JP2002332314A - Carboxyl group-containing polyfumarate, its manufacturing method and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyfumarate having carboxyl groups which excels in alkali solubility and heat resistance, to provide its manufacturing method, and to obtain an alkaline base resin for a photosensitive resin composition using the above polyfumarate. SOLUTION: The polyfumarate having carboxyl groups is composed of a repeating constituting unit derived from a fumaric diester and a constituting unit derived from a substituted ethylene having a carboxyl group. Furthermore, the polyfumarate is a compound having at least one constituting unit based on the fumaric diester and at least one constituting unit based on a carboxyl group-containing monomer and has a molecular weight of 1,000-300,000, and simultaneously, an acid value of 50-250 mgKOH/g.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyfumarate having a carboxyl group having excellent alkali solubility and heat resistance, a method for producing the same, and an alkali developable base resin for various photosensitive resin compositions.

[0002]

2. Description of the Related Art As a method for introducing a carboxyl group into a polymer skeleton while maintaining the inherent heat resistance of polyfumarate, a monomer having a carboxyl group such as acrylic acid, fumaric acid and itaconic acid is used. And a method of copolymerizing However, since fumarate has poor copolymerizability with the monomer having a carboxyl group, a copolymer having a carboxyl group introduced to a practical level could not be obtained.

On the other hand, a method of forming fine images on various materials using a photoresist using a photosensitive resin composition has been proposed.
It is widely used in fields such as printing plates, electronic materials, and metal processing. Among those applications, the permanent resist that leaves the image of the photoresist formed by exposure and development as a film is as follows: 1) The part that is used in the pre-process of soldering electronic components to the printed wiring board, There is a solder resist that forms a film on the entire surface of the circuit conductor except for the resist, and 2) a resist for a photosensitive printing plate used for various printings.

At the beginning of the development of permanent resists, solvent-developable resists were mainly used. However, in order to cope with waste solvent processing costs and environmental problems at workplaces and regions, the currently used resists are alkaline. Developability is becoming mainstream.

The alkali-developable base resin used in the photosensitive resin composition for an alkali-developable resist includes:
For example, a polymer having an unsaturated bond and a carboxyl group (JP-A-5-202330), a polymer composed of a novolak-type epoxy resin, and a reaction product of an anhydride of acrylic acid and a polybasic acid (JP-A-3-71137) JP-A-4-345608), a product obtained by reacting a reaction product of a hydantoin epoxy resin and acrylic acid with a polybasic acid (JP-A-4-345608), a polymer containing a styrene-based monomer and a carboxylic acid-containing monomer. Japanese Unexamined Patent Publication No. Hei 10-26829,
No. 0-10734).

[0006] However, these alkali-developable base resins according to the prior art show excellent alkali-developability, but the further improvement in heat resistance required for various permanent resists is insufficient. For example, in the technical field of solder resist, at present, sufficient heat resistance performance that does not always satisfy the demand for high heat resistance that can respond to lead-free soldering is not obtained.

[0007]

SUMMARY OF THE INVENTION The present invention has been made by focusing on the problems existing in the prior art as described above. An object of the present invention is to provide a polyfumarate having a carboxyl group excellent in alkali solubility and heat resistance, a method for producing the same, and an alkali-developable base resin for a photosensitive resin composition using the polyfumarate.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above problems, and as a result, after polymerizing a polymerizable monomer having a fumaric acid diester and a block carboxylic acid group,
The inventors have found that a polyfumarate having excellent heat resistance and alkali developability can be obtained by the deblocking method, and have completed the present invention. That is, the present invention includes the following [1] to [6]. [1] A polyfumarate containing (A) a structural unit based on a fumaric acid diester and (B) a structural unit based on a carboxyl group-containing monomer.

[2] (A) a compound having at least one structural unit based on a fumaric acid diester represented by the following formula (1) and (B) a structural unit based on a carboxyl group-containing monomer, and having a molecular weight of: Is a polyfumarate having an acid value of 1,000 to 300,000 and an acid value of 50 to 250 mgKOH / g.

[0010]

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(However, X ¹ and X ² in the formula may be the same or different and each represents a branched alkyl group or a substituted branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl group or a substituted alkyl group having 4 to 8 carbon atoms.) Represents a cycloalkyl group.)

[3] A compound having (A) a structural unit based on a fumaric acid diester represented by the following formula (1) and (B) a structural unit based on a carboxyl group-containing monomer,
When the components (A) and (B) are 70% by weight or more in the molecule,
The weight ratio of (A + B) is 0.5 to the entire copolymer composition.
0.95% by weight and a molecular weight of 5,000 to 200,
000 and a polyfumarate having an acid value of 70 to 200 mg KOH / g.

[0013]

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(However, X ¹ and X ² in the formula may be the same or different and each represents a branched alkyl group or a substituted branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl group or a substituted alkyl group having 4 to 8 carbon atoms.) Represents a cycloalkyl group.)

[4] (A) a fumaric acid diester structural unit represented by the following formula (1), (B) a repeating structural unit represented by the following formula (2), and a repetition represented by the following formula (5) By performing a deblocking reaction on a copolymer precursor comprising at least one structural unit selected from the group of structural units based on a block carboxylic acid comprising a structural unit and a repeating structural unit represented by the following formula (6): The obtained carboxyl group-containing polyfumarate according to any one of the first to third inventions.

[0016]

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(However, X ¹ and X ² in the formula may be the same or different and each represents a branched alkyl group or a substituted branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl group or a substituted alkyl group having 4 to 8 carbon atoms.) Represents a cycloalkyl group.)

