isocyanates, and the like.

Examples of the polyfunctional polymerizable monomer include the following compounds.
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexanedimethanol Bifunctional (meth) acrylate compounds such as di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) acrylate; trimethylolpropane tri (meth) acrylate, ditrimethylolpropanetetra (meta ) Acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tet (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) Acrylate, ethylene oxide-added ditrimethylolpropane tetra (meth) acrylate, ethylene oxide-added pentaerythritol tetra (meth) acrylate, ethylene oxide-added dipentaerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added ditrile Methylolpropane tetra (meth) acrylate, propyleneoxy Addition pentaerythritol tetra (meth) acrylate, propylene oxide addition dipentaerythritol hexa (meth) acrylate, ε-caprolactone addition trimethylolpropane tri (meth) acrylate, ε-caprolactone addition ditrimethylolpropane tetra (meth) acrylate, ε-caprolactone Trifunctional or more polyfunctional (meth) acrylate compounds such as addition pentaerythritol tetra (meth) acrylate and ε-caprolactone addition dipentaerythritol hexa (meth) acrylate;

Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrile Methylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethyl Polyfunctional vinyl ethers such as ethylene propane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether; (meth) acrylic acid 2-vinyloxyethyl, (meth) acrylic acid 3-vinyloxypropyl, (meth) 1-methyl-2-vinyloxyethyl acrylate, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 5-vinyloxy (meth) acrylate Pentyl, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, p-vinyloxymethylphenylmethyl (meth) acrylate, (meth) acryl 2- (vinyloxy) ethyl, (meth) vinyl ether group-containing (meth) acrylic acid esters such as ethyl acrylic acid 2- (vinyloxy ethoxy ethoxy ethoxy);

Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, Ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethyl Polyfunctional allyl ethers such as ethylene propane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, ethylene oxide-added dipentaerythritol hexaallyl ether; allyl group-containing (meth) acrylic esters such as allyl (meth) acrylate; Multifunctional (meth) acryloyl groups such as tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri (acryloyloxyethyl) isocyanurate, alkylene oxide-added tri (methacryloyloxyethyl) isocyanurate -Containing isocyanurates; polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; tolylene diisocyanate, isophorone di Polyfunctional urethane obtained by reaction of polyfunctional isocyanates such as socyanate and xylylene diisocyanate with hydroxyl-containing (meth) acrylic esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate (Meth) acrylates; polyfunctional aromatic vinyls such as divinylbenzene;

Among the polymerizable compounds, it is preferable to use a polyfunctional polymerizable compound from the viewpoint of further improving the curability of the resist composition. When a polyfunctional polymerizable compound is used as the polymerizable compound, the functional number is preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more. Further, from the viewpoint of further suppressing curing shrinkage, the functional number is preferably 10 or less, more preferably 8 or less.
The molecular weight of the polymerizable compound is not particularly limited, but is preferably 2000 or less from the viewpoint of handling.

When a polyfunctional polymerizable compound is used as the polymerizable compound, among the polymerizable compounds, from the viewpoint of reactivity, economy, availability, etc., a polyfunctional (meth) acrylate compound, a polyfunctional urethane (meth) acrylate It is preferable to use a compound having a (meth) acryloyl group such as a compound or a (meth) acryloyl group-containing isocyanurate compound. More preferably, it is a polyfunctional (meth) acrylate compound, which makes the resist composition more excellent in photosensitivity and curability, and makes it possible to obtain a cured product having higher hardness and transparency. More preferably, a trifunctional or higher polyfunctional (meth) acrylate compound is used.

The content ratio of the polymerizable compound may be appropriately set according to the purpose and use in addition to the type of the polymerizable compound to be used and the type of the (meth) acrylate-based polymer. Therefore, it is preferably 2% by mass or more, and more preferably 85% by mass or less with respect to 100% by mass of the total solid content of the resist composition. The lower limit is more preferably 5% by mass or more, further preferably 8% by mass or more, particularly preferably 10% by mass or more, and the upper limit is more preferably 83% by mass or less, still more preferably 80% by mass or less, particularly preferably. Is 78% by mass or less, and most preferably 75% by mass or less.

