CN105968001B

CN105968001B - Carboxyl group-containing reactive compound, curable resin composition using same, and cured product

Info

Publication number: CN105968001B
Application number: CN201610140971.5A
Authority: CN
Inventors: 栗桥透; 古江诚; 岩田智史; 清柳典子
Original assignee: Nippon Kayaku Co Ltd
Current assignee: Nippon Kayaku Co Ltd
Priority date: 2015-03-13
Filing date: 2016-03-11
Publication date: 2020-05-08
Anticipated expiration: 2036-03-11
Also published as: TWI681984B; CN105968001A; JP2016169326A; KR20160110139A; JP6362272B2; TW201632565A

Abstract

The invention provides a reactive material which is cured by active energy rays such as ultraviolet rays and can obtain high heat resistance and low coloring property. The solution of the present invention is to provide a carboxyl group-containing reactive compound obtained by reacting a nuclear hydrogenated trimellitic anhydride acid halide or trimellitic anhydride acid halide with a polyhydric alcohol to obtain a polyfunctional acid anhydride, and reacting the polyfunctional acid anhydride with a compound having 1 or more polymerizable ethylenically unsaturated groups and 1 or more hydroxyl groups in 1 molecule; the polyfunctional reactant is obtained by reacting the reactive compound containing a carboxyl group with a compound having 1 or more polymerizable ethylenically unsaturated groups and 1 or more epoxy groups in 1 molecule.

Description

Carboxyl group-containing reactive compound, curable resin composition using same, and cured product

Technical Field

The present invention relates to a reactive compound containing a carboxyl group, a composition thereof, and a use thereof, wherein an acid anhydride group is introduced into a polyol compound, and then the compound is further reacted with a compound having 1 or more polymerizable ethylenically unsaturated groups and 1 or more hydroxyl groups in the molecule.

Background

As a typical display element photoresist material for color filters and a typical solder resist material for printed circuit boards, there is a reactive compound containing a carboxyl group obtained by reacting an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride with an epoxy acrylate or the like. The reactive compound having a carboxyl group is low in acid value and excellent in developability, and can be used in a solder resist ink (patent document 1).

Since conventional acid-modified epoxy acrylates have a wide molecular weight distribution, when used as a negative resist material, if the non-irradiated part is eluted with an alkaline developer, the boundary between the irradiated part and the non-irradiated part cannot be smoothly eluted, and the resolution of the edge line deteriorates.

Further, the acid-modified acrylic epoxy ester uses an epoxy compound as a raw material. Therefore, a halogen component derived from epichlorohydrin, for example, remains as a raw material in the production of the epoxy compound. When the acid-modified acrylic epoxy ester is used as a sealing material for electronic circuits such as solder resists, it is said that the halogen component may adversely affect the long-term reliability of the circuit.

When acid-modified epoxy acrylates are used for color resists for color filters, the acid-modified epoxy acrylates are generally derived from polyfunctional aromatic epoxy groups. This is to maintain the heat resistance of the acid-modified epoxy acrylate. However, the acid-modified acrylic esters have a problem of yellowing or the like due to heat treatment in the production process (patent document 2).

The acid anhydride used for the production of the conventional acid-modified epoxy acrylate is mainly one containing 1 acid anhydride group in 1 molecule. When the acid anhydride group having 2 or more acid groups in 1 molecule is used, the hydroxyl groups in the acid-modified epoxy acrylate 1 increase, and the crosslinking reaction between the molecules proceeds, so that it is difficult to control the molecular weight.

Patent document 3 describes a method for obtaining a composition for a resist, which comprises reacting a compound having 2 anhydride groups in 1 molecule with a compound having hydroxyl groups and unsaturated groups in 1 molecule to obtain a half-esterified compound, and further reacting the half-esterified compound with an epoxy compound, but patent document 3 does not describe a compound or a composition derived from a compound having 3 or more anhydride groups in 1 molecule as in the present invention.

[ Prior art documents ]

[ patent document ]

Patent document 1: international publication No. WO2008/004630

Patent document 2: japanese patent laid-open publication No. 2005-126674

Patent document 3: japanese patent laid-open publication No. 2005-206803

Disclosure of Invention

[ problems to be solved by the invention ]

The present invention addresses the problem of providing a reactive resin having good photoreactivity and developability and suitable characteristics for use as a negative resist material.

[ means for solving the problems ]

The present inventors have found that a carboxyl group-containing reactive compound (C) obtained by reacting a polyfunctional acid anhydride (a) having a specific structure with a compound (B) having 1 or more polymerizable ethylenically unsaturated groups and 1 or more hydroxyl groups in 1 molecule has particularly excellent resin physical properties.

That is, the present invention relates to

(1) A carboxyl group-containing reactive compound (C) obtained by reacting a polyhydric alcohol (a) having at least 3 hydroxyl groups in 1 molecule with a nuclear hydrogenated trimellitic anhydride acid halide (B-1) or trimellitic anhydride acid halide (B-2) to obtain a polyfunctional acid anhydride (A), and further reacting the polyfunctional acid anhydride (A) with a compound (B) having 1 or more polymerizable ethylenically unsaturated groups and 1 or more hydroxyl groups in 1 molecule.

(2) A carboxyl group-containing reactive compound (C) obtained by reacting a polyhydric alcohol (a) having at least 3 hydroxyl groups in 1 molecule with a nuclear hydrogenated trimellitic anhydride acid halide (B-1) or trimellitic anhydride acid halide (B-2) to obtain a polyfunctional acid anhydride (A), and further reacting the polyfunctional acid anhydride (A) with a compound (B) having at least 1 polymerizable ethylenically unsaturated group and at least 1 hydroxyl group in 1 molecule, wherein the polyhydric alcohol (a) is a polyhydric alcohol (a-1) having at least 3 hydroxyl groups in 1 molecule represented by the following general formula (1):

(in the formula, R¹、R²、R³、R⁴、R⁵、R⁶Each independently of the other, R¹、R³、R⁴、R⁵、R⁶Represents a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 11 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms, R²Represents a hydroxyl group or a hydroxyalkyl group having 1 to 4 carbon atoms. l represents an integer of 0 to 11, and m and n each represent an integer of 1 to 11).

(3) A carboxyl group-containing reactive compound (C) obtained by reacting a polyhydric alcohol (a-2) having at least 3 or more hydroxyl groups in 1 molecule with a nuclear hydrogenated trimellitic anhydride acid halide (B-1) or trimellitic anhydride acid halide (B-2) to obtain a polyfunctional acid anhydride (A), and further reacting the polyfunctional acid anhydride (A) with a compound (B) having 1 or more polymerizable ethylenically unsaturated groups and 1 or more hydroxyl groups in 1 molecule, wherein the polyhydric alcohol (a-2) is obtained by reacting the polyhydric alcohol (a) with 1 or more selected from the group consisting of alkylene oxides (i.e., compounds having 3-membered cyclic ethers), 4-membered cyclic ethers, and cyclic esters.