[0018]

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(However, Y ¹ and Y ² in the formula may be the same or different and each represents a branched alkyl group or a substituted branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl group or a substituted alkyl group having 4 to 8 carbon atoms.) A cycloalkyl group, and at least one of Y ^{1 and} Y ^{2 in} the molecule is a group represented by the following formula (3) or (4))

[0020]

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[0021]

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(However, R ¹ and R ^{2 in the} formulas (3) and (4)
And R ³ each represent a hydrogen atom or a C 1-18
R ⁴ is an organic group having 1 to 18 carbon atoms, and Z ¹ is an oxygen atom or a sulfur atom. R ⁵
And R ⁶ are an organic group having 1 to 18 carbon atoms. )

[0023]

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(However, Y ¹ and Y ² in the formula represent the same as in the formula (2).)

[0025]

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(Where Y ³ is represented by the following formula (3) or (4). D is a benzyl group, n is 0 or 1, and E is a hydrogen atom or a methyl group. Represents.)

[0027]

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[0028]

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(However, R ¹ and R ^{2 in the} formulas (3) and (4)
And R ³ each represent a hydrogen atom or a C 1-18
R ⁴ is an organic group having 1 to 18 carbon atoms, and Z ¹ is an oxygen atom or a sulfur atom. R ⁵
And R ⁶ are an organic group having 1 to 18 carbon atoms. )

[5] The method for producing a polyfumarate having a carboxyl group according to any one of the first to third inventions, comprising the following first and second steps: It is a manufacturing method. First step: a fumaric acid diester represented by the following formula (7), a polymerizable monomer represented by the following formula (8), a polymerizable monomer represented by the following formula (9), and Copolymerizing one or more polymerizable monomers selected from the group consisting of the polymerizable monomers represented by the formula (10), the second step: the copolymer obtained in the first step The precursor is deblocked.

[0031]

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(However, X ¹ and X ² in the formula may be the same or different and each represents a branched alkyl group or a substituted branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl group or a substituted alkyl group having 4 to 8 carbon atoms.) Represents a cycloalkyl group.)

[0033]

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(However, Y ¹ and Y ² in the formula may be the same or different and each represents a branched alkyl group or a substituted branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl group or a substituted alkyl group having 4 to 8 carbon atoms.) It represents a group represented by a cycloalkyl group, and at least one of Y ^{1 and} Y ^{2 in} the molecule represents a group represented by the following formula (3) or (4).)

[0035]

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[0036]

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(However, R ¹ and R ^{2 in the} formulas (3) and (4)
And R ³ each represent a hydrogen atom or a C 1-18
R ⁴ is an organic group having 1 to 18 carbon atoms, and Z ¹ is an oxygen atom or a sulfur atom. R ⁵
And R ⁶ are an organic group having 1 to 18 carbon atoms. )

[0038]

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(However, Y ¹ and Y ² in the formula represent the same as in the formula (2).)

[0040]

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(However, Y ³ , D, n and E in the formula represent the same as described above.)

[6] An alkali-developable base resin for a photosensitive resin composition comprising a carboxyl-containing polyfumarate according to any one of the above-mentioned inventions 1 to 4.

[0043]

BEST MODE FOR CARRYING OUT THE INVENTION The carboxyl group-containing polyfumarate of the present invention comprises (A) a repeating structural unit derived from a fumaric acid diester and (B) a repeating structural unit derived from a substituted ethylene having a carboxyl group at least one each. A copolymer having at least 70% by weight of a group based on the components (A) and (B) in the molecule. Further preferred as the polyfumarate having a carboxyl group are 95 to 50% by weight of a repeating structural unit derived from a fumaric acid diester and a structural unit 5 derived from substituted ethylene having a carboxyl group.
It is a polyfumarate having a carboxyl group consisting of 50% by weight.

When the content of repeating structural units derived from fumaric acid diester is less than 50% by weight or the content of structural units derived from substituted ethylene having a carboxyl group exceeds 50% by weight, the heat resistance of polyfumarate having a carboxyl group is reduced. There is a tendency. When the repeating unit derived from fumaric acid diester exceeds 95% by weight or when the structural unit derived from substituted ethylene having a carboxyl group is less than 5% by weight, alkali solubility of polyfumarate having a carboxyl group decreases. This is not preferred because of the tendency.

The polyfumarate having a carboxyl group of the present invention includes a repeating structural unit represented by the above formula (1), a repeating structural unit represented by the above formula (2), and a repeating structural unit represented by the above formula (5). A copolymer precursor having a repeating structural unit represented by the formula (6) and one or more structural units selected from the group consisting of the repeating structural unit represented by the formula (6) is deblocked by heat treatment, chemical treatment or active energy ray treatment. Reaction (that is, the following formula (11) and formula (1)
The compound represented by 2) is eliminated to generate a carboxyl group. ).

[0046]

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[0047]

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(Where R ¹ , R ² , R ³ , R ⁴ , R
⁵ and Z ³ are the same as above. )

The polymerizable monomer as a raw material for forming the polyfumarate having a carboxyl group of the present invention includes:
At least one polymerizable monomer selected from the group consisting of the fumaric acid diester represented by the above formula (7) and the polymerizable monomers represented by the above formulas (8), (9) and (10) Body. Further, in order to balance various physical properties such as copolymerizability, heat resistance, and processability, the fumaric acid diester and the polymerizable monomer represented by the formulas (8), (9) and (10) are used. In addition to the above, another polymerizable monomer may be included. The amount is from 0 to 30% by weight based on the whole in the molecule.

