JP6362272B2 - Carboxyl group-containing reactive compound, curable resin composition using the same, and use thereof. - Google Patents

Description

  The present invention relates to a carboxyl obtained by introducing an acid anhydride group into a polyhydric alcohol compound and then reacting a compound having one or more polymerizable ethylenically unsaturated groups and one or more hydroxyl groups in the molecule. The present invention relates to a group-containing reactive compound, its composition and use.

  Obtained by reacting acid anhydrides such as succinic anhydride and tetrahydrophthalic anhydride with epoxy acrylate, etc., as resist materials for display elements such as color filters, and solder resist materials such as printed wiring boards The resulting carboxyl group-containing reactive compound has excellent developability despite its low acid value, and is used in resist inks (Patent Document 1).

  Since existing acid-modified epoxy acrylate has a relatively wide molecular weight distribution, when it is used as a negative photoresist material, the non-irradiated part is eluted with an alkaline developer. In this case, there was a problem that the edge line resolution could not be eluted smoothly and the edge line resolution deteriorated.

  In addition, since an acid-modified epoxy acrylate or the like uses an epoxy compound as a raw material, a halogen component derived from a raw material for producing the epoxy compound, such as epichlorohydrin, remains. When this is used as a sealing material for electronic circuits such as solder resist, it has been pointed out that the halogen content may adversely affect long-term circuit reliability.

  Furthermore, when used in color resists for color filters, acid-modified epoxy acrylates generally use polyfunctional aromatic epoxies as raw materials in order to maintain heat resistance. For this reason, there existed problems, such as a yellowing color having arisen by the heat processing etc. in a manufacturing process (patent document 2).

  As acid anhydrides used for the production of existing acid-modified epoxy acrylates, those containing one acid anhydride group in one molecule are mainly used. When one having two or more acid anhydride groups in one molecule is used, since epoxy acrylates contain many hydroxyl groups in one molecule, the cross-linking reaction between molecules proceeds and the molecular weight can be controlled. was difficult.

  In Patent Document 3, a compound obtained by reacting a compound having two acid anhydride groups in one molecule with a compound having a hydroxyl group and an unsaturated group in one molecule to make a half ester is further reacted with an epoxy compound. Although a method for obtaining a resist composition from the above is described, a compound or composition derived from a compound having three or more acid anhydride groups in one molecule as in the present invention is not described. .

WO2008 / 004630 Publication Japanese Patent Laid-Open No. 2005-126684 JP 2005-206803 A

  An object of the present invention is to provide a reactive resin having good photoreactivity, developability, and characteristics suitable as a negative resist material.

  In order to solve the above-mentioned problems, the present inventors have added a compound having one or more polymerizable ethylenically unsaturated groups and one or more hydroxyl groups in the molecule to a polyfunctional acid anhydride (A) having a specific structure ( It has been found that the carboxyl group-containing reactive compound (C) obtained by reacting B) has particularly excellent resin properties.

That is, the present invention relates to (1) a polyhydric alcohol (a) having at least three hydroxyl groups in one molecule and a nuclear hydrogenated trimellitic anhydride halide (b-1) or trimellitic anhydride halide (b-2). The compound (B) having one or more polymerizable ethylenically unsaturated groups and one or more hydroxyl groups in one molecule is further reacted with the polyfunctional acid anhydride (A) obtained by reacting The carboxyl group-containing reactive compound (C) thus obtained.
(2) The polyhydric alcohol (a) is represented by the following general formula (1)

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６はそれぞれ独立して、Ｒ^１、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６は水素原子、水酸基、炭素数１〜１１の炭化水素基、もしくは炭素数１〜４のヒドロキシアルキル基を表し、Ｒ^２は水酸基、もしくは炭素数１〜４のヒドロキシアルキルを表す。lは０〜１１、ｍとｎはそれぞれ１〜１１の整数を表す。）で表される一分子中に少なくとも３つの水酸基を含有する多価アルコール（ａ−１）であることを特徴とするカルボキシル基含有反応性化合物（Ｃ）に関する。

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ are a hydrogen atom, hydroxyl group, carbon number 1 Represents a hydrocarbon group having ˜11 or a hydroxyalkyl group having 1 to 4 carbon atoms, R ² represents a hydroxyl group or a hydroxyalkyl having 1 to 4 carbon atoms, l is 0 to 11, m and n are each 1 to 1; 11 represents a carboxyl group-containing reactive compound (C), which is a polyhydric alcohol (a-1) containing at least three hydroxyl groups in one molecule represented by

(3) The polyhydric alcohol (a) obtained by reacting the polyhydric alcohol (a) with at least one selected from the group consisting of alkylene oxide, cyclic ether, and cyclic ester. -2), which relates to a carboxyl group-containing reactive compound (C).

(4) The compound (D) having one or more polymerizable ethylenically unsaturated groups and one or more epoxy groups in one molecule is further reacted with the carboxyl group-containing reactive compound (C). It relates to the polyfunctional reactive compound (E) obtained.

(5) The present invention relates to an active energy ray-curable resin composition comprising the carboxyl group-containing reactive compound (C) or the polyfunctional reactive compound (E).
(6) It relates to the active energy ray-curable resin composition which is a film forming material.
(7) The present invention relates to the active energy ray-curable resin composition, which is a material composition intended for drawing with active energy rays.

(8) It relates to a cured product of the active energy ray-curable resin composition.

The carboxyl group-containing reactive compound (C) and polyfunctional reactive compound (E) of the present invention have excellent reactivity and excellent developability in optical drawing, and give a tough cured product.
The carboxyl group-containing reactive compound (C) and polyfunctional reactive compound (E) of the present invention are used for solder resists for printed wiring boards, interlayer insulating materials for semiconductor package substrates, solder resists for flexible printed wiring boards, plating resists, etc. it can.
In particular, it is suitable for color resists useful for color filters, etc., black matrix materials, spacer materials, etc., taking advantage of its high colorability and heat resistance.
In addition, the carboxyl group-containing reactive compound (C) and the polyfunctional reactive compound (E) of the present invention can also be used for applications such as an optical waveguide by an optical drawing method.

  The carboxyl group-containing reactive compound (C) of the present invention comprises a nuclear hydrogenated trimellitic anhydride halide (b-1) or trimellitic anhydride to a polyhydric alcohol (a) having at least three hydroxyl groups in one molecule. Compound (B) having both one or more polymerizable ethylenically unsaturated groups and one or more hydroxyl groups in one molecule in polyfunctional acid anhydride (A) obtained by reacting acid halide (b-2) ).