(4) A polyfunctional reactive compound (E) obtained by reacting the reactive compound (C) having a carboxyl group described in (1) or (2) with a compound (D) having 1 or more polymerizable ethylenically unsaturated groups and 1 or more epoxy groups in 1 molecule.

(5) A polyfunctional reactive compound (E) obtained by reacting the carboxyl group-containing reactive compound (C) described in (3) with a compound (D) having 1 or more polymerizable ethylenically unsaturated groups and 1 or more epoxy groups in 1 molecule.

(6) An active energy ray-curable resin composition comprising the reactive compound (C) of (1) or (2).

(7) An active energy ray-curable resin composition comprising the reactive compound (C) of (3).

(8) An active energy ray-curable resin composition comprising the polyfunctional reactive compound (E) of (4).

(9) An active energy ray-curable resin composition comprising the polyfunctional reactive compound (E) of (5).

(10) The active energy ray-curable resin composition according to (6), which is a coating film-forming material.

(11) The active energy ray-curable resin composition according to (7) which is a coating film-forming material.

(12) The active energy ray-curable resin composition according to (8) which is a coating film-forming material.

(13) The active energy ray-curable resin composition according to (9) which is a coating film-forming material.

(14) The active energy ray-curable resin composition according to (6), which is a drawing material cured by an active energy ray.

(15) The active energy ray-curable resin composition according to (7) which is a drawing material cured by an active energy ray.

(16) The active energy ray-curable resin composition according to (8), which is a drawing material cured by an active energy ray.

(17) The active energy ray-curable resin composition according to (9), which is a drawing material cured by an active energy ray.

(18) A cured product of the active energy ray-curable resin composition according to (6).

(19) A cured product of the active energy ray-curable resin composition according to (7).

(20) A cured product of the active energy ray-curable resin composition according to (8).

(21) A cured product of the active energy ray-curable resin composition according to (9).

(22) A cured product of the coating forming material according to (10).

(23) A cured product of the coating forming material according to (11).

(24) A cured product of the coating forming material according to (12).

(25) A cured product of the coating forming material according to (13).

(26) A cured product of the mapping material cured by the active energy ray of (14).

(27) A cured product of the mapping material cured by an active energy ray according to (15).

(28) A cured product of the mapping material cured by the active energy ray of (16).

(29) A cured product of the mapping material cured by an active energy ray according to (17).

[ Effect of the invention ]

The carboxyl group-containing reactive compound (C) and the polyfunctional reactive compound (E) of the present invention have excellent reactivity and excellent developability in a photopatterning process, and provide a tough cured product.

The carboxyl group-containing reactive compound (C) and the polyfunctional reactive compound (E) of the present invention can be used for solder resists for printed wiring boards, interlayer insulating materials for semiconductor package substrates, solder resists for flexible printed wiring boards, plating resists, and the like.

In particular, the composition is also suitable for color resists and the like, black matrix materials, spacer materials and the like which are useful for color filters and the like, by utilizing the characteristics of high coloring properties and high heat resistance.

The carboxyl group-containing reactive compound (C) and the polyfunctional reactive compound (E) of the present invention can also be used for optical waveguides and the like by a photolithography method.

Detailed Description

The carboxyl group-containing reactive compound (C) of the present invention is obtained by reacting a polyhydric alcohol (a) having at least 3 or more hydroxyl groups in 1 molecule with a nuclear hydrogenated trimellitic anhydride acid halide (B-1) or trimellitic anhydride acid halide (B-2) to obtain a polyfunctional acid anhydride (A), and further reacting the polyfunctional acid anhydride (A) with a compound (B) having 1 or more polymerizable ethylenically unsaturated groups and 1 or more hydroxyl groups in 1 molecule.

The polyfunctional reactive compound (E) of the present invention is obtained by reacting the reactive compound (C) having a carboxyl group of the present invention with the compound (D) having 1 or more polymerizable ethylenically unsaturated groups and 1 or more epoxy groups in 1 molecule.

The polyol (a) used in the present invention has at least 3 or more hydroxyl groups in 1 molecule. When the number of hydroxyl groups is 2 or less in 1 molecule, a strong crosslinked structure cannot be formed when the final cured product is obtained.

The polyol (a) in the present invention preferably has a structure represented by the following general formula (1).

(in the formula, R¹、R²、R³、R⁴、R⁵、R⁶Each independently of the other, R¹、R³、R⁴、R⁵、R⁶Represents a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 11 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms, R²Represents a hydroxyl group or a hydroxyalkyl group having 1 to 4 carbon atoms. l represents an integer of 0 to 11, and m and n each represent an integer of 1 to 11).

In the general formula (1), when l or m is 2 or more, there are a plurality of R¹、R³、R⁴、R⁶In (1), each R¹、R³、R⁴、R⁶May be different substituents. For example, when l is 4, there are 4R¹There may be 4 identical substituents or all substituents may be different. R³、R⁴、R⁶Is also reacted with R¹The same is true.

Specific examples of the polyol (a) include: triols such as 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-decanetriol, and tris-2-hydroxyethyl isocyanurate; tetraols such as di (trimethylolpropane), 1,2, 2-ethaneditetraol, erythritol, neopentyltetraol, 1,2,3, 5-pentaerythriol, 1,2,4, 5-pentaerythriol, 1,5, 5-pentaerythriol, 1,2,5, 6-hexanetetraol, 1,2,7, 8-octaerythriol, and 1,2,9, 10-decanetetraol; polyols such as bis (neopentyltetraol) and polyglycerin.

Among these, when a polyol having 4 to 6 hydroxyl groups in the molecule represented by the general formula (1) is used, the properties of the resulting cured product are excellent. In particular, pentaerythritol, ditrimethylolpropane and bis (pentaerythritol) are more preferable from the viewpoint of good properties of the cured product and easiness of obtaining the material.

The polyol (a-2) of the present invention is a compound having a structure of 1 or more selected from the group consisting of alkylene oxides (i.e., compounds of cyclic ethers having 3-membered rings), cyclic ethers having 4 or more-membered rings, and cyclic esters, which are addition-polymerized to the polyol (a). The polyol (a-2) can also optimize the reactivity and the properties of the cured product depending on the application.

In the general formula (1), R¹The hydrocarbon group shown refers to an atomic group consisting of only carbon atoms and hydrogen atoms.