<Photopolymerization initiator>
The photopolymerization initiator is preferably a radical polymerizable photopolymerization initiator. A radical polymerizable photopolymerization initiator is one that generates a polymerization initiating radical by irradiation with an active energy ray such as an electromagnetic wave or an electron beam, and one or more commonly used ones can be used. . Moreover, you may use together 1 type (s) or 2 or more types of photosensitizers, radical photopolymerization promoters, etc. as needed. A photosensitizer and / or photoradical polymerization accelerator may be used together with the photopolymerization initiator, or may not be used. Even if a photosensitizer and / or a radical photopolymerization accelerator are not used in combination, the effects of the present invention can be sufficiently exerted, but when used together, sensitivity and curability are further improved.

Specific examples of the photopolymerization initiator include the following compounds.
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-methylpropionyl) 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) Nyl] -1-butanone and other alkylphenone compounds; benzophenone, 4,4′-bis (dimethylamino) benzophenone, benzophenone compounds such as 2-carboxybenzophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin Benzoin compounds such as 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 Halomethylated triazine compounds such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine; 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-1,2 ′ -Biimidazole compounds such as biimidazole; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and other oxime ester compounds; bis (η5-2,4-cyclopentadien-1-yl) -bis (2, 6-Difluoro-3- (1H Pyrrol-1-yl) - phenyl) titanocene compounds such as titanium; p-dimethylaminobenzoic acid, p- benzoic acid ester compounds such as diethyl benzoate; acridine compounds such as 9-phenyl acridine or the like.

Examples of the photosensitizer and photoradical polymerization accelerator that may be used in combination with the photopolymerization initiator include dye compounds such as xanthene dyes, coumarin dyes, 3-ketocoumarin compounds, and pyromethene dyes; 4-dimethylamino Examples thereof include dialkylaminobenzene compounds such as ethyl benzoate and 2-ethylhexyl 4-dimethylaminobenzoate; mercaptan hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and 2-mercaptobenzimidazole.

The content of the photopolymerization initiator may be appropriately set according to the purpose, application, etc., and is not particularly limited, but is 0.1% with respect to 100 parts by mass of the total solid content of the resist composition excluding the photopolymerization initiator. It is preferable that the amount is not less than part by mass. Thereby, the hardened | cured material excellent by adhesiveness can be obtained, and peeling is suppressed more fully even after high temperature exposure. In consideration of the balance between the influence of the decomposition product of the photopolymerization initiator, economy, and the like, the amount is preferably 30 parts by mass or less. The lower limit is more preferably 0.5 parts by mass or more, further preferably 1 part by mass or more, particularly preferably 2 parts by mass or more, and the upper limit is more preferably 25 parts by mass or less, and still more preferably 20 parts by mass or less. is there.

The photosensitizer and the photoradical polymerization accelerator do not have to be used as described above, but when used, from the viewpoint of balance between curability, influence of degradation products and economy. It is preferable that it is 0.001-20 mass% with respect to 100 mass% of solid content total amount. More preferably, it is 0.01-15 mass%, More preferably, it is 0.05-10 mass%.

<Other ingredients>
-Solvent-
It is preferable that the resist composition also contains a solvent. A solvent is preferably used as a diluent or the like. Specifically, the viscosity is lowered to improve the handleability; the coating film is formed by drying; the coloring material is used as a dispersion medium; and the like in the resist composition. It is a low-viscosity organic solvent or water that can dissolve or disperse the components.

As the solvent, those usually used can be used, and may be appropriately selected according to the purpose and application, and are not particularly limited, and examples thereof include the following compounds. These may be used alone or in combination of two or more.