  The polyfunctional reactive compound (E) of the present invention comprises one or more polymerizable ethylenically unsaturated groups and one or more epoxy groups in one molecule in the carboxyl group-containing reactive compound (C) of the present invention. It can be obtained by reacting the compound (D) having it together.

  The polyhydric alcohol (a) used in the present invention has three or more hydroxyl groups in at least one molecule. When the number of hydroxyl groups is 2 or less in one molecule, a strong crosslinked structure cannot be formed when the final cured product is obtained.

  In the present invention, the polyhydric alcohol (a) preferably has a structure represented by the following general formula (1).

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６はそれぞれ独立して、Ｒ^１、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６は水素原子、水酸基、炭素数１〜１１の炭化水素基、もしくは炭素数１〜４のヒドロキシアルキル基を表し、Ｒ^２は水酸基、もしくは炭素数１〜４のヒドロキシアルキルを表す。ｌは０〜１１、ｍとｎはそれぞれ１〜１１の整数を表す。）

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ are a hydrogen atom, hydroxyl group, carbon number 1 Represents a hydrocarbon group having ˜11 or a hydroxyalkyl group having 1 to 4 carbon atoms, R ² represents a hydroxyl group or a hydroxyalkyl having 1 to 4 carbon atoms, l is 0 to 11, m and n are each 1 to 1; Represents an integer of 11.)

In the above general formula (1), when l or m is 2 or more, a plurality of R ¹ , R ³ , R ⁴ , and R ⁶ are the same as R ¹ , R ³ , R ⁴ , and R ⁶ , respectively. Different substituents may be taken. For example, when 1 = 2, four R ^{1 s} may be the same or different from each other. R ³ , R ⁴ and R ⁶ are the same as R ¹ .

  Specific examples of the polyhydric alcohol (a) include glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 1,2,4-butanetriol, 2-hydroxyalkylmethyl-1,4-butanediol, 1, 2,5-pentanetriol, 1,3,5-pentanetriol, 3-methylpentane-1,3,5-triol, 1,2,6-hexanetriol, 1,2,8-octanetriol, 1,2 , 9-nonanetriol, 1,2,10-decantriol, triols such as tris-2-hydroxyethyl isocyanurate, ditrimethylolpropane, 1,1,2,2-ethanetetraol, erythritol, pentaerythritol, 1 , 2,3,5-pentanetetraol, 1,2,4,5-pentaneteto All, 1,1,5,5-pentanetetraol, 1,2,5,6-hexanetetraol, 1,2,7,8-octanetetraol, 1,2,9,10-decanetetraol, etc. And polyols such as dipentaerythritol and polyglycerin.

  Among these, when a polyhydric alcohol having 4 to 6 hydroxyl groups in the molecule represented by the general formula (1) is used, the properties of the obtained cured product are excellent. In particular, pentaerythritol, ditrimethylolpropane, and dipentaerythritol are preferable from the viewpoint of good properties of the cured product and easy availability of the material.

  In the present invention, the polyhydric alcohol (a-2) has a structure in which any one or more selected from the group consisting of alkylene oxides, cyclic ethers, and cyclic esters are added to the polyhydric alcohol (a). Refers to a compound. Moreover, polyhydric alcohol (a-2) can also optimize the characteristic of reactivity and hardened | cured material according to a use.

The hydrocarbon group represented by R ¹ in the general formula (1) refers to an atomic group composed of only carbon atoms and hydrogen atoms.

  As for carbon number of a hydrocarbon group, 1-11 are preferable. Specific examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, linear or branched pentyl group, linear or branched Aliphatic hydrocarbon groups such as hexyl group, straight chain or branched heptyl group, straight chain or branched octyl group, alicyclic hydrocarbon groups such as cyclohexyl group, methylcyclohexyl group, ethylcyclohexyl group, Examples thereof include aromatic groups such as phenyl group, tolyl group, naphthyl group, and methylnaphthyl group, and aromatic substituted alkyl groups such as benzyl group and naphthylmethyl group. Among these, in the present invention, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group is preferable in terms of good transparency of the cured product of the present invention, and a methyl group and an ethyl group have good toughness and heat resistance. It is more preferable from the point which gives the hardened | cured material of invention.

The hydroxyalkyl group represented by R ¹ or R ² refers to an atomic group in which one or more hydrogen atoms of a linear or branched alkyl group are substituted with a hydroxyl group.

  As for carbon number of a hydroxyalkyl group, 1-4 are preferable. Specific examples include those in which one or more hydrogen atoms of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group are substituted with a hydroxyl group. Of these, in the present invention, one in which one hydroxyl group is substituted on the terminal carbon is preferable in terms of easy reaction. Hydroxymethyl groups and hydroxyethyl groups are more preferred from the viewpoint of good toughness and heat resistance of the cured product of the present invention.

  The alkylene oxide used in the present invention refers to a compound having a three-membered cyclic ether.

  As for carbon number of alkylene oxide, 2-8 are preferable. Examples thereof include ethylene oxide, propylene oxide, butylene oxide, and styrene oxide. These alkylene oxides may be one kind or a mixture of two or more kinds as required. Among these, at least one selected from ethylene oxide and propylene oxide is preferable in the present invention because it is easily available and inexpensive.

  The amount of alkylene oxide used is usually 0.1 to 6.0 equivalents of a 3-membered cyclic ether, preferably 0.2 to 2.0 equivalents, per equivalent of hydroxyl group of the polyhydric alcohol (a). . Within this range, the resulting cured product has good heat resistance and toughness.

  The cyclic ether used in the present invention is not particularly limited as long as it is a compound having a structure in which one or more carbons of a cyclic hydrocarbon having 4 or more members are substituted with oxygen.

  The cyclic ether is preferably a 4- to 6-membered ring, and specific examples include oxetane, tetrahydrofuran, and tetrahydropyran. These cyclic ethers may be one kind or a mixture of two or more kinds as necessary. Of these, tetrahydrofuran is preferred in the present invention because it is readily available and inexpensive.

  The usage-amount of cyclic ether is 0.1-6.0 equivalent of cyclic ether with respect to 1 equivalent of hydroxyl groups of a polyhydric alcohol (a), Preferably, it is 0.2-2.0 equivalent. Within this range, the resulting cured product has good heat resistance and toughness.

  The cyclic ester used in the present invention is not particularly limited as long as it is a compound having a structure containing an ester bond in a cyclic hydrocarbon.

  It is preferable that carbon number of cyclic ester is 2-6. Specific examples of the cyclic ester include acetolactone, propiolactone, butyrolactone, valerolactone, caprolactone and the like. These cyclic esters may be one kind or a mixture of two or more kinds as required. Of these, caprolactone is preferred in the present invention because it is readily available and inexpensive.