The fumaric acid diester includes a branched alkyl group having 3 to 8 carbon atoms or a substituted branched alkyl group;
Or a symmetric diester or an asymmetric diester having a cycloalkyl group or a substituted cycloalkyl group having 4 to 8 carbon atoms can be exemplified. As a specific example,
Diisopropyl fumarate, di-sec-butyl fumarate, di-tert-butyl fumarate, diisobutyl fumarate, di-tert-amyl fumarate, di-4
-Methyl-2-pentyl fumarate, di-sec-amyl fumarate, di-3-pentyl fumarate, di-4-
Methyl-pentyl fumarate, bis (2,4-dimethyl-3-pentyl) fumarate, isopropyl-sec-butyl fumarate, tert-butyl-4-methyl-2-
Pentyl fumarate, isopropyl-tert-butyl fumarate, sec-butyl-tert-butyl fumarate, sec-butyl-tert-amyl fumarate,
tert-butyl-isoamyl fumarate, isopropyl-cyclobutyl fumarate, 1-chloro-2-propyl-cyclopentyl fumarate, 1,3-dichloro-2
-Propyl-cyclohexyl fumarate, sec-butyl-cyclohexyl fumarate, 3-chloro-2-propyl-cyclohexyl fumarate, tert-butyl-
Cyclopentyl fumarate, tert-butylcyclohexyl fumarate, sec-amyl-cyclohexyl fumarate, 3-pentyl-bornyl fumarate, 2,3
-Dimethyl-3-pentyl-adamantyl fumarate,
tert-amyl-cyclohexyl fumarate, neopentyl-cyclopentyl fumarate, 4-methyl-2-
And pentyl-cyclohexyl fumarate.

The polymerizable monomer represented by any one of the formulas (8), (9) and (10) is combined with the polymerizable monomer having a carboxyl group and the formula (11) or (12) )
, Ie, a vinyl ether compound, a vinyl thioether compound, or a heterocyclic compound having a vinyl type double bond having an oxygen atom or a sulfur atom as a hetero atom.

The formula (8), (9) or (1)
Specific examples of the polymerizable monomer having a carboxyl group used for synthesizing the polymerizable monomer represented by 0) include the following. For formula (8), for example, fumaric acid, maleic acid, citraconic acid, mesaconic acid, etc. For formula (9), for example, itaconic acid, etc., formula (10)
For example, acrylic acid, methacrylic acid, β-methacryloyloxyethyl hydrogen succinate, β-acryloyloxyethyl hydrogen succinate, 4-vinylphenylacetic acid and the like can be mentioned.

Specific examples of the compound represented by the formula (11) include aliphatic vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, amyl vinyl ether, cyclohexyl vinyl ether, octyl vinyl ether, behenyl vinyl ether, and stearyl vinyl ether. And corresponding aliphatic vinyl thioether compounds. Furthermore, specific examples of the compound represented by the formula (12) include 2,3-dihydrofuran,
4-dihydrofuran, 2,3-dihydro-2H-pyran, 3,4-dihydro-2H-pyran, 3,4-dihydro-2-methoxy-2H-pyran, 3,4-dihydro-
4,4-dimethoxy-2H-pyran-2-one, 3,4
-Dihydro-2H-pyran, 3,4-dihydro-2H-
Examples include cyclic vinyl ether compounds such as sodium pyran-2-carboxylate, and corresponding cyclic vinyl thioether compounds. More preferred are isobutyl vinyl ether, cyclohexyl vinyl ether, tert-butyl vinyl ether, tert-amyl vinyl ether, 2-ethylhexyl vinyl ether, and 2-ethylhexyl acid phosphate.

The polymerizable monomer represented by the formula (8), (9) or (10) used in the present invention comprises a monomer having a carboxyl group and the formula (11) or the formula (12). By reacting with a compound represented by the formula at a temperature in the range of room temperature to 150 ° C. At this time, an acid catalyst can be used for the purpose of accelerating the reaction. Examples of such a catalyst include a compound obtained by neutralizing a protonic acid with a Lewis base, a compound obtained by neutralizing a Lewis acid with a Lewis base,
Mixtures of Lewis acids and trialkyl phosphates, sulfonic esters, phosphoric esters, and onium compounds, inorganic acids.

Examples of the compound obtained by neutralizing the protonic acid with a Lewis base include halogenocarboxylic acids, sulfonic acids, sulfuric acid monoesters, phosphoric acid mono- and diesters, polyphosphate esters, boric acid mono- and diesters, and the like. , Ammonia, monoethylamine, triethylamine, pyridine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoamineamine, diethanolamine, various amines such as triethanolamine or trialkylphosphine, triarylphosphine, trialkylphosphine, triamine Compounds neutralized with reel phosphite, and Nailure 2500X, X-47-110, 3525, 525 which are commercially available as acid-base blocking catalysts
225 (both are trade names, manufactured by King Industry)
And the like.

Compounds obtained by neutralizing a Lewis acid with a Lewis base include, for example, BF ₃ , FeCl ₃ , SnCl ₄ ,
Examples include compounds obtained by neutralizing a Lewis acid such as AlCl ₃ or ZnCl ₂ with the above-mentioned Lewis base. The sulfonic acid ester is, for example, a compound represented by the following formula (14).

[0057]

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(Wherein R ⁷ is a phenyl group, a substituted phenyl group, a naphthyl group, a substituted naphthyl group or an alkyl group, and R ⁸ is a carbon atom bonded to a sulfonyloxy group via a primary carbon or a secondary carbon. An alkyl group of the number 3 to 18,
An alkenyl group, an aryl group, an alkaryl group, an alkanol group, a saturated or unsaturated cycloalkyl or hydroxycycloalkyl group. )

More specifically, sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, nonylnaphthalenesulfonic acid, and n-propanol;
primary alcohols such as n-butanol, n-hexanol, n-octanol or isopropanol;
-Butanol, 2-hexanol, 2-octanol,
Examples thereof include esterified products with secondary alcohols such as cyclohexanol, and β-hydroxyalkylsulfonic acid esters obtained by reacting the sulfonic acids with an oxirane group-containing compound. Examples of the phosphoric esters include an acidic phosphoric ester compound represented by the formula (15).

[0060]

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(Wherein R ⁹ is an alkyl group, cycloalkyl group or aryl group having 3 to 10 carbon atoms, and m is 1 or 2.) More specifically, n-propanol, n-hexanol, n Phosphoric acid monoesters or phosphoric acid diesters of primary alcohols such as octanol and n-ethylhexanol; secondary alcohols such as isopropanol, 2-butanol, 2-hexanol, 2-octanol and cyclohexanol Phosphoric acid monoesters or phosphoric acid diesters are exemplified.