Monoalcohols such as methanol, ethanol, isopropanol, n-butanol, s-butanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol monoethers such as 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, ethylene glycol Jie Ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, glycol ethers such as 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 monoethyl ether acetate, propylene glycol Esters of glycol monoethers such as monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 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, Alkyl esters such as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl acetoacetate, ethyl acetoacetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; benzene, toluene, xylene, ethylbenzene, etc. Aromatic hydrocarbons; Aliphatic hydrocarbons such as hexane, cyclohexane, and octane; Amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; Water;

The amount of the solvent used may be appropriately set according to the purpose and application, and is not particularly limited, but is preferably 10 to 90% by mass in the total amount of 100% by mass of the resist composition. More preferably, it is 20-80 mass%.

The resist composition further includes, for example, a coloring material (also referred to as a colorant); a dispersant; a heat resistance improver; a leveling agent; a development aid; Inorganic fine particles; coupling agents such as silane, aluminum and titanium; thermosetting resins such as fillers, epoxy resins, phenol resins and polyvinylphenols; curing aids such as polyfunctional thiol compounds; plasticizers; polymerization inhibitors UV absorber, antioxidant, matting agent, antifoaming agent, antistatic agent, slip agent, surface modifier, thixotropic agent, thixotropic agent, quinonediazide compound, polyhydric phenol compound, cationic polymerizable compound 1 type or 2 or more types, such as; acid generator; For example, when the resist composition is used for a color filter, it is preferable to include a coloring material. Thus, the form in which the resist composition further contains a colorant is also one of the preferred forms of the present invention. A form containing at least one selected from the group consisting of a colorant, a dispersant, a heat resistance improver, a leveling agent, a coupling agent, and a development aid is also suitable.

<Method for producing resist composition>
It does not specifically limit as a manufacturing method of the said resist composition, For example, it can prepare by mixing and disperse | distributing the containing component mentioned above using various mixers and dispersers. The mixing / dispersing step is not particularly limited, and may be performed by a normal method. Further, it may further include other steps that are normally performed. In addition, when the said resist composition contains a coloring material, it is suitable to manufacture through the dispersion processing process of a coloring material.

The color material dispersion treatment step includes, for example, first weighing each of a predetermined amount of a color material (preferably an organic pigment), a dispersant and a solvent, and paint conditioner, bead mill, roll mill, ball mill, jet mill, homogenizer, kneader, blender. And the like, and using a dispersing machine such as a method, a color material is dispersed in fine particles to form a liquid color material dispersion (also referred to as a mill base). Preferably, after kneading and dispersing with a roll mill, kneader, blender or the like, fine dispersion is performed with a media mill such as a bead mill filled with 0.01 to 1 mm beads. A composition containing a (meth) acrylate polymer, a polymerizable monomer, a photopolymerization initiator, and, if necessary, a solvent, a leveling agent, and the like, which are separately stirred and mixed with the obtained mill base. A resist composition can be obtained by adding (preferably a transparent liquid) and mixing to obtain a uniform dispersion solution.
The obtained resist composition is preferably filtered with a filter or the like to remove fine dust.

[Cured product]
As described above, the resist composition of the present invention is particularly excellent in photosensitivity and curability, and is excellent in basic properties such as developability, solvent resistance, adhesion to a substrate (base material), heat resistance, and transparency. It gives a cured product. Such a cured product is also excellent in image formability and surface smoothness, and has, for example, no unexposed residue or background stains after development. A cured product obtained by curing such a resist composition is also one preferred embodiment of the present invention.

The cured product (cured film) preferably has a film thickness (thickness) of 0.1 to 20 μm. Thereby, it can fully respond to the request | requirement of low profile, such as a member using the said hardened | cured material, a display apparatus, etc. More preferably, it is 0.5-10 micrometers, More preferably, it is 0.5-8 micrometers.