  The usage-amount of cyclic ester is 0.1-6.0 equivalent of cyclic ester with respect to 1 equivalent of hydroxyl groups of a polyhydric alcohol (a), Preferably, it is 0.2-2.0 equivalent. Within this range, the resulting cured product has good heat resistance and toughness.

  Specific examples of the polyhydric alcohol (a-2) include trimethylolpropane ethylene oxide adduct, trimethylolpropane propylene oxide adduct, trimethylolpropane tetrahydrofuran adduct, trimethylolpropane caprolactone adduct, pentaerythritol ethylene. Oxide adduct, pentaerythritol propylene oxide adduct, pentaerythritol tetrahydrofuran adduct, pentaerythritol caprolactone adduct, dipentaerythritol ethylene oxide adduct, dipentaerythritol propylene oxide adduct, dipentaerythritol tetrahydrofuran adduct, dipentaerythritol caprolactone Adducts and the like.

Anhydrous hydrogenated trimellitic acid halide (b-1) is used to introduce an acid anhydride group into a polyhydric alcohol to obtain a polyfunctional acid anhydride compound. Thereby, an acid anhydride group can be introduced without ring-opening esterification of the acid anhydride group.
Moreover, since it is nuclear hydrogenated, there is little coloring under heat and light resistance, and the cured product is excellent in heat resistance and toughness while maintaining high optical properties.

  Trimellitic anhydride halide (b-2) is also used for the same purpose as (b-1). (B-2) has higher heat resistance than (b-1).

  Halides (b-1) and (b-2) can be used in combination, and the balance between colorability and heat resistance can be appropriately adjusted according to the application.

  Examples of the halide (b-1) or (b-2) include a fluorinated product, a chlorinated product, a brominated product, and an iodinated product, and among them, a chlorinated product is preferable because of easy reaction.

  The synthesis of the polyfunctional acid anhydride (A) can be performed by a known method. There is no particular limitation on the method of adding the reagent in the reaction between the polyhydric alcohol (a) and the halide (b-1) or (b-2), and any addition method can be adopted. For example, a method in which a polyhydric alcohol (a) and a basic substance are dissolved in a solvent, and the above-mentioned halide (b-1) or (b-2) dissolved in the solvent is slowly added dropwise, or vice versa Depending on the method, a method of dropping a mixed solution of a polyhydric alcohol (a) and a basic substance into the halide (b-1) or (b-2) dissolved in a solvent, halide (b-1) or (b -2) A method of dropping a basic substance into a mixed solution of polyhydric alcohol (a), and further, a solution of nuclear hydrogenated trimellitic anhydride halide and a base in a solution of polyhydric alcohol (a) It is possible to adopt a method in which a solution of a sex substance is dropped simultaneously.

  In the reaction between the polyhydric alcohol (a) and the halide (b-1) or (b-2) in the presence of the basic substance, a hydrochloride formed by neutralization of the basic substance is generated as the reaction proceeds. After removing this by filtration, the filtrate is concentrated to obtain the desired polyfunctional acid anhydride (A) crude product in high yield. This is dissolved in a suitable solvent, washed with water, concentrated and dried under reduced pressure to obtain a polyfunctional acid anhydride (A) having a high purity. Furthermore, a polyfunctional acid anhydride (A) with higher purity can be obtained by performing recrystallization with an appropriate solvent as required.

  The use amount of the polyhydric alcohol (a) is usually a hydroxyl group equivalent, and is 0.6 to 1.0, preferably 0.8 to 1.0 with respect to the halide 1. If it is this range, all the hydroxyl groups of polyhydric alcohol (a) are esterified, and an unreacted halide does not remain in the system.

  The solvent that can be used in the reaction of the halide (b-1) or (b-2) and the polyhydric alcohol (a) is not particularly limited as long as it is inert to the raw material, but tetrahydrofuran, 1,4-dioxane, 1 , Ether solvents such as 2-dimethoxyethane-bis (2-methoxyethyl) ether, aromatic amine solvents such as picoline and pyridine, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, toluene, xylene and the like Aromatic hydrocarbon solvents, halogen-containing solvents such as dichloromethane, chloroform, 1,2-dichloroethane, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N- Amide solvents such as dimethylformamide and the like, including hexamethylphosphoramide and the like. A phosphorus solvent, a sulfur-containing solvent such as dimethyl sulfoxide, an ester solvent such as γ-butyrolactone, ethyl acetate, butyl acetate, a nitrogen-containing solvent such as 1,3-dimethyl-2-imidazolidinone, Examples thereof include aromatic solvents having a hydroxyl group such as phenol, o-cresol, m-cresol, p-cresol, o-chlorophenol, m-chlorophenol, and p-chlorophenol. These solvents may be used alone or in combination of two or more.

  The solvents mentioned here include cyclic ethers and cyclic esters used in the production of polyhydric alcohol (a-2) from polyhydric alcohol (a). Halides are added to polyhydric alcohol (a). When making it react, reaction temperature is -10 degreeC-80 degreeC, Preferably it is 0 degreeC-70 degreeC, More preferably, it is 10 degreeC-60 degreeC. When the reaction temperature is higher than 80 ° C., the polyhydric alcohol (a) reacts with the cyclic ether or cyclic ester to obtain the polyhydric alcohol (a-2), and the reaction rate between the polyhydric alcohol (a) and the halide is high. descend. The reaction time is not particularly limited, but is usually 10 minutes to 48 hours, preferably 30 minutes to 24 hours. The reaction is usually carried out at normal pressure, but can be carried out under pressure or under reduced pressure as necessary.

  When the polyhydric alcohol (a) is reacted with a cyclic ether or cyclic ester to produce the polyhydric alcohol (a-2), the reaction temperature is 80 ° C to 250 ° C, preferably 90 ° C to 220 ° C, more preferably. 100 to 200 ° C. The reaction time is not particularly limited, but is usually 10 minutes to 48 hours, preferably 30 minutes to 24 hours. The reaction is usually carried out at normal pressure, but can be carried out under pressure or under reduced pressure as necessary.

  The concentration of the solute in the reaction for obtaining the polyfunctional acid anhydride (A) is usually 5% by mass to 50% by mass, preferably 10% by mass to 40% by mass in consideration of side reaction control and precipitation filtration step. . More preferably, it is carried out in the range of 10 mass% or more and 40 mass% or less.

  The reaction atmosphere in the reaction for obtaining the polyfunctional acid anhydride (A) is usually performed under nitrogen. The reaction vessel may be a closed type reaction vessel or an open type reaction vessel, but in order to keep the reaction system in an inert atmosphere, an open type vessel that can be sealed with an inert gas is used.