The number of carbons of the hydrocarbon group is more preferably 1 to 11. Specific examples thereof include: aliphatic hydroxyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, straight-chain or branched pentyl, straight-chain or branched hexyl, straight-chain or branched heptyl, and straight-chain or branched octyl; alicyclic hydrocarbon groups such as cyclohexyl, methylcyclohexyl, and ethylcyclohexyl; aromatic groups such as phenyl, tolyl, naphthyl, and methylnaphthyl; and aromatic substituted alkyl groups such as benzyl and naphthylmethyl. In the present invention, from the viewpoint of good transparency of the cured product of the present invention, aliphatic hydrocarbon groups and alicyclic hydrocarbon groups are more preferable, and from the viewpoint of imparting good toughness and heat resistance to the cured product of the present invention, methyl groups and ethyl groups are more preferable.

R¹Or R²The hydroxyalkyl group means an atomic group in which 1 or 2 or more hydrogen atoms in a linear or branched alkyl group are substituted with a hydroxyl group.

The number of carbons of the hydroxyalkyl group is more preferably 1 to 4. Specific examples thereof include: 1 or 2 or more hydrogen atoms of methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl are substituted by hydroxyl. In the present invention, from the viewpoint of easy reaction, a compound in which 1 hydrogen of the terminal carbon is substituted with a hydroxyl group is more preferable. Among them, hydroxymethyl and hydroxyethyl are more preferable from the viewpoint that the cured product of the present invention has good toughness and heat resistance.

The alkylene oxide used in the present invention refers to a compound of cyclic ether having 3-membered ring.

The carbon number of the alkylene oxide (i.e., the compound of a cyclic ether having 3-membered rings) is preferably 2 to 8. Examples thereof include: ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and the like. The alkylene oxide may be 1 kind or 2 or more kinds may be mixed as required. Among them, in the present invention, at least one selected from ethylene oxide and propylene oxide is preferable because of easy availability and low cost.

The epoxy ring (i.e., the compound of the cyclic ether having a 3-membered ring) is used in an amount of usually 0.1 to 6.0 equivalents, more preferably 0.2 to 2.0 equivalents, relative to 1 equivalent of the hydroxyl group of the polyol (a). Within this range, the resulting cured product is excellent in heat resistance and toughness.

The cyclic ether having 4 or more membered rings used in the present invention is not particularly limited as long as it is a compound having a structure in which 1 or more carbons in the cyclic hydrocarbon having 4 or more membered rings are substituted.

The cyclic ether having 4 or more membered rings is more preferably 4 to 6 membered rings, and specific examples thereof include oxetane, tetrahydrofuran, tetrahydropyran and the like. The number of the cyclic ethers having 4 or more ring members may be 1 or 2 or more, if necessary. Among them, tetrahydrofuran is preferred in the present invention because it is easily available and inexpensive.

The amount of the 4-or more-membered cyclic ether to be used is usually 0.1 to 6.0 equivalents, and preferably 0.2 to 2.0 equivalents, of the 4-or more-membered cyclic ether to 1 equivalent of the hydroxyl group of the polyol (a). 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.

The carbon number of the cyclic ester is more preferably 2 to 6. Specific examples of the cyclic ester include: and caprolactone, propiolactone, butyrolactone, valerolactone, caprolactone and the like. The cyclic esters may be 1 or more than 2 kinds mixed as necessary. Among these, caprolactone is preferred in the present invention because it is easy to obtain and inexpensive.

The amount of the cyclic ester to be used is usually 0.1 to 6.0 equivalents, and preferably 0.2 to 2.0 equivalents, based on 1 equivalent of the hydroxyl group of the polyol (a). Within this range, the resulting cured product has good heat resistance and toughness.

Specific examples of the polyol (a-2) include: trimethylolpropane ethylene oxide adduct, trimethylolpropane propylene oxide adduct, trimethylolpropane tetrahydrofuran adduct, trimethylolpropane caprolactone adduct, neopentyltetraol ethylene oxide adduct, neopentyltetraol propylene oxide adduct, neopentyltetraol tetrahydrofuran adduct, neopentyltetraol caprolactone adduct, bis (neopentyltetraol) ethylene oxide adduct, bis (neopentyltetraol) propylene oxide adduct, bis (neopentyltetraol) tetrahydrofuran adduct, bis (neopentyltetraol) caprolactone adduct, and the like.

The nuclear hydrogenated trimellitic anhydride acid halide (b-1) is used for introducing an acid anhydride group into the polyol (a) to convert it into a polyfunctional acid anhydride compound. Thus, the acid anhydride group can be introduced without being subjected to ring-opening esterification. In the present specification, the nuclear hydrogenated trimellitic anhydride acid halide (b-1) will be hereinafter abbreviated as "(b-1)".

Further, since the core is hydrogenated, the coloring is not reduced even under heat resistance and light resistance, and the cured product has excellent heat resistance and toughness while maintaining high optical characteristics.

Trimellitic anhydride acid halide (b-2) and (b-1) are used for the same purpose. In the present specification, trimellitic anhydride acid halide (b-2) will be hereinafter abbreviated as "(b-2)". (b-2) has higher heat resistance than (b-1).

The (b-1) and (b-2) may be used in combination, and the balance between the coloring property and the heat resistance may be suitably adjusted depending on the application. In the present specification, (b-1) or (b-2) will be hereinafter collectively referred to as "acid halide".

Examples of the acid halide include an acid fluoride, an acid chloride, an acid bromide, and an acid iodide. Among them, a chlorinated substance is more preferable in terms of easiness of reaction.

The polyfunctional acid anhydride (a) can be synthesized by a conventional method. The method of adding the reagent in the reaction of the polyol (a) and the acid halide is not particularly limited, and any addition method can be employed. For example, the following may be employed: a method in which the polyol (a) and the basic substance are dissolved in a solvent, and the acid halide dissolved in the solvent is slowly dropped therein; or, conversely, a method of dropping a mixture solution of the polyol (a) and the basic substance into a solvent in which the above acid halide is dissolved as necessary; a method of dropping a basic substance into a solution of an acid halide and a polyhydric alcohol (a); and a step of dropping a solution of an acid halide and a solution of a basic substance simultaneously into a solution of the polyol (a). In the present specification, the polyol (a) will be hereinafter referred to simply as "(a)".

The reaction of (a) with an acid halide in the presence of a basic substance is carried out while producing a hydrochloride produced by neutralizing the basic substance. After this is removed by filtration, the crude product of the objective polyfunctional acid anhydride (A) is obtained in high yield by concentrating the filtrate. The crude product is dissolved in an appropriate solvent, washed with water, concentrated, and dried under reduced pressure to obtain a high-purity polyfunctional acid anhydride (a). Further, recrystallization is carried out with an appropriate solvent as necessary, whereby a polyfunctional acid anhydride (A) of higher alcohol degree is obtained.

(a) The amount of (b) to be used is usually 0.6 to 1.0 equivalent, more preferably 0.8 to 1.0 equivalent, in terms of hydroxyl equivalent, to 1 acid halide. Within this range, all of the hydroxyl groups of (a) are esterified without leaving an unreacted acid halide in the system.