The cured product is used for various optical members such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, etc. used in liquid crystal display devices, solid-state imaging devices, etc., and electrical / electronic devices. Are preferably used. Especially, it is preferable to use for a color filter. Thus, a color filter using the resist composition, specifically, a color filter having a cured product formed of the resist composition on a substrate is one of the preferred embodiments of the present invention. It is. Moreover, the display apparatus member and display apparatus which have the hardened | cured material formed with the said resist composition are also contained in suitable embodiment of this invention. As the display device, a liquid crystal display device, a solid-state imaging device, a touch panel display device, or the like is suitable, and the cured product is particularly useful as a protective film or an insulating film in various display devices.

Since the method for producing an alkali-soluble resin of the present invention has the above-described configuration, it has a structural unit derived from a tertiary carbon-containing (meth) acrylate monomer and an acid group-containing monomer, and is transparent. An alkali-soluble resin having a desired acid value can be obtained efficiently and easily. Therefore, a resist composition containing an alkali-soluble resin obtained by such a production method is particularly excellent in photosensitivity and curability, developability, solvent resistance, adhesion to a substrate (base material), heat resistance, and transparency. It is possible to give a cured product excellent in basic performance such as properties, and is extremely useful in various technical fields such as the optical field.

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, “v” means “volume%”, and “%” and “wt%” mean “mass%”.
In the following examples and the like, various physical properties and the like were measured as follows.

(1) Weight average molecular weight: Mw
GPC (HLC-8220GPC, manufactured by Tosoh Corporation) was used as an eluent, and TSKgel SuperHZM-N (manufactured by Tosoh Corporation) was used as a column for the measurement.

(2) Solid content About 0.3 g of the copolymer solution prepared in Examples and the like was weighed into an aluminum cup, dissolved by adding about 1 g of acetone, and then naturally dried at room temperature. Thereafter, using a hot air dryer (trade name: PHH-101, manufactured by ESPEC Corp.), it was dried at 140 ° C. for 3 hours, then allowed to cool in a desiccator, and the weight was measured. From the weight loss, the weight of the solid content (resin) of the polymer solution was calculated.

(3) Acid value 1.5 g of the copolymer solution prepared in Examples and the like was accurately weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and titrated with a 0.1 N aqueous KOH solution. Titration was performed using an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of polymer was determined from the solid content concentration (mgKOH / g).

Production Example 1
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, in the monomer dropping tank, 15 g of (α-allyloxymethyl) methyl acrylate (AMA-M), 31 g of methacrylic acid (MAA), 54 g of t-butyl methacrylate (tBuMA), t-butyl per 2 g of oxy-2-ethylhexanoate (trade name “Perbutyl (registered trademark) O”, manufactured by NOF Corporation, hereinafter also referred to as “PBO”) was added and mixed with stirring. Moreover, as a chain transfer agent solution, 1.8 g of β-mercaptopropionic acid (β-MPA) and 18 g of propylene glycol methyl ether acetate (PGMEA) were put into a chain transfer agent dropping tank and mixed with stirring.

The reactor was charged with 37.7 g of PGMEA and 130 g of propylene glycol monomethyl ether (PGME), purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reactor to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition was added dropwise over 180 minutes and the chain transfer agent solution was added dropwise over 210 minutes. After completion of the dropwise addition of the chain transfer agent solution, 0.5 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, the weight average molecular weight (Mw) and acid value of the base polymer (BP) were measured. At this time, Mw was 9200, and the acid value was 208 mgKOH / g. A gas introducing tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 27 g of glycidyl methacrylate (GMA) in the reaction vessel, 0.04 g of 6-tert-butyl-2,4-xylenol (trade name “Topanol”, manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor, and dimethylbenzyl as a catalyst 0.4 g of amine (DMBA) was charged and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution containing 39.9 weight% of side chain double bond containing polymers (DP). The weight average molecular weight (Mw) of DP was 11000, and the acid value was 92 mgKOH / g.
The production conditions, solid content concentration, weight average molecular weight (Mw) and acid value of the copolymer solution are shown in Table 1 together with Production Examples 2-9.