Examples of the onium compound include compounds of the formulas (16) to (19). _{^{[R 11 3 NR 12] +}} X - ... (16) [R 13 3 PR 14] + X - ... (17) [R 15 2 OR 16] + X - ... (18) [R 17 2 SR 18] + X ^- ... (19)

In the formula, R ¹¹ , R ¹³ , R ¹⁵ and R ¹⁷ are an alkyl group having 1 to 12 carbon atoms, alkenyl group, aryl group, alkaryl group, alkanol group or cycloalkyl group. When two R ¹¹ , R ¹³ , R ¹⁵ and R ¹⁷ are bonded to each other, they form a heterocyclic ring having N, P, O or S as a hetero atom. R ¹² , R ¹⁴ , R ¹⁶ and R
¹⁸ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an aryl group, an alkaryl group, X ^- is Sb
F ₆ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ or BF ₄ ⁻ . Examples of the inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, and mixtures thereof.

Further, an organic solvent can be used for the purpose of making the reaction system uniform and facilitating the reaction. Examples of such an organic solvent include n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane,
n-heptane, n-octane, mineral spirit, isooctane, nonane, trimethylhexane, decane, isodecane, cyclopentane, methylcyclopentane, decalin, isobar (Exxon Chemical Co., Ltd., registered trademark), New Solderlux (Nippon Oil ( Aliphatic hydrocarbons, such as Shellsol 70 (Shell Chemical Co., registered trademark); benzene, toluene, xylene,
Ethylbenzene, aromatic petroleum naphtha, tetralin, turpentine, Solvesso # 100 (Exxon Chemical Co., Ltd., registered trademark), Solvesso # 150 (Exxon Chemical Co., Ltd.)
Ethers such as dioxane and tetrahydrofuran; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate and methoxy butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone and the like. Ketones; phosphates such as trimethyl phosphate, triethyl phosphate and tributyl phosphate; and dimethyl sulfoxide, N, N-dimethylformamide and the like.

Specific examples of the other polymerizable monomers include the following (a) to (h). (A) C1-C1 such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octadecyl (meth) acrylate, docosyl (meth) acrylate
An acrylate ester having 22 alkyl groups. Here, (meth) acrylate means methacrylate and / or acrylate. (B) dimethyl itaconate, diethyl itaconate,
Itaconic esters such as diisobutyl itaconate, di-sec-butyl itaconate, di-tert-butyl itaconate and dicyclohexyl itaconate.

(C) Styrene derivatives such as styrene, α-methylstyrene and chlorostyrene. (D) Unsaturated ketones such as methyl vinyl ketone and butyl vinyl ketone. (E) Vinyl esters such as vinyl acetate and vinyl butyrate. (F) methyl vinyl ether, butyl vinyl ether,
Vinyl ethers such as cyclohexyl vinyl ether. (G) Allyl compounds such as phenyl allyl ether, methyl allyl ether, cyclohexyl allyl ether, allyl propionate, allyl myristate, allyl cyclohexyl propionate. (H) N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide.

The weight fraction of each polymerizable monomer charged when forming a polymer is determined from the viewpoint of the alkali solubility of the polyfumarate having a carboxyl group. The weight fraction of fumaric acid diester is usually 95 to 50% by weight, preferably 90 to 55% by weight. The total weight fraction of the polymerizable monomer represented by the formula (8), (9) or (10) is 5 to 50% by weight, preferably 10 to 50% by weight.
３０30% by weight. When the weight fraction of the fumaric acid diester is less than 50% by weight or when the total weight fraction of the polymerizable monomers represented by the formulas (8), (9) or (10) exceeds 50% by weight The heat resistance of polyfumarate having a carboxyl group tends to decrease. When the weight fraction of the fumaric acid diester exceeds 95%, or when the total weight fraction of the polymerizable monomers represented by the formulas (8), (9) or (10) is less than 5% by weight. In this case, the alkali solubility of the polyfumarate having a carboxyl group tends to decrease. Further, the weight fraction of the other polymerizable monomers is determined by the fumaric acid diester and the formula (8),
It is 0 to 30% by weight, preferably 0 to 20% by weight, based on the total amount of the polymerizable monomer represented by (9) or (10).

As the copolymer precursor and the polyfumarate having a carboxyl group obtained therefrom, those having a weight average molecular weight in any range can be used as long as the desired alkali solubility is obtained. The weight average molecular weight of the polyfumarate is usually preferably from 5,000 to
200,000, more preferably 10,000 to 10
000. When the weight average molecular weight is less than 5,000, the alkali dissolution rate of the carboxyl group-containing polyfumarate tends to be too high, and when the weight average molecular weight exceeds 200,000, the alkali dissolution of the carboxyl group-containing polyfumarate becomes difficult. Speed tends to be too low.

As the structure of the copolymer precursor, various structures such as random, block, graft, and ladder are possible, but the random structure is preferable in that the alkali solubility of the copolymer can be maintained well. It is preferable to have

Next, a method for producing a polyfumarate having a carboxyl group will be described in detail. The production comprises, as a first step, synthesis of a copolymer precursor by a radical copolymerization reaction, and as a second step, a deblocking reaction of the compound represented by the formula (11) or (12).

First, the first step will be described. In the radical polymerization reaction, a polymerization initiator that thermally generates radicals is added to a mixture of the fumaric acid diester and the polymerizable monomer represented by the formula (8), (9) or (10), Perform bulk polymerization as it is, perform suspension polymerization by dispersing in an aqueous solution containing a water-soluble polymer or inorganic dispersant, or an organic solvent that dissolves each polymerizable monomer and copolymer precursor Solution polymerization in water.

Examples of the polymerization initiator include, for example, 2,
2′-azobisisobutyronitrile (AIBN), 2,
2'-azobiscyclohexanecarbonitrile (AC
Azo organic compounds such as N); dibenzoyl peroxide (B
PO), tert-butyl hydroperoxide (TBH
P), di-tert-butyl peroxide (DtB
P) and organic peroxides such as dicumyl peroxide (DCP).