  The basic substance is used to neutralize hydrogen chloride generated as the reaction proceeds. The type of basic substance used at this time is not particularly limited, but organic basic amines such as pyridine, triethylamine and N, N-dimethylaniline, and inorganic basic substances such as potassium carbonate and sodium hydroxide are used. be able to. Pyridine and triethylamine are preferable in that they can be obtained at low cost and are easy to operate because they are liquid and highly soluble. Moreover, an inorganic basic substance is preferable in that it can be obtained at low cost.

  The amount of the basic substance to be used is not particularly limited, but if it is used excessively, it will be mixed into the product and the purification load will increase, so it is usually 1 for the nuclear hydrogenated trimellitic anhydride halide. 0.0 mol times to 30 mol times, preferably 1.2 mol times to 20 mol times, more preferably 1.5 mol times to 10 mol times are employed.

  During the water washing operation, the polyfunctional acid anhydride (A) undergoes partial hydrolysis and changes to a polycarboxylic acid, which is produced by partial hydrolysis by heat treatment under reduced pressure. The polyvalent carboxylic acid thus obtained can be easily returned to the polyfunctional acid anhydride. The temperature employed in the heat treatment step under reduced pressure is 80 ° C. to 200 ° C., preferably 100 ° C. to 180 ° C., the degree of reduced pressure is 10 MPa or less, preferably 1 MPa or less, and the upper limit of the heating time is particularly limited. However, it is usually 10 minutes to 48 hours, preferably 30 minutes to 24 hours.

  The polyfunctional acid anhydride (A) thus obtained can be further purified. As a purification method in that case, recrystallization, sublimation, washing, activated carbon treatment, column chromatography and the like can be arbitrarily performed. These purification methods can be repeated or combined. The purity of the polyfunctional acid anhydride (A) thus obtained is usually 90% or more, preferably 95% or more as an area ratio of peaks obtained by analysis such as gel permeation chromatography (hereinafter referred to as “GPC”). More preferably, it is 98% or more

  In the compound (B) having one or more polymerizable ethylenically unsaturated groups and one or more hydroxyl groups in one molecule shown in the present invention, the acid anhydride group and the hydroxyl group are half-esterified by addition reaction. Thus, it is intended to impart photoreactivity and solubility with an alkali developer by introducing an unsaturated bond into the molecule and simultaneously generating a free carboxyl group.

  The number of hydroxyl groups possessed by the compound (B) is preferably one per molecule. If two or more are included, it will have the effect of crosslinking (A). This can be used to positively increase the molecular weight, but excessive use causes an increase in viscosity and deterioration in developability.

  Specifically, as a compound (B) having one or more polymerizable ethylenically unsaturated groups and one or more hydroxyl groups in a generally available molecule, for example, hydroxyethyl (meth) acrylate, hydroxypropyl ( Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate and hydroxybutyl (meth) acrylate.

  Furthermore, hydroxyl group-containing polyfunctional (meth) acrylates such as pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are exemplified.

  Further, methyl glycidyl ether (meth) acrylic acid adducts, ethyl glycidyl ether (meth) acrylic acid adducts are compounds obtained by carboxylating by adding an unsaturated carboxylic acid such as (meth) acrylic acid to an epoxy compound. , Octyl glycidyl ether (meth) acrylic acid adduct, decyl glycidyl ether (meth) acrylic acid adduct, stearyl glycidyl ether (meth) acrylic acid adduct, phenyl glycidyl ether (meth) acrylic acid adduct, butylphenyl glycidyl ether ( A meth) acrylic acid adduct, a glycidyl (meth) acrylate (meth) acrylic acid adduct, etc. are mentioned.

  In addition, diol monovinyl ethers such as ethylene glycol monovinyl ether, propylene glycol monovinyl ether, and butylene glycol monovinyl ether can also be used.

  A known method can be applied to the reaction of the polyfunctional acid anhydride (A), the compound (B) having both an ethylenically unsaturated group and one or more hydroxyl groups.

  In this case, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is a reaction in which a reactant, that is, a polyfunctional acid anhydride (A), a compound (B), and a solvent or the like is added in some cases. It is 0.1-10 mass% with respect to the total amount of a thing. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, Examples include zirconium octoate.

  The acid addition reaction can be performed without a solvent or diluted with a solvent. The solvent that can be used here is not particularly limited as long as it is an inert solvent for this reaction. A preferable amount of the solvent to be used should be appropriately adjusted depending on the viscosity and use of the resin to be obtained, and is preferably 90 to 30% by mass, more preferably 80 to 50% by mass as a solid content.

Specifically, for example, aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane and decane, and mixtures thereof, petroleum ether, white Examples include gasoline and solvent naphtha.
Examples of ester solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, Mono- or polyalkylene glycol monoalkyl ether monoacetates such as triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, adipine Polyesters of polycarboxylic acids such as dialkyl acids Kind, and the like.
Examples of ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether. Glycol ethers, and cyclic ethers such as tetrahydrofuran.
Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

  In the present invention, the carboxyl group-containing reactive compound (C) of the present invention is further imparted with reactivity, or for the purpose of adjusting the acid value to be imparted, one or more polymerizable ethylenic monomers in one molecule. A polyfunctional reactive compound (E) obtained by reacting a compound (D) having both an unsaturated group and one or more epoxy groups is also included. The polyfunctional reactive compound (E) of the present invention has a carboxyl group depending on the reaction amount of the compound (D) having one or more polymerizable ethylenically unsaturated groups and one or more epoxy groups in one molecule used. And a polyfunctional reactive compound (E) having no polyfunctional reactive compound (E).

  The number of epoxy groups that the compound (D) has is preferably one in one molecule. When two or more are included, the reactive compound (C) has a function of crosslinking. This can be used to positively increase the molecular weight, but excessive use causes an increase in viscosity and deterioration in developability.

  Specific examples of the compound (D) having one or more polymerizable ethylenically unsaturated groups and one or more epoxy groups in one molecule include glycidyl (meth) acrylate, hydroxybutyl (meth) acrylate glycidyl ether, etc. Is mentioned.

  A known method can be applied to the reaction between the carboxyl group-containing reactive compound (C) and the compound (D). In this reaction, the catalyst and solvent used when reacting the reactive compound (C) can be used in the same manner. In this case, the amount of the catalyst used is 0.1 to 10% by mass based on the total amount of the reactants, that is, the reactive compound (C), the compound (D), and the reactants optionally added with a solvent or the like. The reaction temperature is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours.