Production Example 2
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 15 g of benzylmaleimide (BzMI), 31 g of MAA, 54 g of tBuMA, 2 g of PBO, and 30 g of PGME were added as a monomer composition to the monomer dropping tank and mixed with stirring. In addition, as a chain transfer agent solution, 1.8 g of β-MPA and 18 g of PGMEA were added to a chain transfer agent dropping tank, and mixed with stirring.

After charging 37.7g of PGMEA and 100g of PGME into the reaction tank and replacing with nitrogen, the temperature of the reaction tank was raised to 90 ° C by heating with an oil bath while stirring. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition was added dropwise over 180 minutes and the chain transfer agent solution was added dropwise over 210 minutes. After completion of the dropwise addition of the chain transfer agent solution, 0.5 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, the weight average molecular weight (Mw) and acid value of the base polymer (BP) were measured. At this time, Mw was 9300, and the acid value was 207 mgKOH / g. A gas introducing tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 27 g of GMA, 0.04 g of topanol as a polymerization inhibitor, and 0.4 g of DMBA as a catalyst were charged in a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution containing 39.8 weight% of side chain double bond containing polymers (DP). The weight average molecular weight (Mw) of DP was 11200, and the acid value was 91 mgKOH / g.

Production Example 3
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, as a monomer composition, 15 g of dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate (MD), 31 g of MAA, 54 g of tBuMA, and 2 g of PBO were added to the monomer dropping tank and mixed. In addition, as a chain transfer agent solution, 1.8 g of β-MPA and 18 g of PGMEA were added to a chain transfer agent dropping tank, and mixed with stirring.

After charging 37.7 g of PGMEA and 130 g of PGME in the reaction vessel and replacing with nitrogen, the reaction vessel was heated to an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition was added dropwise over 180 minutes and the chain transfer agent solution was added dropwise over 210 minutes. After completion of the dropwise addition of the chain transfer agent solution, 0.5 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, the weight average molecular weight (Mw) and acid value of the base polymer (BP) were measured. At this time, Mw was 9200, and the acid value was 207 mgKOH / g. A gas introducing tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 27 g of GMA, 0.04 g of topanol as a polymerization inhibitor, and 0.4 g of DMBA as a catalyst were charged in a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution containing 39.7 weight% of side chain double bond containing polymers (DP). The weight average molecular weight (Mw) of DP was 10900, and the acid value was 91 mgKOH / g.

Production Example 4
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 15 g of AMA-M, 31 g of MAA, 54 g of t-amyl methacrylate (tAMA), and 2 g of PBO were added as a monomer composition to the monomer dropping tank and mixed with stirring. In addition, as a chain transfer agent solution, 1.8 g of β-MPA and 18 g of PGMEA were added to a chain transfer agent dropping tank, and mixed with stirring.

After charging 37.7 g of PGMEA and 130 g of PGME in the reaction vessel and replacing with nitrogen, the reaction vessel was heated to an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition was added dropwise over 180 minutes and the chain transfer agent solution was added dropwise over 210 minutes. After completion of the dropwise addition of the chain transfer agent solution, 0.5 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, the weight average molecular weight (Mw) and acid value of the base polymer (BP) were measured. At this time, Mw was 9100, and the acid value was 209 mgKOH / g. A gas introducing tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 27 g of GMA, 0.04 g of topanol as a polymerization inhibitor, and 0.4 g of DMBA as a catalyst were charged in a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution containing 39.6 weight% of side chain double bond containing polymers (DP). The weight average molecular weight (Mw) of DP was 10700, and the acid value was 92 mgKOH / g.