Next, the second step will be described. When the obtained copolymer precursor is subjected to a heat treatment, a chemical treatment, or a treatment by irradiation with an active energy ray such as an ultraviolet ray or an electron beam, the copolymer precursor is expressed by the above formula (11) or (12). Carboxyl group is generated by the elimination of the compound (may be called deblocking reaction),
The desired polyfumarate having a carboxyl group can be obtained. This carboxyl group formation reaction is promoted by an acid catalyst or a photoacid catalyst. Such acid catalysts include, for example, halogenocarboxylic acids, sulfonic acids,
Protonic acids such as sulfuric acid monoesters, phosphoric acid mono- and diesters, polyphosphate esters, boric acid mono- and diesters; BF ₃ , FeCl ₃ , SnCl ₄ , Al
Lewis acids such as Cl ₃ and ZnCl ₂ can be mentioned. Adeka Optomer SP series (trade name, manufactured by Asahi Denka Kogyo KK) can be used as the photoacid catalyst.

The conditions for performing the deblocking reaction of the compound represented by the formula (11) or (12) vary depending on the type and amount of the acid catalyst or the photoacid catalyst. 2% to 15% by weight of concentrated hydrochloric acid based on the copolymer precursor in a dioxane solution at 50% to 100 ° C
By performing the reaction for 3 to 12 hours, the deblocking reaction can proceed almost quantitatively. for that reason,
By adjusting the copolymer composition of the fumaric acid derivative, the acid value of the resulting polyfumarate having a carboxyl group can be freely controlled. Preferably the acid number is 50
~ 250mgKOH / g, more preferably 70 ~ 200
mg KOH / g.

The deblocked compound represented by the formula (11) or (12) may be removed as a precipitate when the solution obtained after the deblocking reaction is poured into water, It may be removed by topping (azeotropic removal) with a solvent while stirring under reduced pressure in a reaction vessel.

The polyfumarate having a carboxyl group of the present invention can be used as an alkali-developable base resin which is a main component of a photosensitive resin composition for an alkali-developable resist. At that time, generally, the photosensitive resin composition for an alkali-developable resist contains, as essential components, an alkali-developable base resin, a polymerizable monomer, and a polymerization initiator for initiating polymerization by active energy rays. ing. If necessary, a polymerization initiator for initiating polymerization by heat can be further blended. This is used as a polymerization initiator when performing post-curing to completely cure the developed resist coating film.

The polymerizable monomers used in the photosensitive resin composition include various acrylates such as butyl acrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate; divinyl adipate, cyclohexane diacrylate and the like. Vinyl compounds such as methanol divinyl ether, diallyl isophthalate, dicyclohexyl fumarate and diisopropyl fumarate are used. One or more of these polymerizable monomers can be used.

Examples of the polymerization initiator using active energy rays include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1- [4- (methylthio)
Phenyl] -2-morpholinopropanone, benzoin isopropyl ether and the like are used. One or more polymerization initiators based on these active energies may be used.

Examples of the polymerization initiator used in the thermal polymerization include ketone peroxides such as methyl ethyl ketone peroxide, 3,3,5-trimethylcyclohexane, cyclohexane peroxide and acetylacetone peroxide; 1,1-bis (tert-butylperoxy). ) Cyclohexane, tert-butyl peroxide, te
organic peroxides such as rt-butylperoxyacetate and diisopropylbenzene hydroperoxide;
2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), azobis (2
An azo compound such as 4-dimethylvaleronitrile) is used. One or more polymerization initiators by the above-mentioned thermal polymerization may be used.

The content of the polyfumarate having a carboxyl group of the present invention is preferably 20 to 80% by weight, more preferably 40 to 70% by weight in the photosensitive resin composition for an alkali developable resist. On the other hand, the content of the polymerizable monomer is preferably 80 to 20% by weight, more preferably 60 to 20% by weight in the photosensitive resin composition for an alkali developable resist.
30% by weight. Further, the content of the polymerization initiator by the active energy ray or heat is usually from the viewpoint of rapid curability by the active energy ray or heat, the amount used in the photosensitive resin composition for the alkali developable resist is usually 0.1.
It is 1 to 20% by weight, preferably 0.2 to 10% by weight.

In the photosensitive resin composition for an alkali developable resist, if necessary, a photosensitizer such as thioxanthone, anthracene and perylene; a polymerization inhibitor such as phenothiazine and hydroquinone; an antioxidant, a thermosetting catalyst, Dyes, pigments, thixotropic agents, plasticizers, surfactants and the like may be added. In addition, in the photosensitive resin composition for an alkali developable resist, a phenol resin, a melamine resin, a thermosetting resin such as a polyimide, a polyolefin resin, a polystyrene resin, and nylon, as long as the effects of the present invention are not impaired. And a thermoplastic resin such as polyethylene terephthalate and polycarbonate.

By mixing the above-mentioned components,
A photosensitive resin composition for an alkali developable resist can be prepared. Further, when the photosensitive resin composition is used, benzene, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethyl lactate, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether acetate, propylene glycol By dissolving or dispersing in a solvent such as monoethyl ether acetate and water, the viscosity and coatability can be adjusted.

Hereinafter, a method for producing a resist using a photosensitive resin composition for an alkali developable resist formed by blending the polyfumarate having a carboxyl group of the present invention and the use thereof will be described in detail. The photosensitive resin composition for an alkali developable resist is transferred,
Commercially available glass epoxy substrate with copper coated on both sides or one side by bar coater, roll coater, spin coater, screen printing, gravure printing, etc., polyphenylene ether (PPE, PPO) substrate, BT (bismaleimide-triazine) resin A thin film is applied to an adherend such as a substrate, a Teflon (registered trademark) substrate, a glass substrate, or an aluminum alloy. It can also be pasted.