  The active energy ray-curable resin composition containing the reactive compound (C) or the reactive compound (E) of the present invention is mixed with other substances according to each application, and imparts characteristics according to the intended use. The composition is shown.

  Examples thereof include other reactive compounds (F), active energy ray reactive initiators (G), colored pigments (H), extender pigments (I), curing agents (J), and other materials.

  Specific examples of the reactive compound (F) include so-called reactive oligomers such as radical-reactive acrylates, cation-reactive other epoxy compounds, and vinyl compounds sensitive to both.

  Examples of acrylates that can be used include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, other epoxy acrylates, polyester acrylates, urethane acrylates, and the like.

  Monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether, Examples include phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.

  As polyfunctional (meth) acrylates, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, glycol di (meth) acrylate, Diethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (meth) acrylate, adipic acid epoxy di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, hydrogen Ε-Caprola of bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, and neopent glycol hydroxybivalate Tone adduct di (meth) acrylate, poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, reaction product of dipentaerythritol and ε-caprolactone, trimethylolpropane tri (meth) acrylate, triethylolpropane tri ( (Meth) acrylate and its ethylene oxide adduct, pentaerythritol tri (meth) acrylate and its ethylene oxide adduct, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and its ethylene oxide adduct, etc. Is mentioned.

  Examples of vinyl compounds that can be used include vinyl ethers, styrenes, and other vinyl compounds. Examples of vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of styrenes include styrene, methyl styrene, and ethyl styrene. Other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

  Furthermore, as so-called reactive oligomers, urethane acrylate having a functional group capable of acting on active energy rays and a urethane bond in the same molecule, and similarly a functional group capable of acting on active energy rays and an ester bond in the same molecule. Examples thereof include polyester acrylate, epoxy acrylate derived from an epoxy resin, and epoxy acrylate having a functional group capable of acting on active energy rays in the same molecule, and a reactive oligomer in which these bonds are used in combination.

  The cation reactive monomer is not particularly limited as long as it is generally a compound having an epoxy group. For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4, -epoxycyclohexanecarboxylate (manufactured by Union Carbide) "Syracure UVR-6110" etc.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (such as "ELR-4206" manufactured by Union Carbide), limonene dioxide (Daicel Chemical) “Celoxide 3000” manufactured by Kogyo Co., Ltd.), allyl cyclohexylene dioxide, 3,4, -epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxy Cycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate (such as “Syracure UVR-6128” manufactured by Union Carbide), bis (3 4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane and the like.

  Of these, the reactive compound (F) is most preferably a radical curable acrylate. In the case of the cationic type, the carboxylic acid and the epoxy react with each other, so that it is necessary to use a two-component mixed type.

  The active energy ray-curable resin composition of the present invention has a carboxyl group-containing reactive compound (C) or a polyfunctional reactive compound (E) of 97 to 5% by mass, preferably 87 to 10% by mass in the composition. It contains 3-95% by mass of the reactive compound (F), more preferably 3-90% by mass. Other components may be included as necessary.

  Examples of the active energy ray reactive initiator (G) used in the present invention include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyhexylphenylketone, 2 -Acetophenones such as methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one; 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone Anthraquinones such as 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone, 4-benzoyl- Benzophenones such as 4′-methyldiphenyl sulfide and 4,4′-bismethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, etc. Well-known general radical type photoinitiators such as phosphine oxides may be mentioned.

  Also, Lewis acid diazonium salt, Lewis acid iodonium salt, Lewis acid sulfonium salt, Lewis acid phosphonium salt, other halides, triazine-based initiator, borate-based initiator, and other cationic initiators, Examples include photoacid generators.

  Examples of the diazonium salt of Lewis acid include p-methoxyphenyldiazonium fluorophosphonate, N, N-diethylaminophenyldiazonium hexafluorophosphonate (Sun Shine SI-60L / SI-80L / SI-100L, etc. manufactured by Sanshin Chemical Industry Co., Ltd.) and the like. Examples of the iodonium salt of Lewis acid include diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate. Examples of the sulfonium salt of Lewis acid include triphenylsulfonium hexafluorophosphonate (Cyracure UVI-6990 manufactured by Union Carbide). And triphenylsulfonium hexafluoroantimonate (such as Cyracure UVI-6974 manufactured by Union Carbide) and the like, and the phosphonium salt of Lewis acid includes triphenylphosphonium hexafluoroantimonate and the like. .

  Examples of other halides include 2,2,2-trichloro- [1-4 ′-(dimethylethyl) phenyl] ethanone (such as Trigonal PI manufactured by AKZO), 2,2-dichloro-1--4- (phenoxyphenyl). ) Ethanone (Sandray 1000 manufactured by Sandoz, etc.), α, α, α-tribromomethylphenylsulfone (BMPS manufactured by Iron Chemical Co., Ltd.) and the like. Examples of triazine initiators include 2,4,6-tris (trichloromethyl) -triazine, 2,4-trichloromethyl- (4′-methoxyphenyl) -6-triazine (such as Triazine A manufactured by Panchim), 2, 4-trichloromethyl- (4′-methoxystyryl) -6-triazine (such as Triazine PMS manufactured by Panchim), 2,4-trichloromethyl- (pipronyl) -6-triazine (such as Triazine PP manufactured by Panchim), 2, 4-trichloromethyl- (4′-methoxynaphthyl) -6-triazine (such as Triazine B manufactured by Panchim), 2 [2 ′ (5 ″ -methylfuryl) ethylidene] -4,6-bis (trichloromethyl) -s -Triazine (manufactured by Sanwa Chemical Co., Ltd.), 2 (2'-furylethylidene) -4,6-bis (trichloromethyl) -s-triazine (manufactured by Sanwa Chemical Co., Ltd.), etc. It is.

  Examples of the borate initiator include NK-3876 and NK-3881 manufactured by Nippon Photosensitizer, and other photoacid generators include 9-phenylacridine, 2,2′-bis (o-chlorophenyl)- 4,4 ′, 5,5′-tetraphenyl-1,2-biimidazole (such as biimidazole manufactured by Kurokin Kasei), 2,2-azobis (2-amino-propane) dihydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) V50), 2,2-azobis [2- (imidazolin-2-yl) propane] dihydrochloride (VA044 manufactured by Wako Pure Chemical Industries, Ltd.), [η-5-2-4- (cyclopentadecyl) (1, 2,3,4,5,6, η)-(methylethyl) -benzene] iron (II) hexafluorophosphonate (Irgacure 261 manufactured by Ciba Geigy), bis (y5-cyclopentadienyl) bis [2, 6-Difluoro-3- (1H Pyridinium-1-yl) phenyl] such as titanium (Ciba Geigy Corp. CGI-784), and the like.