The solvent that can be used in the reaction of the acid halide and (a) is not particularly limited as long as it is inert to the raw material, and there may be mentioned: ether solvents such as tetrahydrofuran, 1, 4-dioxane, and 1, 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; aromatic hydrocarbon solvents such as toluene and xylene; halogen-containing solvents such as dichloromethane, chloroform, 1, 2-dichloroethane, etc.; amide solvents such as N-methyl-2-pyrrolidone, N-dimethylacetamide, N-diethylacetamide, and N, N-dimethylformamide; phosphorus-containing solvents such as hexamethylphosphoramide; sulfur-containing solvents such as dimethyl sulfoxide; ester-based solvents such as γ -butyrolactone, ethyl acetate, butyl acetate, etc.; nitrogen-containing solvents such as 1, 3-dimethyl-2-imidazolidinone; and 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 2 or more.

Among the solvents listed herein, a 4-or more-membered cyclic ether or cyclic ester used in the production of the polyol (a-2) from (a) is contained, but when (a) is reacted with an acid halide, the reaction temperature is from-10 ℃ to 80 ℃, more preferably from 0 ℃ to 70 ℃, and still more preferably from 10 ℃ to 60 ℃. When the reaction temperature is higher than 80 ℃, the reaction rate of (a) with the acid halide decreases when (a) is reacted with a 4-membered or higher cyclic ether or cyclic ester to obtain the polyol (a-2). The reaction time is not particularly limited, and is usually 10 minutes to 48 hours, more preferably 30 minutes to 24 hours. The reaction is usually carried out under normal pressure, and if necessary, under increased pressure or reduced pressure.

When the polyol (a-2) is produced by reacting (a) with a cyclic ether or cyclic ester having 4 or more ring members, the reaction temperature is 80 to 250 ℃, preferably 90 to 220 ℃, and more preferably 100 to 200 ℃. The reaction time is not particularly limited, and is usually 10 minutes to 48 hours, more preferably 30 minutes to 24 hours. The reaction is usually carried out under normal pressure, and if necessary, under increased pressure or reduced pressure.

The solubility concentration in the reaction for obtaining the polyfunctional acid anhydride (a) is usually 5 to 50% by mass, and is preferably 10 to 40% by mass in view of the control of side reactions and the filtration step of precipitation. More preferably, the content is in the range of 10 to 40 mass%.

The reaction gas atmosphere in the reaction to obtain the polyfunctional acid anhydride (a) is usually carried out under nitrogen. The reaction vessel may be a closed type or an open type, but in order to maintain the reaction system in an inert gas atmosphere, an inert gas-sealable reaction vessel may be used in the open type.

The basic substance is used for neutralizing hydrochloric acid generated while the reaction is proceeding. The type of the basic substance used in this case is not particularly limited, and organic 3-grade amines such as pyridine, triethylamine, and N, N-dimethylaniline; inorganic alkaline substances such as potassium carbonate and sodium hydroxide. Pyridine and triethylamine are more preferable from the viewpoint of being inexpensive and from the viewpoint of being soluble in a liquid and facilitating the reaction operation. Further, from the viewpoint of being inexpensive, an inorganic basic substance is more preferable.

The amount of the basic substance to be used is not particularly limited, but when it is used in an excessive amount, the basic substance may be mixed into the product and the purification load may be increased, and therefore, the basic substance is usually used in an amount of 1.0 to 30 molar times, preferably 1.2 to 20 molar times, and more preferably 1.5 to 10 molar times, based on the acid halide.

In the washing operation, a part of the polyfunctional acid anhydride (a) is hydrolyzed to be converted into a polycarboxylic acid, but the polycarboxylic acid produced by the hydrolysis of the part can be easily converted back into the polyfunctional acid anhydride by subjecting the polycarboxylic acid to a heat treatment under reduced pressure. The temperature used in this heat treatment step under reduced pressure is 80 ℃ to 200 ℃, more preferably 100 ℃ to 180 ℃, and the degree of reduced pressure is 10MPa or less, more preferably 1MPa or less, and the upper limit of the heating time is not particularly limited, but is usually 10 minutes to 48 hours, more preferably 30 minutes to 24 hours.

The polyfunctional acid anhydride (A) thus obtained can be further purified. As the purification method, recrystallization, sublimation, washing, activated carbon treatment, column chromatography, and the like can be optionally performed. Moreover, these refining methods can be repeated or performed in combination. The purity of the polyfunctional acid anhydride (A) thus obtained is, for example, usually 90 ℃ or higher, preferably 95 ℃ or higher, and more preferably 98 ℃ or higher in terms of the peak area ratio obtained by analysis such as gel permeation chromatography (hereinafter referred to as "GPC").

The compound B having 1 or more polymerizable ethylenically unsaturated groups and 1 or more hydroxyl groups in 1 molecule shown in the present invention is intended to impart photoreactivity and solubility in an alkaline developer by half-esterification through addition reaction of an acid anhydride group and a hydroxyl group, introduction of an unsaturated bond into the molecule, and generation of a free carboxyl group.

The hydroxyl group of the compound (B) is preferably 1 in 1 molecule. When the number of the (B) atoms is 2 or more, the crosslinking of (A) is effected. Although this is used for positively increasing the molecular weight, excessive use of this leads to increase in viscosity and deterioration in developability.

Specifically, examples of the generally available compound (B) having 1 or more polymerizable ethylenically unsaturated groups and 1 or more hydroxyl groups in 1 molecule include: hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and the like.

Further, there may be mentioned: polyfunctional (meth) acrylates having a hydroxyl group such as neopentyltetraol tri (meth) acrylate and dineopentylenetetraol tri (meth) acrylate.

Further, as carboxylic acid esterified compounds obtained by adding an unsaturated carboxylic acid such as (meth) acrylic acid to an epoxy compound, there can be mentioned: methyl glycidyl ether (meth) acrylic acid adduct, ethyl glycidyl ether (meth) acrylic acid adduct, 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, butyl phenyl glycidyl ether (meth) acrylic acid adduct, glycidyl (meth) acrylate (meth) acrylic acid adduct, and the like.

Furthermore, glycol monovinyl ethers such as so-called ethylene glycol monovinyl ether, propylene glycol monovinyl ether, and butylene glycol monovinyl ether may also be used.

The reaction of the polyfunctional acid anhydride (A) with the compound (B) having an ethylenically unsaturated group and 1 or more hydroxyl groups can be carried out by a conventional method.

In this case, in order to accelerate the reaction, it is preferable to use a catalyst in an amount of 0.1 to 10 parts by mass relative to the total amount of the reactants, i.e., the reactants other than the polyfunctional acid anhydride (a), the compound (B) and the solvent added as the case may be. The reaction temperature at this time is 60 to 150 ℃ and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include: triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylantimony, methyltriphenylantimony, chromium octanoate, zirconium octanoate, and the like.