After the application or the attachment, an active energy ray such as an ultraviolet ray, an electron beam, an X-ray or a γ-ray is irradiated through a photomask to be cured. Thereafter, development is performed to remove the unirradiated portions, thereby forming a photomask-shaped image. For development, an aqueous alkali solution such as sodium carbonate, sodium hydrogen carbonate, or tetramethylammonium hydroxide is usually used.
It is performed at the following temperature. Further, after development, in order to further promote the polymerization of the polymerizable monomer remaining in the resist, post-curing is usually performed at a temperature of 80 ° C. or higher to obtain a further cured resist.

(Use of Photosensitive Resin Composition) The photosensitive resin composition for an alkali developable resist formed by blending the polyfumarate having a carboxyl group of the present invention is P
It can be used for a printing plate resist such as an S plate or a solder resist.

(Usage of each application) (Resist for printing plate) An aluminum plate (2S material) having a thickness of 0.3 mm is immersed in a 10% aqueous solution of sodium tertiary phosphate maintained at 80 ° C. for 30 seconds. And degrease. Next, the bumish slurry was rubbed with a nylon brush while flowing on the aluminum plate to form a grain, then etched with sodium aluminate at 60 ° C. for 10 seconds, and subsequently washed with a 3% aqueous solution of sodium hydrogen sulfate. The aluminum plate was anodized in a 20% aqueous sulfuric acid solution at a current density of 2 A / dm ² for 2 minutes, then treated with a 2.5% aqueous sodium silicate solution at 70 ° C. for 1 minute, then washed with water and dried. Subsequently, the photosensitive resin composition is applied by a bar coater, and the solvent is removed by drying to form a coating film of about several tens of μm to form a photosensitive lithographic printing plate. The photosensitive lithographic printing plate is irradiated with ultraviolet light through a negative mask. Subsequently, for example, a PS processor 400 manufactured by Fuji Photo Film Co., Ltd.
S is used for development to produce a lithographic printing plate.

(Solder Resist) The photosensitive resin composition was dried on a substrate by a curtain coater to a thickness of several tens μm.
m, and then the solvent is removed by drying to form a smooth coating film. Next, after irradiating ultraviolet rays through a photomask on which the circuit diagram is printed, by removing the unirradiated portions by developing with an alkaline aqueous solution,
The film of the image according to the circuit pattern is formed. The film on which the image is formed is post-cured to form a solder resist film.

[0088]

According to the polyfumarate having a carboxyl group of the first to fourth inventions, excellent heat resistance can be exhibited while maintaining alkali developability. According to the method for producing a polyfumarate having a carboxyl group of the fifth invention, it has excellent alkali developability,
In addition, polyfumarate having a carboxyl group having excellent heat resistance can be easily obtained. According to the alkali developable base resin for a photosensitive resin composition containing a carboxyl group-containing polyfumarate of the sixth invention, an alkali developable photosensitive resin composition having excellent heat resistance can be obtained.

[0089]

Next, the present invention will be described more specifically based on examples and comparative examples. Also, parts and% in each example
Is by weight unless otherwise noted. The analysis values and evaluation results of the polyfumarate used were obtained by the following methods.

(Average molecular weight) After preparing a 1% by weight solution of polyfumarate having a carboxyl group in tetrahydrofuran (hereinafter, tetrahydrofuran is abbreviated as THF), a SEC (size exclusion chromatography) method using THF as a mobile phase was used. It is a measured polystyrene equivalent value. The weight average molecular weight and number average molecular weight were determined.

(Acid value) About 1 g of the weighed polyfumarate was dissolved in 25 ml of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMAc), and measured according to the method of JIS K0070.

(Alkali developability) Polyfumarate 20
% PGMAc solution was prepared and applied on a glass plate using a spin coater so that the film thickness became 10 μm,
It was dried with hot air at 150 ° C. for 30 minutes. After cooling, 25 ℃
Immersed in 1% aqueous sodium carbonate for 1 minute,
Wash with deionized water. Next, after drying at 150 ° C. for 30 minutes, the state of the coating film of the sample was visually observed and evaluated according to the following criteria. Symbol: Evaluation ：: Good alkali developability, ×: Poor alkali developability.

(Heat resistance) 20% PGM of polyfumarate
An Ac solution was prepared and applied to a glass plate using a spin coater to a thickness of 10 μm.
For 30 minutes with hot air. Next, the coating film was scraped off with a spatula, pulverized in a mortar, vacuum-dried at 150 ° C. for 30 minutes, and subjected to thermogravimetric analysis (TGA) using the sample as a sample. The analysis conditions were as follows: the temperature was raised from room temperature to 250 ° C. at a rate of 10 ° C./min, and kept at 250 ° C. for 1 hour.
The residual weight ratio (%) of the sample after that was expressed as heat resistance.

The abbreviations in Table 1, Table 2, Table 3, and Table 4 are as follows. FA: fumaric acid, IA: itaconic acid, VPAA: vinylphenylacetic acid, iBuVE: isobutyl vinyl ether, CHVE: cyclohexyl vinyl ether, tBVE: tert-butyl vinyl ether, tAVE: tert-amyl vinyl ether, EH
VE: 2-ethylhexyl vinyl ether, 2-ethylhexyl acid phosphate), DcHF: dicyclohexyl fumarate, DiPF: diisopropyl fumarate, DtBF: di-tert-butyl fumarate, D
sBF: di-sec-butyl fumarate, St: styrene, PTS: p-toluenesulfonic acid, PGMAc: propylene glycol monomethyl ether acetate.

Reference Example 1 In a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, fumaric acid (abbreviated as FA in the table) 117.1
g, a mixture of 202.1 g of isobutyl vinyl ether (abbreviated as iBuVE in the table) and 0.2 g of AP-8, and then refluxing temperature conditions (80 to 100).
C). The reaction was terminated when the acid value of the mixture became 2 mgKOH / g or less, and a polymerizable monomer (a) having a gas chromatography (GC) purity of 99.2% was obtained at a yield of 95%. Table 1 shows the results.