  In addition, an azo initiator such as azobisisobutyronitrile, a peroxide radical initiator sensitive to heat such as benzoyl peroxide, and the like may be used in combination. Further, both radical and cationic initiators may be used in combination. One type of initiator can be used alone, or two or more types can be used in combination.

  The colored pigment (H) used in the present invention is used for using the active energy ray resin composition of the present invention as a coloring material. These are classified into organic pigments and inorganic pigments depending on the configuration, and these are appropriately selected according to the intended color and application.

  Organic pigments are classified according to their basic skeleton. For example, polycyclic rings such as isoindolinone, isoindoline, azomethine, anthraquinone, anthrone, xanthene, diketopyrrolopyrrole, perylene, perinone, quinacridone, indigoid, dioxazine, phthalocyanine Examples thereof include pigments, azo pigments such as monoazo, disazo, and condensed disazo, lake pigments, and fluorescent pigments.

  Examples of inorganic pigments include titanium dioxide, calcium carbonate, barium sulfate, zinc oxide, mica, carbon black, bengara, and aluminum flakes.

  The extender pigment (I) shown in the present invention is a pigment not intended for coloring, and is used for the purpose of obtaining the viscosity and flowability of the composition and the mechanical properties of the cured product. .

  For example, barium sulfate, calcium carbonate, talc, clay, glass flakes, glass beads, graphite, aluminum oxide, aluminum hydroxide, polystyrene beads, polyethylene beads, polypropylene beads, polytetrafluoroethane beads and the like can be mentioned.

  Moreover, the hardening | curing agent (J) shown by this invention is used in order to raise the crosslinking degree of hardened | cured material further. For example, when the composition of the present invention is used as a resist material, water resistance and heat resistance are deteriorated if carboxyl remains after development. For this reason, a carboxyl group derived from a carboxyl group-containing reactive compound (C) or a polyfunctional reactive compound (E) is obtained by blending a compound having an epoxy group as a curing agent and performing a heating step after the development is completed. It is possible to carboxylate by using a compound having an epoxy group as the curing agent (J) to improve the characteristics.

  Furthermore, as other materials, for the purpose of adapting the active energy ray-curable resin composition of the present invention to various applications, other components can be added up to 70 mass%. Examples of other components include resins that are not reactive to active energy rays, various additives, and volatile solvents that are added for viscosity adjustment for the purpose of imparting coating suitability. Examples of other components that can be used are shown below.

  Other resins that are not reactive with active energy rays (so-called inert polymers), such as other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, styrene Resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof can also be used. These are preferably used in a range of up to 40% by mass.

  Other additives include, for example, thermosetting catalysts such as melamine, thixotropy imparting agents such as Aerosil, silicone-based and fluorine-based leveling agents and antifoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, stabilizers, oxidation An inhibitor or the like can be used.

  Depending on the purpose of use, for the purpose of adjusting the viscosity, a volatile solvent can be added in the resin composition of the present invention in a range of 50 mass%, more preferably 35 mass%.

  The active energy ray-curable resin composition of the present invention is easily cured by active energy rays. Specific examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X rays, gamma rays and laser rays, particle rays such as alpha rays, beta rays and electron rays. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in view of suitable applications of the present invention.

  In the present invention, the film forming material is used for the purpose of coating the surface of a substrate. Specific applications include gravure inks, flexo inks, silk screen inks, offset inks and other ink materials, hard coats, top coats, overprint varnishes, clear coats and other coating materials, laminating, optical disk and other various adhesives. This corresponds to adhesive materials such as adhesives and adhesives, resist materials such as solder resists, etching resists, and resists for micromachines. Furthermore, after the film forming material is temporarily applied to the peelable substrate and formed into a film, it is bonded to the original target substrate to form a film, so-called dry film also corresponds to the film forming material. .

  Since the carboxyl group-containing reactive compound (C) and the polyfunctional reactive compound (E) having a carboxyl group of the present invention have improved adhesion to the substrate due to the carboxyl group, a plastic substrate or a metal substrate film Suitable for forming material. Since the polyfunctional reactive compound (E) which does not have a carboxyl group also gives a cured product having excellent hardness, adhesion and impact properties, it is suitable for a film-forming material.

  Furthermore, since the carboxyl group-containing reactive compound (C) and the polyfunctional reactive compound (E) having a carboxyl group are soluble in an alkaline aqueous solution, they should be used as a material composition for drawing with active energy rays. Can do.

  In the present invention, the material composition for drawing with active energy rays means that a film layer of the composition is formed on a substrate, and then the active energy rays such as ultraviolet rays are partially irradiated to irradiate the irradiated portion, It refers to an active energy ray-sensitive composition to be drawn using the physical property difference of the irradiated part. Specifically, the composition is used for the purpose of removing the irradiated part or the unirradiated part by dissolving the irradiated part or the non-irradiated part with, for example, a solvent or an alkaline solution.

  These can be applied to various materials that can be patterned, and are particularly useful for solder resist materials, interlayer insulation materials for build-up methods, and also as printed circuit boards, optoelectronic substrates, and optical substrates as optical waveguides. It is also used for various electrical / electronic / optical substrates.

  As a particularly suitable application, it can be suitably used as a color resist material or a circuit forming material for an optical waveguide by taking advantage of its high heat resistance and high transparency.

  There are no particular restrictions on the method for forming the film, but an intaglio printing method such as gravure, a relief printing method such as flexo, a stencil printing method such as silk screen, a lithographic printing method such as offset, a roll coater, a knife coater, a die coater, Various coating methods such as curtain coater and spin coater can be arbitrarily adopted.

  The cured product of the active energy ray-curable resin composition of the present invention refers to a product obtained by irradiating and curing the active energy ray-curable resin composition of the present invention with active energy rays.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.

Synthesis Example 1: Synthesis 1 of polyfunctional acid anhydride (A)
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen, while the amount of anhydride chloride (b) listed in the table was listed (1.1 equivalents relative to the hydroxyl group in (a)). And 45 g of THF was added to make a uniform solution. The solution was cooled to 5 ° C. with stirring, and (a) described in the table was added in the amount shown in the table, and pyridine (1.2 equivalents relative to the hydroxyl group of (a)) and 54 g of THF were added to obtain a uniform solution. The liquid temperature was gradually dropped while maintaining the liquid temperature at 10 ° C or lower. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour, then heated to 50 ° C., and the reaction was continued for 8 hours. Subsequently, the reaction solution was cooled to 20 ° C., and pyridine hydrochloride as an insoluble component was removed by filtration, and then the filtrate was concentrated. The concentrate was dissolved in 120 ml of ethyl acetate, washed 3 times with 30 ml of water, and then dried over anhydrous magnesium sulfate. After anhydrous magnesium sulfate was removed by filtration, the filtrate was concentrated, and the resulting concentrate was dissolved in 15 ml of ethyl acetate and recrystallized from toluene to obtain a product. In the synthesis of the compound, the reaction was terminated when the disappearance of the raw alcohols was confirmed by gel permeation chromatography (hereinafter referred to as “GPC”).