The acid addition reaction may be a reaction without a solvent or a reaction diluted with a solvent. The solvent to be used herein is not particularly limited as long as it is a solvent inert to the present reaction. The amount of the solvent to be used is preferably adjusted as appropriate depending on the viscosity or the use of the resin to be obtained, but the solid content is preferably 90 to 30% by mass, more preferably 80 to 50% by mass.

Specific examples thereof include: aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene; aliphatic hydrocarbon solvents such as hexane, octane and decane; and petroleum ether, unleaded gasoline, naphtha (petroleumnaphtha) and the like as a mixture thereof.

Further, as the ester-based solvent, there can be mentioned: alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate, cyclic esters such as γ -butyrolactone, mono-or poly-alkylene glycol monoalkyl ether monoacetates such as ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate and butanediol monomethyl ether acetate, and polycarboxylic acid alkyl esters such as glutaric acid dialkyl ester, succinic acid dialkyl ester and adipic acid dialkyl ester.

Further, as the ether solvent, there can be mentioned: alkyl ethers such as diethyl ether and ethyl butyl ether, alcohol ethers such as 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, and cyclic ethers such as tetrahydrofuran.

Further, as the ketone solvent, there can be mentioned: acetone, methyl ethyl ketone, cyclohexanone, isophorone, and the like.

The present invention further includes a polyfunctional reactive compound (E) obtained by reacting the carboxyl group-containing reactive compound (C) of the present invention with a compound (D) having 1 or more polymerizable ethylenically unsaturated groups and 1 or more epoxy groups in 1 molecule, for the purpose of imparting reactivity or adjusting the acid value to be imparted. The polyfunctional reactive compound (E) of the present invention includes a polyfunctional reactive compound (E) having a carboxyl group and a polyfunctional reactive compound (E) having no carboxyl group depending on the amount of the compound (D) having 1 or more polymerizable ethylenically unsaturated groups and 1 or more epoxy groups in 1 molecule used.

The compound (D) preferably has 1 epoxy group in 1 molecule. When the number of the reactive compound (C) is 2 or more, the reactive compound (C) is crosslinked. Although this is used for positively increasing the molecular weight, excessive use of this leads to increase in viscosity and deterioration in developability.

Specific examples of the compound (D) having 1 or more polymerizable ethylenically unsaturated groups and 1 or more epoxy groups in 1 molecule include: glycidyl (meth) acrylate, hydroxybutyl (meth) acrylate glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether and the like.

The reaction of the reactive compound (C) having a carboxyl group with the compound (D) can be carried out by a conventional method. In the present reaction, the same catalyst and solvent as those used in the reaction of the reactive compound (C) can be used. In this case, the catalyst is used in an amount of 0.1 to 10% by mass based on the total amount of the reactants, i.e., the reactants other than the reactive compound (C), the compound (D), and the solvent added as the case may be. The reaction temperature is 60 to 150 ℃ 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 a composition which is mixed with other substances according to various uses and further provides characteristics according to the uses.

Examples thereof include: other reactive compound (F), active energy ray-reactive initiator (G), coloring pigment (H), extender pigment (I), curing agent (J), other material, and the like.

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

Examples of the usable acrylates include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, other epoxy acrylates, polyester acrylates, and amine ester acrylates.

Examples of monofunctional (meth) acrylates include: methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether, phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and the like.

Examples of the polyfunctional (meth) acrylates include: butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, diol di (meth) acrylate, diethylene glycol 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, hydrogenated bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, di (meth) acrylate of an epsilon-caprolactone adduct of neopentyl glycol hydroxytrimethylacetate, poly (meth) acrylate of a reactant of dineoerythritol and epsilon-caprolactone, dineopentylenetetraol poly (meth) acrylate, neopentylglycol di (meth), Trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate and ethylene oxide adducts thereof, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and ethylene oxide adducts thereof, and the like.

As the vinyl compound that can be used, there can be mentioned: vinyl ethers, styrenes, and other vinyl compounds. Examples of the vinyl ethers include: ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, and the like. Examples of the styrenes include: styrene, methylstyrene, ethylstyrene, etc. Examples of other vinyl compounds include: triallyl isocyanurate, trimethylallyl isocyanurate, and the like.

Further, examples of the reactive oligomers include: amine ester acrylate having a functional group capable of inducing active energy rays and an amine ester bond in the same molecule; polyester acrylate having functional groups and ester bonds in the same molecule, which are also sensitive to active energy rays; an epoxy acrylate derived from another epoxy resin and having a functional group which is sensitive to active energy rays in the same molecule; and reactive oligomers used in combination.

In general, the cationic reactive monomer is not particularly limited as long as it is a compound having an epoxy group. Examples thereof include: glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate (e.g., "CYRACURE UVR-6110" from Union Carbide), 3, 4-epoxycyclohexylethyl-3, 4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (e.g., "ELR-4206" from Union Carbide), limonene dioxide (e.g., "CELLOXIDE 3000" from Daicel chemical industries, Ltd.), allyl cyclohexene dioxide, 3, 4-epoxy-4-methylcyclohexyl-2-epoxypropane, 2- (3, 4-epoxycyclohexyl-5, 5-spiro-3, 4-epoxy group) cyclohexane-m-dioxane, bis (3, 4-epoxycyclohexyl) adipate (e.g., "CYRACURE 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.

Among 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 group are reacted, and therefore, the resulting product is required to be mixed as a 2-liquid mixture.

The active energy ray-curable resin composition of the present invention contains the carboxyl group-containing reactive compound (C) or the polyfunctional reactive compound (E) in an amount of 97 to 5% by mass, preferably 87 to 10% by mass, and the other reactive compound (F) in an amount of 3 to 95% by mass, more preferably 3 to 90% by mass. Other ingredients may also be included as desired.

As the active energy ray-reactive initiator (G) used in the present invention, for example, there can be mentioned: benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenones such as acetophenone, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinyl-propan-1-one; anthraquinones such as 2-ethylanthraquinone, 2-tributylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; thioxanthones such as 2, 4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4 '-methyldiphenylsulfide, 4' -bismethylaminobenzophenone and the like; conventional general radical type photoreaction initiators such as phosphine oxides including 2,4, 6-trimethylbenzoyl diphenylphosphine oxide and bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide.

Further, there may be mentioned: diazonium salts of lewis acids, iodonium salts of lewis acids, sulfonium salts of lewis acids, phosphonium salts of lewis acids, other acid halides, triazine-based initiators, borate-based initiators and other cationic initiators, photoacid generators, and the like.