Production Example 5
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 15 g of AMA-M, 31 g of MAA, 54 g of tBuMA, and 2 g of PBO were added as a monomer composition into the monomer dropping tank and mixed with stirring. Moreover, as a chain transfer agent solution, 2.1 g of β-MPA and 18 g of PGMEA were put into a chain transfer agent dropping tank, and mixed with stirring.

PGMEA (27 g) and PGME (105 g) were charged into a reaction vessel, and after the atmosphere was replaced with nitrogen, the reaction vessel was heated to an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition was added dropwise over 180 minutes and the chain transfer agent solution was added dropwise over 210 minutes. After completion of the dropwise addition of the chain transfer agent solution, 0.5 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, the weight average molecular weight (Mw) and acid value of the base polymer (BP) were measured. At this time, Mw was 8900, and the acid value was 209 mgKOH / g. A gas introducing tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 27 g of GMA, 0.04 g of topanol as a polymerization inhibitor, 0.4 g of DMBA, 12.2 g of PGMEA, and 28.3 g of PGME were charged in a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Thereafter, the mixture was cooled to room temperature to obtain a copolymer solution containing 39.3% by weight of a side chain double bond-containing polymer (DP). The weight average molecular weight (Mw) of DP was 10500, and the acid value was 92 mgKOH / g.

Production Example 6
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 15 g of AMA-M, 31 g of MAA, 54 g of tBuMA, and 2 g of PBO were added as a monomer composition into the monomer dropping tank and mixed with stirring. In addition, as a chain transfer agent solution, 1.8 g of β-MPA and 18 g of PGMEA were added to a chain transfer agent dropping tank, and mixed with stirring.

After adding 75 g of PGMEA and 93 g of PGMEA to the reaction vessel and replacing with nitrogen, the reaction vessel was heated to 90 ° C. by heating in an oil bath while stirring. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition was added dropwise over 180 minutes and the chain transfer agent solution was added dropwise over 210 minutes. After completion of the dropwise addition of the chain transfer agent solution, 0.5 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, the weight average molecular weight (Mw) and acid value of the base polymer (BP) were measured. At this time, Mw was 9600, and the acid value was 207 mgKOH / g. A gas introducing tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 27 g of GMA, 0.04 g of topanol as a polymerization inhibitor, and 0.4 g of DMBA as a catalyst were charged in a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution containing 39.4 weight% of side chain double bond containing polymers (DP). The weight average molecular weight (Mw) of DP was 12000, and the acid value was 91 mgKOH / g.

Production Example 7
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 15 g of AMA-M, 31 g of MAA, 54 g of tBuMA, and 2 g of PBO were added as a monomer composition into the monomer dropping tank and mixed with stirring. Moreover, as a chain transfer agent solution, 2.1 g of β-MPA and 18 g of PGMEA were put into a chain transfer agent dropping tank, and mixed with stirring.

After 87 g of PGMEA and 45 g of PGME were charged into the reaction vessel and purged with nitrogen, the reaction vessel was heated to 90 ° C. by heating in an oil bath while stirring. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition was added dropwise over 180 minutes and the chain transfer agent solution was added dropwise over 210 minutes. After completion of the dropwise addition of the chain transfer agent solution, 0.5 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, the weight average molecular weight (Mw) and acid value of the base polymer (BP) were measured. At this time, Mw was 9700, and the acid value was 228 mgKOH / g. A gas introducing tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 27 g of GMA, 0.04 g of topanol as a polymerization inhibitor, 0.4 g of DMBA, 28.3 g of PGMEA, and 12.2 g of PGME were charged in a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution containing 39.0 weight% of side chain double bond containing polymers (DP). The weight average molecular weight (Mw) of DP was 12200, and the acid value was 110 mgKOH / g.

Production Example 8
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, as a monomer composition, 15 g of BzMI, 31 g of MAA, 54 g of tBuMA, 2 g of PBO, and 30 g of PGMEA were added to the monomer dropping tank and mixed with stirring. Moreover, as a chain transfer agent solution, 2.1 g of β-MPA and 18 g of PGMEA were put into a chain transfer agent dropping tank, and mixed with stirring.