Comparative Synthesis Example 1-1: Synthesis of Bifunctional Acid Anhydride A bifunctional acid anhydride was synthesized according to Synthesis Example 1. The results are shown in the following table together with Synthesis Example 1.

Abbreviations in the table: TMP: trimethylolpropane PE: pentaerythritol DPE: dipentaerythritol DPE6EO: dipentaerythritol 6 mol ethylene oxide adduct DPE6CL: dipentaerythritol 6 mol caprolactone adduct PE4EO: pentaerythritol 4 mol ethylene oxide adduct BPA2EO: Bisphenol A 2 mol ethylene oxide adduct THI: Tris-2-hydroxyethyl isocyanurate HTAC: Nuclear hydrogenated trimellitic anhydride chloride TMAC: Trimellitic anhydride chloride * HTAC / TMAC (mol ratio) = 1/1

Example 1 Preparation of Carboxyl Group-containing Reactive Compound (C) 20 mmol of polyfunctional acid anhydride (A) prepared in Synthesis Example 1 was added to a flask equipped with a stirrer, reflux condenser, and stirrer (mass in the table). Description) Propylene glycol monomethyl ether acetate is added in an amount of 60% by mass of solid content with respect to the total amount of (A) and (B), and 0.3% by mass of pyridine as a catalyst, including the solvent, is added and stirred. Dissolved.
Furthermore, the compound shown in the table was added as a compound (B) having one or more polymerizable ethylenically unsaturated groups and one or more hydroxyl groups in one molecule, and reacted at 100 ° C. for 10 hours.
It cooled after completion | finish of reaction, the acid value (AV, mgKOH / g) in a solution was measured, it converted into solid content acid value, and the reaction end point was confirmed.
The acid value was measured by a method according to JIS K0070: 1992.

Comparative Example 1 Preparation of Bifunctional Carboxy Group-Containing Reactive Compound In the same manner as in Example 1, the reaction was carried out using 20 mmol (mass described in the table) of the other bifunctional acid anhydrides described in the table.

Abbreviations HEA in Table: Hydroxyethyl acrylate OHV = 116 g / OHeq
PE3A: pentaerythritol triacrylate, pentaerythritol tetraacrylate mixture, tri / tetra ratio = about 50/50 (mol) OHV = 650 g / OHeq
GMA-AA: Glycidyl ether-acrylic acid carboxylate compound, Kyoeisha Chemical Light Ester G-201P, OHV = 214 g / OHeq
PGE-AA: Phenyl glycidyl ether-acrylic acid carboxylate compound, Nippon Kayaku Kayarad R-128H, OHV = 222 g / OHeq
TMEG-100: Ethylene glycol bisan hydrotrimellitate, New Nippon Rika Rikacid TMEG-100

Example 2: Preparation of reactive compound (E) 0.01 mol (mass in the table) of reaction solution of reactive compound (C) prepared in Example 1 in a flask equipped with a stirrer, reflux condenser, and stirrer Description, in terms of solid content), the compound described in the table is added in the stated amount as a compound (D) having one or more polymerizable ethylenically unsaturated groups and one or more epoxy groups in one molecule, Propylene glycol monomethyl ether acetate was added and adjusted so that the solid content was finally 60% by mass, and then reacted at 100 ° C. for 24 hours to obtain a reactive compound (E).

Abbreviations GMA in the table: Glycidyl methacrylate 4HBAGE: 4-hydroxybutyl acrylate glycidyl ether

Example 3: Preparation of white negative resist composition The carboxyl group-containing reactive compound (C) solution synthesized in Example 1 and Comparative Example 1 or the reactive compound (E) solution prepared in Example 2 was solidified. 7g in terms of fraction (actual charge is divided by 60% by mass of solid), other reactive compound (F), radical curable monomer DPHA (dipentaerythritol hexaacrylate, Nippon Kayaku Co., Ltd.) 4 g, Barium sulfate B-30 (Sakai Chemical Industry Co., Ltd.) 5 g as extender pigment (I), Titanium oxide pigment Typaque CR-90 (Ishihara Sangyo Co., Ltd.) 3 g as color pigment (H) J), 4 g of TEPIC-SP (Trisepoxypropylisocyanurate, Nissan Chemical Co., Ltd.), and Irgaku as an active energy ray reactive initiator (G) 0.5 g of A907 (BASF Japan Ltd.) and 4 g of propylene glycol monomethyl ether acetate as a solvent were kneaded using a three-roll mill to obtain a white negative resist composition.

The obtained resist composition was coated on a copper-clad laminate by a silk screen method, and the solvent was volatilized in an oven at 80 ° C. for 15 minutes. Next, in order to estimate the sensitivity of the mask on which the circuit pattern was drawn and the sensitivity using an ultraviolet exposure device (Oak Manufacturing Co., Ltd., model HMW-680GW), UV radiation of 500 mJ / cm ² was irradiated through Kodak Step Tablet No. 2. did. Thereafter, the film on the dry film was peeled off and the peeled state was confirmed. Thereafter, spray development was performed with a 1% aqueous sodium carbonate solution to remove the resin on the non-irradiated part of the ultraviolet rays. After washing with water and drying, the printed circuit board was subjected to a heat curing reaction in a hot air drier at 150 ° C. for 60 minutes to obtain a cured film.