As diazonium salts of Lewis acids, mention may be made of: p-methoxybenzyl diazoniafluorophosphonate, N-diethylamino diazoniahexafluorophosphonate (SUN-AID SI-60L/SI-80L/SI-100L manufactured by Sanxin chemical industries, Ltd.), etc.; examples of the iodonium salt of a lewis acid include: iodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and the like; as sulfonium salts of lewis acids, mention may be made of: triphenylsulfonium hexafluorophosphate (e.g., Cyracure UVI-6990 available from Union Carbide), triphenylsulfonium hexafluoroantimonate (e.g., Cyracure UVI-6974 available from Union Carbide), and the like; examples of lewis acid phosphonium salts include: triphenylphosphonium hexafluoroantimonates and the like.

Examples of the other acid halides include 2,2, 2-trichloro- [1-4 '- (dimethylethyl) phenyl ] ethanone (Trigonal PI manufactured by AKZO), 2, 2-dichloro-1-4- (phenoxyphenyl) ethanone (Sandray 1000 manufactured by Sandoz), α -tribromomethylphenylsulfone (BMPS manufactured by Ferro chemical Co., Ltd.) examples of the Triazine initiator include 2,4, 6-tris (trichloromethyl) -tris, 2, 4-trichloromethyl- (4' -methoxyphenyl) -6-tris (Triazone A manufactured by Panchim), 2, 4-trichloromethyl- (4 '-methoxystyryl-6-Triazine (Triazone PMS manufactured by Panchim), 2, 4-trichloromethyl- (piperonyl) -6-Triazine (Triazone PP manufactured by Panchim), 2, 4-trichloromethyl- (4' -methoxynaphthyl) -6-Triazine (Triazone B manufactured by Panchim), 2, 4-trichloromethyl- (4 '-trichloroethyl) -6-Triazine (Triazone PP manufactured by 2, 4' -trichloroethylene) -6-Triazine, 2,5 '-bis- (4' -methylethylidene) -furan manufactured by 2,4 '-bis (2' -ethyl) -6-Triazine manufactured by Panchium), and the like.

Examples of borate initiators include NK-3876 and NK-3881, manufactured by Nippon Photosensitve pigment, and other photoacid generators, including 9-phenylacridine, 2 ' -bis (o-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyl-1, 2-biimidazole (biimidazole, manufactured by Nippon Metal Co., Ltd.), 2-azobis (2-aminopropane) dihydrochloride (V50, manufactured by Wako pure chemical industries, Ltd.), 2-azobis [2- (imidazolin-2-yl) propane ] dihydrochloride (VA 044, manufactured by Wako pure chemical industries, Ltd.), and [ η -5-2-4- (cyclopentadecyl) (1,2,3,4,5,6, η) - (methylethyl) -benzene ] iron (II) hexafluorophosphate (Irgacure 261, manufactured by Ciba Geigy Co., Ltd.), bis (y 5-cyclopentadienyl) bis [2, 6-difluoro-3- (1H-pyridin-1-yl) phenyl ] hexafluorophosphate (manufactured by Ciba Geigy Co., Ltd.).

In addition, an azo initiator such as azobisisobutyronitrile, a thermally sensitive peroxide radical initiator such as benzoyl peroxide, and the like may be used in combination. Furthermore, both radical initiators and cationic initiators may be used in combination. The initiator may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The coloring pigment (H) used in the present invention is used for coloring the active energy ray resin composition of the present invention. The organic pigments and the inorganic pigments are classified according to the composition, and may be appropriately selected depending on the target color or the application.

Organic pigments are classified by their basic skeleton. Examples thereof include: isoindolinone-, methine-, anthraquinone-, anthrone-, xanthene-, diketopyrrolopyrrole-, perylene-, perinone-, quinacridone-, indigo-, dioxazine-, phthalocyanine-and other polycyclic pigments, monoazo pigments, disazo pigments, condensed disazo pigments, lake pigments, fluorescent pigments, etc.

Examples of the inorganic salt include: titanium dioxide, calcium carbonate, barium sulfate, zinc oxide, mica, carbon black, red lead, aluminum sheets and the like.

The extender pigment (I) of the present invention is a pigment not intended for coloring but intended for obtaining viscosity, fluidity and mechanical properties of a cured product of the composition.

Examples thereof include: barium sulfate, calcium carbonate, talc, clay, glass flake, glass bead, graphite, alumina, aluminum hydroxide, polystyrene bead, polyethylene bead, polypropylene bead, polytetrafluoroethylene bead, and the like.

The curing agent (J) of the present invention is used for the purpose of further increasing the crosslinking degree of the cured product. For example: when the composition of the present invention is used as a resist material, water resistance, heat resistance, and the like deteriorate if carboxyl groups remain after completion of development. Therefore, by preparing a compound having an epoxy group as a curing agent and performing a heating step after completion of development, the carboxyl group derived from the carboxyl group-containing reactive compound (C) or the polyfunctional reactive compound (E) is carboxylated as a compound having an epoxy group or the like of the curing agent (J), and the characteristics can be improved.

In addition, as another material, in order to adapt the active energy ray-curable resin composition of the present invention to various uses, another component may be added in an amount of 70 wt% as an upper limit. Other ingredients may be listed: resins which do not exhibit reactivity with active energy rays, various additives, and volatile solvents added for viscosity adjustment for the purpose of imparting suitability for coating. Other components that can be used are exemplified below.

Other resins (so-called inert polymers) that are not reactive to active energy rays include, for example: other epoxy resins, phenol resins, amine ester resins, polyester resins, ketone-formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, styrene resins, guanamine (guanamine) resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof. The content of these is preferably in a range up to 40% by weight.

Other additives may be used, for example: a thermosetting catalyst such as melamine, a thixotropic agent such as Aerosil, a silicone-based or fluorine-based leveling agent, an antifoaming agent, a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether, a stabilizer, an antioxidant, and the like.

In addition, the viscosity can be adjusted according to the purpose of use, but the addition of 50 mass% of the volatile solvent to 35 mass% of the resin composition of the present invention is more preferable.

The active energy ray-curable resin composition of the present invention can be easily cured by active energy rays, and specific examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible light rays, infrared rays, X-rays, gamma rays, and laser light rays, and particle rays such as α rays, β rays, and electron rays.

The coating film-forming material in the present invention means a material for coating the surface of a base material. Specific uses include: ink materials such as gravure ink, flexographic ink, screen ink, and overprint ink, coating materials such as hard coat, top coat, overprint, and clear coat (clearcoat), adhesive materials such as various adhesives and adhesives for lamination and optical disks, and resist materials such as solder resists, and resists for microcomputers. Further, a so-called dry film in which a coating film is formed by temporarily applying a coating film-forming material to a releasable substrate and then laminating the resultant film on the substrate as an original object is also included as a coating film-forming material.