The reaction vessel was charged with 57 g of PGMEA and 45 g of PGME, purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition was added dropwise over 180 minutes and the chain transfer agent solution was added dropwise over 210 minutes. After completion of the dropwise addition of the chain transfer agent solution, 0.5 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, the weight average molecular weight (Mw) and acid value of the base polymer (BP) were measured. At this time, Mw was 9800, and the acid value was 230 mgKOH / g. A gas introducing tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 7/93 (v / v) mixed gas was started. Next, 27 g of GMA, 0.04 g of topanol as a polymerization inhibitor, 0.4 g of DMBA, 28.3 g of PGMEA, and 12.2 g of PGME were charged in a reaction vessel, and reacted at 110 ° C. for 1 hour and 115 ° C. for 7 hours. Then, it cooled to room temperature and obtained the copolymer solution containing 38.9 weight% of side chain double bond containing polymers (DP). The weight average molecular weight (Mw) of DP was 12100, and the acid value was 111 mgKOH / g.

Production Example 9
A separable flask equipped with a cooling tube was prepared as a reaction vessel. On the other hand, 15 g of AMA-M, 31 g of MAA, 54 g of tBuMA, and 2 g of PBO were added as a monomer composition into the monomer dropping tank and mixed with stirring. Moreover, as a chain transfer agent solution, 2.1 g of β-MPA and 18 g of PGMEA were put into a chain transfer agent dropping tank, and mixed with stirring.

After charging 132 g of PGMEA into the reaction vessel and replacing with nitrogen, the reaction vessel was heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., the monomer composition and the chain transfer agent solution were added dropwise. While maintaining the temperature at 90 ° C., the monomer composition was added dropwise over 180 minutes and the chain transfer agent solution was added dropwise over 210 minutes. After completion of the dropwise addition of the chain transfer agent solution, 0.5 g of PBO was added. After an additional 30 minutes, the bath was heated to 115 ° C. After maintaining at 115 ° C. for 1.5 hours, the copolymer solution was clouded due to polymer precipitation. The acid value of the base polymer (BP) was measured. At this time, the acid value was 251 mgKOH / g.

From the above production example, the following was confirmed.
Production Examples 1 and 5 to 7 and Production Example 9 are mainly different in that an alcohol solvent is used as a polymerization solvent. In Production Example 9 in which the polymerization step was performed without using an alcohol solvent, elimination of the tertiary carbon in the tertiary carbon-containing (meth) acrylate monomer (tBuMA) occurred during the polymerization, and an acid was generated. The polymerization solution became cloudy and the polymer could not be synthesized easily. On the other hand, by introducing an alcohol solvent (Production Examples 1 and 5 to 7), generation of acid due to elimination of tertiary carbon is suppressed, and the resin solution is transparent and has a reduced acid value (polymer solution). ) Among them, in Production Examples 1, 5, and 6 in which the content of the alcohol solvent is 20% by mass or more (preferably 30% by mass or more) with respect to 100% by mass of the polymerization solution, the content of the alcohol solvent is 17.7% by mass. It can be seen that the elimination of the tertiary carbon is further suppressed and the acid value is further reduced as compared to Production Example 7 in which the acid value is%.

Production Examples 2 to 4 are examples in which only a part of the monomer components are different from Production Example 1, but the generation of acid due to elimination of tertiary carbon is sufficiently suppressed as in Production Example 1. Thus, a transparent resin solution (polymer solution) having a sufficiently reduced acid value could be obtained. Of these, Production Example 2 is an example in which the use amount of the alcohol solvent is mainly different from Production Example 8, but the content of the alcohol solvent is 20% by mass or more (preferably 30% by mass) with respect to 100% by mass of the polymerization solution. In Production Example 2 in which the content of the alcohol solvent was 17.7% by mass, the elimination of tertiary carbon was further suppressed and the acid value was further reduced compared to Production Example 8 in which the content of the alcohol solvent was 17.7% by mass. I understand.