Evaluation item of white resist composition <Sensitivity evaluation>
Sensitivity was determined by how many density portions remained in the exposed portion that passed through the step tablet during development. The higher the number of steps (value), the higher sensitivity is determined in the dark part of the tablet (unit: step).
<Developability evaluation>
The developability was evaluated as the developability based on the so-called break time, which is the time from when the developer was jetted until the pattern-shaped portion was completely developed when developing the exposed portion that passed through the pattern mask (unit: seconds). . About 20 to 40 seconds is preferable.
<Resolution evaluation>
The resolution was determined using an optical microscope to determine whether the line and space pattern included in the pattern mask was finely patterned (unit: micrometers). A small value is determined to be a fine pattern.
<Yellow discoloration evaluation>
Regarding the yellow discoloration property, the resist after the 150 ° C. curing reaction was further put into a hot air oven at 180 ° C. for 72 hours to check the heat resistant colorability. Yellow discoloration was evaluated visually. The evaluation criteria are as follows.
◎: No discoloration ○: Slightly yellowish △: Yellow discoloration is observed ×: Brown discoloration
<Light resistance evaluation>
For light resistance, the resist after the 150 ° C. curing reaction was irradiated with ultraviolet light for 20 hours with a super UV tester (Iwasaki Electric), and the colorability of the white resist after the irradiation was visually evaluated. The evaluation criteria are as follows.
◎: No discoloration ○: Slightly yellowish △: Yellow discoloration is observed ×: Brown discoloration
<Heat resistance evaluation>
For heat resistance, the substrate on which the resist film after the 150 ° C. curing reaction has been prepared is floated in a 260 ° C. solder bath for 1 minute, and then placed in water and rapidly cooled. After repeating this three times, scratches were made in an X shape with a cutter knife, and adhesion evaluation with a cellophane tape was performed.
○: No peeling △: There is a slight peeling trace in the X-shaped part ×: There is peeling

Abbreviations in the table: CCR-1218H: Cresol novolak-type acid-modified epoxy acrylate (Nippon Kayaku)
ZCR-1569H: Biphenyl acid-modified epoxy acrylate (Nippon Kayaku)
ASP-010: Methyl methacrylate, butyl methacrylate, methacrylic acid copolymer (Nippon Kayaku)

  From the above results, the carboxyl group-containing reactive compound (C) and the polyfunctional reactive compound (E) of the present invention are excellent in sensitivity, developability, and resolution, and further have a balance of yellowness, light resistance, and heat resistance. Can be obtained.

Example 4: Coating material composition for metal 10 g of the carboxyl group-containing reactive compound (C) prepared in Example 1 or the polyfunctional reactive compound (E) prepared in Example 2 in terms of solid content (actual The amount charged was divided by 60% by mass of solid content), and as other reactive compounds (F), 15 g of bisphenol ethylene oxide diacrylate, 15 g of tripropylene glycol diacrylate, 10 g of urethane acrylate (UX-5000, Nippon Kayaku), As an active energy ray reactive initiator (G), 1.5 g of Irgacure 184 (BASF Japan) was added and kneaded well until uniform to prepare a curable composition.

The obtained composition was coated on a TFS substrate (tin-free steel plate) with a wire bar coater # 8, and the solvent was volatilized in an oven at 100 ° C. for 10 minutes. Then, 500 mJ / cm < ² > ultraviolet-ray was irradiated, the curing reaction was performed, and the cured film was obtained.

Evaluation of metal coating materials <Curability evaluation>
The hardness of the coating film after curing was evaluated according to a pencil hardness test (JIS-K5600-5-4: 1999).
<Adhesion evaluation>
The adhesion to the metal substrate was evaluated according to a cross-cut peel test (JIS-K5600-5-6: 1999).
Evaluation criteria were also based on JIS-K5600 and evaluated according to the following classification.
Category 0: No peeling, good Classification 1: Slight peeling at the corners Category 2: Peeling at the corners Category 3: Peeling less than half of the squares Category 4: Peeling more than half of the squares Category 5: There is almost complete peeling, poor <impact resistance evaluation>
The impact resistance of the coating film was evaluated according to the DuPont impact test (JIS-K5600-5-6: 1999). The weight was 500 g, the impact type was 6.35 mm, and the drop height was 250 mm.
○: No cracking △: Cracking but no peeling ×: Peeling

Abbreviations in the table: HOA-HH: hydroxyethyl acrylate hexahydrophthalic acid monoester TPGDA: tripropylene glycol diacrylate

  From the above results, the resin composition containing the carboxyl group-containing reactive compound (C) and / or the polyfunctional reactive compound (E) of the present invention is a coating composition excellent in adhesion, curability, and impact resistance. It was shown that it can be.

The carboxyl group-containing reactive compound (C) and polyfunctional reactive compound (E) of the present invention have little discoloration, high resolution, and high heat resistance. For this reason, in addition to the solder resist material, it is suitable for a film forming material, a curable material that is required to be colorless and transparent, or for the purpose of coloring, such as an active energy ray curable coating material, and printing ink.
Furthermore, since the carboxyl group-containing reactive compound (C) and the polyfunctional reactive compound (E) having a carboxyl group of the present invention have a carboxyl group in the molecule, they are also suitable for negative-type optical drawing by alkali development. Therefore, it can be suitably used for resist materials and color resists that are required to be less colored, especially color resists for LCDs, black matrices, spacer resists, optical waveguide materials, and the like.

Claims (9)

Obtained by reacting a polyhydric alcohol (a) having at least three hydroxyl groups in one molecule with nuclear hydrogenated trimellitic anhydride halide (b-1) or trimellitic anhydride halide (b-2). Carboxyl group-containing reactive compound obtained by reacting polyfunctional acid anhydride (A) with compound (B) having one or more polymerizable ethylenically unsaturated groups and one or more hydroxyl groups in one molecule (C). The polyhydric alcohol (a) according to claim 1 is represented by the following general formula (1):

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ are a hydrogen atom, hydroxyl group, carbon number 1 Represents a hydrocarbon group having ˜11 or a hydroxyalkyl group having 1 to 4 carbon atoms, R ² represents a hydroxyl group or a hydroxyalkyl having 1 to 4 carbon atoms, l is 0 to 11, m and n are each 1 to 1; The carboxyl group-containing reactive compound (C), which is a polyhydric alcohol (a-1) containing at least three hydroxyl groups in one molecule represented by The polyhydric alcohol (a) obtained by reacting the polyhydric alcohol (a) according to claim 1 or 2 with at least one selected from the group consisting of alkylene oxide, cyclic ether, and cyclic ester. Carboxyl group-containing reactive compound (C) which is alcohol (a-2). The carboxyl group-containing reactive compound (C) according to any one of claims 1 to 3, wherein one or more polymerizable ethylenically unsaturated groups and one or more epoxy groups are contained in one molecule. The polyfunctional reactive compound (E) obtained by making the compound (D) which it has together react. An active energy ray-curable resin composition comprising the reactive compound (C) according to any one of claims 1 to 3. An active energy ray-curable resin composition comprising the polyfunctional reactive compound (E) according to claim 4. The active energy ray-curable resin composition according to claim 5, which is a film-forming material. The active energy ray-curable resin composition according to claim 5 or 6, wherein the active energy ray-curable resin composition is a material composition intended for drawing with active energy rays. A cured product of the active energy ray-curable resin composition according to any one of claims 5 to 8.