The carboxyl group-containing reactive compound (C) and the carboxyl group-containing polyfunctional reactive compound (E) of the present invention are suitable for a material for forming a coating film on a plastic substrate or a metal substrate, because the adhesion to the substrate is improved by the carboxyl group. The polyfunctional reactive compound (E) having no carboxyl group is also excellent in hardness, adhesion and impact resistance to the cured product, and is therefore suitable as a material for forming a coating film.

Further, the carboxyl group-containing reactive compound (C) and the carboxyl group-containing polyfunctional reactive compound (E) are soluble in an aqueous alkali solution, and therefore can be used as a patterning material composition by an active energy ray.

The active energy ray-sensitive composition of the present invention is characterized in that the active energy ray-sensitive composition is prepared by forming a coating layer of the composition on a substrate, and then locally irradiating the coating layer with an active energy ray such as ultraviolet ray to thereby draw a figure by utilizing the difference in physical properties between the irradiated portion and the non-irradiated portion. Specifically, the composition is used for the purpose of drawing by dissolving or removing the irradiated portion or the non-irradiated portion by a certain method, for example, with a solvent or an alkaline solution.

These are applicable to various patternable materials such as solder resist materials, interlayer insulating materials for build-up processes, and electrical/electronic/optical substrates for optical waveguides such as printed circuit boards, optoelectronic substrates, and optical substrates.

Particularly suitable applications are color resists and circuit-forming materials for optical waveguides, which utilize the characteristics of high heat resistance and high transparency.

The method for forming the coating is not particularly limited, and the following methods can be used: gravure printing methods such as gravure printing, relief printing methods such as flexographic printing, stencil printing methods such as screen printing, offset printing methods such as sleeve printing, and various coating methods such as roll coating, knife coating, die coating, curtain coating, and spin coating.

The cured product of the active energy ray-curable resin composition of the present invention is a cured product obtained by irradiating the active energy ray-curable resin composition of the present invention with an active energy ray.

[ examples ]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Synthesis example: synthesis of polyfunctional acid anhydride (A) 1

In a flask equipped with a stirrer, a reflux condenser and a stirrer, 45g of THF was added to the acid halide shown in the table in the amount shown in the table (1.1 equivalent to the hydroxyl group of (a)) while purging with nitrogen gas to obtain a homogeneous solution. After cooling to 5 ℃ while stirring the solution, a homogeneous solution of pyridine (1.2 equivalents relative to the hydroxyl group of (a)) and 54g of THF was added to (a) shown in the tables indicating the amounts of the components shown in the tables, and the solution was slowly dropped while maintaining the temperature at 10 ℃ or lower. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour, then warmed to 50 ℃ and reacted for 8 hours. Subsequently, the reaction solution was cooled to 20 ℃, pyridine hydrochloride which was an insoluble component was removed by filtration, and the filtrate was concentrated. The concentrate was dissolved in 120ml of ethyl acetate, washed 3 times with 30ml of water, and dried over anhydrous magnesium sulfate. After anhydrous magnesium sulfate was removed by filtration, the filtrate was concentrated, and the obtained concentrate was dissolved in 15ml of ethyl acetate and recrystallized from toluene to obtain a product. In the synthesis of the compound, the time point at which the starting alcohol disappeared was confirmed by gel permeation chromatography (hereinafter referred to as "GPC"), and this time point was taken as the completion of the reaction.

Comparative synthesis example 1-1: synthesis of 2-functional anhydrides

A bifunctional acid anhydride was synthesized according to Synthesis example 1. The results are shown in the following table together with synthetic example 1.

[ Table 1]

Synthesis example	(a)	Number of functional groups	(b)	Yield of
					Synthesis example 1-1	TMP(13.4g)	n＝3	HTAC(59.4g)	75％
Synthesis examples 1 and 2	PE(13.6g)	n＝4	HTAC(79.3g)	80％
					Synthesis examples 1 to 3	DPE(25.4g)	n＝4	HTAC(118.9g)	75％
Synthesis examples 1 to 4	DPE6EO(25.9g)	n＝6	HTAC(59.4g)	70％
					Synthesis examples 1 to 5	DPE6CL(29.5g)	n＝6	HTAC(35.7g)	70％
Synthesis examples 1 to 6	PE4EO(31.2g)	n＝6	HTAC(79.3g)	65％
					Synthesis examples 1 to 7	PE(13.6g)	n＝4	HTAC/TMAC(77.9g)*	75％
Synthesis examples 1 to 8	PE(13.6g)	n＝4	TMAC(76.6g)	75％
					Synthesis example 1-9	THI(26.1g)	n＝3	HTAC(59.4g)	60％
Comparative Synthesis example 1-1	BPA2EO(31.6g)	n＝2	HTAC(39.6g)	70％

In the table, abbreviation

TMP: trimethylolpropane

PE: neopentyltetraol

DPE: dineopentanetetraol

DPE6 EO: 6 mol ethylene oxide adduct of dipentaerythritol

DPE6 CL: 6 mol caprolactone adduct of dipentaerythritol

PE4 EO: neopentyl glycol 4 mol ethylene oxide adduct

BPA2 EO: 2 mol ethylene oxide adduct of bisphenol A

THI: trihydroisomic acid tris-2-hydroxyethyl ester

HTAC: nuclear hydrogenated trimellitic anhydride acid chloride

TMAC: trimellitic anhydride acid chloride

＊ HTAC/TMAL (mol ratio) ═ 1/1

Example 1 preparation of carboxyl group-containing reactive Compound (C)

In a flask equipped with a stirrer, a reflux condenser and a stirrer, 20mmol (mass shown in the table) of the polyfunctional acid anhydride (a) prepared in synthesis example 1 was added, propylene glycol monomethyl ether acetate was added in an amount of 60 mass% of a solid content based on the total amount of (a) and (B), and pyridine as a catalyst was added in an amount of 0.3 mass% of the total amount including the solvent and dissolved by stirring.

Further, a compound described in the table as the compound (B) having 1 or more polymerizable ethylenically unsaturated groups and 1 or more hydroxyl groups in 1 molecule was added, and the reaction was carried out at 100 ℃ for 10 hours.

After completion of the reaction, the reaction mixture was cooled, and the acid value (AV, mgKOH/g) in the solution was measured, and the reaction end point was confirmed by converting the acid value into a solid acid value.

The acid value was measured in accordance with JIS K0070: 1992.

Comparative example 1 preparation of reactive Compound having 2-functional carboxyl group

The reaction was carried out in the same manner as in example 1 using 20mmol of the other 2-functional acid anhydride shown in the Table.