[0096]

[Table 1]

Reference Examples 2 to 6 Except that the charge composition of the mixture was changed as shown in Table 1, the polymerization represented by the above formula (8), (9) or (10) was carried out in the same manner as in Reference Example 1. The synthetic monomers (b) to (f) were synthesized. Table 1 shows the results.

Example 1 (1) Production of copolymer precursor Dicyclohexyl fumarate (DcHF) 70.7 was placed in a four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer.
g, polymerizable monomer (a) 32.6 g and toluene 6
6.7 g of the mixture were charged. Next, the air in the reactor was replaced with nitrogen under stirring, and the temperature was raised to 40 ° C. There diisopropyl peroxy dicarbonate (IPP)
After charging 1 g, the mixture was kept at 40 ° C. for 25 hours. Thereafter, by cooling to room temperature, a solution of the copolymer precursor was obtained. Next, the solution of the copolymer precursor was subjected to reprecipitation purification using methanol as a precipitant, followed by vacuum drying at 60 ° C. for 5 hours to obtain a copolymer precursor 1 with a yield of 92%. . The average molecular weight was measured by the method described above. Table 2 shows the results.

(2) Production of polyfumarate having a carboxyl group In a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, as shown in Table 3, 167.5 g of the copolymer precursor and 155.6 g of dioxane And 0.675 g of concentrated hydrochloric acid. Next, the temperature was raised to 80 ° C., kept at 80 ° C. for 4 hours, and then cooled to room temperature to obtain a solution of polyfumarate having a carboxyl group. Thereafter, the solution of the polyfumarate having a carboxyl group is subjected to reprecipitation purification using water as a precipitant, and then dried under vacuum at 60 ° C. for 5 hours to give a yield of 95.
% Of polyfumarate 1 having a carboxyl group.
Table 4 shows the measurement results of the average molecular weight and the acid value, and the evaluation results of the alkali developability and heat resistance.

(3) Preparation and Evaluation of Resin Composition for Alkali Developable Resist A solution prepared by uniformly mixing 6 g of polyfumarate 1 and 6 g of ethyl acetate was mixed with 3.0 g of trimethylolpropane triacrylate as a polymerizable monomer. 0.12 g of Darocure 1173 was mixed as an initiator. Then, the mixture was stirred at room temperature for 10 minutes to prepare a photosensitive resin composition for an alkali developable resist. Furthermore, the basic characteristics of the resist (sensitivity and resolution) and the characteristics when used as a solder resist (solder heat resistance) were examined in the following manner, and the resin composition for resist and solder resist were evaluated. 9 steps, resolution 10μ
m, and the solder heat resistance was ○. <Sensitivity> (i) A resin composition for a solder resist was applied to an aluminum plate having a surface grained using a spin coater ASS-300 manufactured by Able Co., Ltd. to a film thickness of 10 μm. (Ii) The solvent was removed by drying in a hot air dryer at 100 ° C. for 10 minutes. (Iii) Exposure was performed for 10 seconds using a 20 mW / cm ultra-high pressure mercury lamp in air through a gray scale (Photographic Step Tablet No. 2 manufactured by Eastman Kodak Company). (Iv) The exposed coating film was spray-developed with a 1% aqueous solution of sodium carbonate at a pressure of 0.29 MPa (3 kg / cm ² ) by a gas-liquid mixing method to remove unexposed portions. (V) Post-curing was performed at 150 ° C. for 1 hour. The maximum number of gray scale steps of the remaining resist film was determined and used as the sensitivity. A large number of steps indicates that the sensitivity is high.

<Resolution> In (iii) of the sensitivity test, a line &
Exposure, development, and post cure were performed in the same manner as in the sensitivity test, except that exposure was performed through a photomask having a space. The resolution of the line and space at the minimum portion where the image of the line and space of the photomask was missing was defined as the resolution (μm). A lower resolution value indicates a higher resolution.

<Solder Heat Resistance> The solder heat resistance is measured according to JIS.
Performed according to the method of -6481. In the sensitivity test, the coating film on the substrate after the exposure-development-post-curing was immersed in a 260 ° C. solder bath for 2 minutes, and the appearance of the sample was visually observed. The presence or absence was observed. The appearance of the sample after the test was visually observed.
When the coating film did not swell or peel off, it was evaluated as ○, and when the coating film swelled or peeled off, it was evaluated as ×.

Examples 2 to 6 As shown in Table 2, except that the type and amount of the polymerizable monomer, the type and the amount of the fumarate, and the amount of the solvent (toluene) were changed. In the same manner as in Example 1, a copolymer precursor was produced. Next, as shown in Table 3, the carboxyl group was changed in the same manner as in Example 1 except that the type of the copolymer precursor and the amount added, the type of the catalyst and the amount added, the type of the solvent and the reaction temperature were changed. The production of polyfumarate was carried out. Table 2 shows the analysis results of the copolymer precursor, and Table 4 shows various evaluation results of the polyfumarate having a carboxyl group. Here, (B) is a structural unit based on a monomer having a carboxyl group.

[0104]

[Table 2]

[0105]

[Table 3]

[0106]

[Table 4]

Comparative Example 1 In a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 84.7 g of methyl methacrylate and 1 methacrylic acid were placed.
A mixture of 5.3 g and 66.7 g of PGMAc was charged.
Next, the air in the reactor was replaced with nitrogen under stirring, and then
The temperature was raised to 0 ° C. Then, 1 g of diisopropyl peroxydicarbonate (IPP) was added thereto, and 25 g at 40 ° C.
After keeping for a time, the mixture was cooled to room temperature to obtain a copolymer solution.
Next, the obtained copolymer solution was subjected to reprecipitation purification using methanol as a precipitant, followed by vacuum drying at 60 ° C. for 5 hours to obtain Comparative Copolymer 1 with a yield of 92%. . Various evaluations were performed in the same manner as in Example 1. Table 4 shows the results.