Claims (5)

A method for producing an alkali-soluble resin, comprising:
The production method has a step of polymerizing a monomer component including a tertiary carbon-containing (meth) acrylate monomer and an acid group-containing monomer by a radical polymerization mechanism in the presence of a saturated alcohol,
The amount of the saturated alcohol used is 20 to 80% by mass with respect to 100% by mass of the total amount of the polymerization solution,
The saturated alcohol is methanol, ethanol, isopropanol, n-butanol, s-butanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, At least one selected from the group consisting of diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, and 3-methoxybutanol ;
The tertiary carbon-containing (meth) acrylate monomer has a structure in which an oxygen atom adjacent to a (meth) acryloyl group is bonded to a tertiary carbon atom,
The monomer component further includes at least one compound selected from the group consisting of N-substituted maleimide, acrylic ether dimer, and α- (allyloxymethyl) acrylate,
The acrylic ether dimer is a compound represented by the following general formula (2):

(In the formula, R ⁴ represents a hydrogen atom or an organic group having 1 to 25 carbon atoms which may have a substituent. R ⁵ may have a hydrogen atom or a substituent. Represents a good organic group having 1 to 25 carbon atoms.)
The content of the tertiary carbon-containing (meth) acrylate monomer is 15% by mass to 75% by mass with respect to 100% by mass of the monomer component, and the content of the acid group-containing monomer Is 5 mass% or more and 70 mass% or less, The content rate of this compound is 5-50 mass%, The manufacturing method of alkali-soluble resin characterized by the above-mentioned. The method for producing an alkali-soluble resin according to claim 1, wherein the amount of the saturated alcohol used is 20 to 100% by mass with respect to 100% by mass of the total amount of the solvent used in the polymerization step. The polymerization temperature in the polymerization step, the manufacturing method of the alkali-soluble resin according to claim 1 or 2 which is 50 to 150 ° C.. The said alkali-soluble resin is used for a resist composition, The manufacturing method of the alkali-soluble resin in any one of Claims 1-3 characterized by the above-mentioned. A method for producing a resist composition comprising:
A step of producing an alkali-soluble resin by polymerizing a monomer component containing a tertiary carbon-containing (meth) acrylate monomer and an acid group-containing monomer by a radical polymerization mechanism in the presence of a saturated alcohol; and
Including a step of mixing and dispersing the alkali-soluble resin, the polymerizable compound and the photopolymerization initiator obtained in the step,
In the step of producing the alkali-soluble resin, the amount of the saturated alcohol used is 20 to 80% by mass with respect to 100% by mass of the total amount of the polymerization solution.
The saturated alcohol is methanol, ethanol, isopropanol, n-butanol, s-butanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, At least one selected from the group consisting of diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, and 3-methoxybutanol ;
The tertiary carbon-containing (meth) acrylate monomer has a structure in which an oxygen atom adjacent to a (meth) acryloyl group is bonded to a tertiary carbon atom,
The monomer component further includes at least one compound selected from the group consisting of N-substituted maleimide, acrylic ether dimer, and α- (allyloxymethyl) acrylate,
The acrylic ether dimer is a compound represented by the following general formula (2):

(In the formula, R ⁴ represents a hydrogen atom or an organic group having 1 to 25 carbon atoms which may have a substituent. R ⁵ may have a hydrogen atom or a substituent. Represents a good organic group having 1 to 25 carbon atoms.)
The content of the tertiary carbon-containing (meth) acrylate monomer is 15% by mass to 75% by mass with respect to 100% by mass of the monomer component, and the content of the acid group-containing monomer Is 5 mass% or more and 70 mass% or less, and the content rate of this compound is 5-50 mass%, The manufacturing method of the resist composition characterized by the above-mentioned.