Comparative Example 2 In a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 87.2 g of methyl acrylate and 12.8 of acrylic acid were placed.
g, 66.7 g of PGMAc. Next, the air in the reactor was replaced with nitrogen under stirring, and the temperature was raised to 40 ° C. Then, 1 g of diisopropyl peroxydicarbonate (IPP) was charged therein, kept at 40 ° C. for 25 hours, and then cooled to room temperature to obtain a copolymer solution. next,
The solution of the obtained copolymer was subjected to reprecipitation purification using methanol as a precipitant, followed by vacuum drying at 60 ° C. for 5 hours to obtain Comparative Copolymer 2 at a yield of 96%. Example 1
Various evaluations were performed in the same manner as in the above. Table 4 shows the results.

As is apparent from Table 4, the polyfumarate having a carboxyl group obtained from each of Examples 1 to 6 of the present invention has excellent heat resistance in addition to excellent alkali developability. It is clear that. On the other hand, the comparative copolymers 1 and 2 of Comparative Examples 1 and 2 each containing methacrylate or acrylate as a main component are excellent in alkali developability, but inferior in heat resistance.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA04 AA10 AB01 AB17 AB20 AC01 CB06 CB43 FA03 FA17 4J100 AB02R AB03R AB08R AE02R AE03R AE09R AF01R AG02R AG04R AL03R AL05R AL34P AL34R AL39P AL92Q BC16P02 BC01 BC02P HA08 JA37

Claims (6)

[Claims] 1. A polyfumarate comprising (A) a structural unit based on a fumaric diester and (B) a structural unit based on a carboxyl group-containing monomer. 2. A compound having (A) a structural unit based on a fumaric acid diester represented by the following formula (1) and (B) one or more structural units based on a carboxyl group-containing monomer, and having a molecular weight of: A polyfumarate having an acid value of 1,000 to 300,000 and an acid value of 50 to 250 mgKOH / g. Embedded image (However, X ¹ and X ² in the formula may be the same or different, and are a branched alkyl group or substituted branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl group or substituted cycloalkyl group having 4 to 8 carbon atoms.) Represents.) 3. A compound having (A) a structural unit based on a fumaric acid diester represented by the following formula (1) and (B) a structural unit based on a carboxyl group-containing monomer, wherein (A) ), (B) component is 70% by weight or more and A / (A
+ B) is from 0.5 to 0.
95% by weight and having a molecular weight of 5,000 to 200,00
A polyfumarate whose acid number is from 70 to 200 mg KOH / g at 0; Embedded image (However, X ¹ and X ² in the formula represent the same as described above.) (A) a structural unit based on a fumaric acid diester represented by the following formula (1); (B) a repeating structural unit represented by the following formula (2); By performing a deblocking reaction on a copolymer precursor comprising at least one structural unit selected from a structural unit group based on a block carboxylic acid comprising a repeating structural unit and a repeating structural unit represented by the following formula (6): Claim 1 obtained
4. The polyfumarate having a carboxyl group according to any one of 3. Embedded image (However, X ¹ and X ² in the formula may be the same or different, and are a branched alkyl group or substituted branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl group or substituted cycloalkyl group having 4 to 8 carbon atoms.) Represents the following.) (However, Y ¹ and Y ² in the formula may be the same or different, and are a branched alkyl group or substituted branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl group or substituted cycloalkyl group having 4 to 8 carbon atoms. Wherein at least one of Y ^{1 and} Y ^{2 in} the molecule is represented by the following formula (3) or (4):
Represents a group represented by ) Embedded image (However, R ¹ , R ² and R ³ in the formulas (3) and (4) are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is an organic group having 1 to 18 carbon atoms. And Z ¹ is an oxygen atom or a sulfur atom, and R ⁵ and R ^{6 each} have 1 carbon atom.
~ 18 organic groups. ) (However, Y ¹ and Y ² in the formula represent the same as those in the formula (2).) (However, Y ³ in the formula is represented by the following formula (3) or (4). D is a benzyl group, n is 0 or 1, and E represents a hydrogen atom or a methyl group.) Embedded image Embedded image (However, R ¹ , R ² , R ³ , R ⁴ and R ⁵ in the formulas (3) and (4) represent the same as described above.) 5. A method for producing a polyfumarate having a carboxyl group according to any one of claims 1 to 3, which comprises the following first and second steps: . First step: a fumaric acid diester represented by the following formula (7), a polymerizable monomer represented by the following formula (8), a polymerizable monomer represented by the following formula (9), and A copolymer precursor is obtained by copolymerizing with at least one polymerizable monomer selected from the group consisting of polymerizable monomers represented by the formula (10), second step: first Deblocking reaction of the copolymer precursor obtained in the step. Embedded image (However, X ¹ and X ² in the formula may be the same or different, and are a branched alkyl group or a substituted branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl group or a substituted cycloalkyl group having 4 to 8 carbon atoms.) [Image Omitted] (However, Y ¹ and Y ² in the formula may be the same or different, and are a branched alkyl group or substituted branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl group or substituted cycloalkyl group having 4 to 8 carbon atoms. Wherein at least one of Y ^{1 and} Y ^{2 in} the molecule is represented by the following formula (3) or (4):
Represents a group represented by ) Embedded image (However, R ¹ , R ² and R ³ in the formulas (3) and (4) are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is an organic group having 1 to 18 carbon atoms. And Z ¹ is an oxygen atom or a sulfur atom, and R ⁵ and R ^{6 each} have 1 carbon atom.
To 18 organic groups. ) (However, Y ¹ and Y ² in the formula represent the same as in the formula (2).) (However, Y ³ , D, n and E in the formula represent the same as described above.) 6. An alkali-developable base resin for a photosensitive resin composition comprising the polyfumarate having a carboxyl group according to claim 1.