[ Table 2]

In the table, abbreviation

HEA: hydroxyethyl acrylate, OHV 116 g/Oreq

PE 3A: mixtures of neopentyltetraol triacrylate and neopentyltetraol tetraacrylate, the neopentyltetraol triacrylate/neopentyltetraol tetraacrylate ratio being about 50/50 (mol), OHV 650g/OHEq

GMA-AA: glycidyl ether-acrylic acid carboxylate compound (LIGHTESTER G-201P, OHV 214 g/Oreq, manufactured by Kyoeisha chemical Co., Ltd.)

PGE-AA: phenyl glycidyl ether-acrylic acid carboxylate compound, KAYARAD R-128H, KAYARAD, OHV 222g/OHEq

TMEG-100: ethylene glycol bis (trimellitic anhydride), new date chemical RIKACID TMEG-100

Example 2: preparation of reactive Compound (E)

In a flask equipped with a stirrer, a reflux condenser and a stirrer, 0.01mol (mass is shown in table in solid content) of the reaction solution to which the reactive compound (C) prepared in example 1 was added, the compound shown in table as the compound (D) having 1 or more polymerizable ethylenically unsaturated groups and 1 or more epoxy groups in 1 molecule was added in the amount shown in table, propylene glycol monomethyl ether acetate was added so that the final solid content became 60 mass%, and then the mixture was reacted at 100 ℃ for 24 hours to obtain the reactive compound (E).

[ Table 3]

Examples	Compound (C)	Compound (D)	Actual measurement AV	Theoretical AV
					Example 2-1	Examples 1-2(13.2g)	GMA 2.8g(0.005mmol)	66	60
Examples 2 to 2	Examples 1-2(13.2g)	GMA 1.14g(0.002mmol)	100	95
					Examples 2 to 3	Examples 1-2(13.2g)	GMA 5.6g(0.0098mmol)	4.4	2.4
Examples 2 to 4	Examples 1 to 6(15.0g)	GMA 1.42g(0.0025mmol)	87	82
					Examples 2 to 5	Examples 1-2(13.2g)	4HBGE 2.0g(0.0025mmol)	85	79

In the table, abbreviation

GMA: glycidyl methacrylate

4 HBAGE: 4-hydroxybutyl acrylate glycidyl ether

Example 3: preparation of composition for white negative resist

The carboxyl group-containing reactive compound (C) solution synthesized in example 1 and comparative example 1 in terms of solid content (the actual loading was 60 mass% of solid content) or the reactive compound (E) solution prepared in example 2, 4G of a radical-hardening monomer DPHA (di-neopentylglycol hexaacrylate) as another reactive compound (F) (manufactured by Nippon chemical Co., Ltd.), 5G of barium sulfate B-30 (manufactured by Nippon chemical industries Co., Ltd.) as an extender pigment (I), 3G of a titanium oxide pigment TIPAQUE CR-90 (manufactured by Shikuyao chemical Co., Ltd.) as a coloring pigment (H), 4G of a TESP-PIC (tri-isopropyl isocyanate epoxide (manufactured by Nippon chemical industries Co., Ltd.) as a hardener (J)), 0.5G of an IRGAPAN (manufactured by JAF Co., Ltd.) as an active energy ray-reactive initiator (G) (manufactured by JAF Co., Ltd.), and 0.5G of a JAPAN (JAPAN) as an active energy-ray-reactive initiator (G) (manufactured by JAF), 4g of propylene glycol monomethyl ether acetate as a solvent was kneaded by a three-roll mill to obtain a white negative resist composition.

The obtained resist composition was coated on the copper clad laminate by screen printing, and the solvent was evaporated in an oven at 80 ℃ for 15 minutes. Next, 500mJ/cm was irradiated with ultraviolet light through a mask on which a circuit pattern was drawn and a kodak step plate (step table) No.2 for sensitivity evaluation using an ultraviolet exposure apparatus (HMW-680 GW, manufactured by ORC Ltd.)²Ultraviolet rays of (1). After that, the film on the dry film was peeled off and the peeled state was confirmed. Then, the resin was spray-developed with a 1% aqueous solution of sodium carbonate to remove the resin not irradiated with ultraviolet rays. After washing and drying, the printed wiring board was heated and cured for 60 minutes in a hot air dryer at 150 ℃ to obtain a cured film.

Evaluation items of white resist composition

< sensitivity evaluation >

Sensitivity is determined as the concentration of the exposed portion that penetrates the gradation plate during development until the stage ii. The one with a large number of stages (value) is judged as high sensitivity (unit: stage) in the thick portion of the plate.

< evaluation of developability >

The developability is a time from the time when the developer is ejected to the time when the pattern shape portion is completely developed when the exposed portion penetrating the pattern mask is developed, that is, the developability (unit: seconds) is evaluated as a so-called development time (break time). More preferably about 20 seconds to 40 seconds.

< evaluation of analytical Property >

The resolution is to determine whether or not a Line space pattern (Line and space) included in the pattern mask is finely patterned (unit: μm) using an optical microscope. The smaller value can be determined as a fine pattern.

< evaluation of yellowing >

Yellowing is obtained by further placing the resist after curing reaction at 150 ℃ in a hot air oven at 180 ℃ for 72 hours and observing the resistance to thermal coloration. Yellowing was assessed visually. The evaluation criteria are as follows:

◎ no color change

○ slight yellowing

△ confirmation of yellow color

X: turning brown

< evaluation of light resistance >

The light resistance was evaluated by irradiating the resist after the curing reaction at 150 ℃ with ultraviolet light for 20 hours using a SUPER UV tester (manufactured by Kawasaki electric Co., Ltd.) to visually evaluate the coloring property of the white resist after completion of the irradiation. The evaluation criteria are as follows:

◎ no color change

○ slight yellowing

△ confirmation of yellow color

X: turning brown

< evaluation of Heat resistance >

The heat resistance was obtained by floating a substrate made of a resist film after curing reaction at 150 ℃ in a solder bath at 260 ℃ for 1 minute, and then rapidly cooling the substrate in water. After repeating this operation 3 times, an X-shaped flaw was cut with a cutter knife, and adhesion evaluation was performed with a transparent adhesive tape.

○ No peeling

△ trace of slight peeling only at the X-shaped part

X: with peeling-off

[ Table 4]

In the table, abbreviation

CCR-1218H: cresol novolak type acid-modified epoxy acrylate (manufactured by Nippon Kagaku)

ZCR-1569H: biphenyl type acid modified epoxy acrylate (manufactured by Nippon chemical)

ASP-010: methyl methacrylate, butyl methacrylate, methacrylic acid copolymer (manufactured by Nippon Kagaku Co., Ltd.)

From the above results, it is understood that 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, a cured product having an excellent balance among yellowing, light resistance and heat resistance can be obtained.

Example 4: coating material composition for metal

A carboxyl group-containing reactive compound (C) prepared in example 1 or the reactive compound (E) prepared in example 2 was charged in an amount of 10G in terms of solid content (the actual loading amount was 60 mass% divided by solid content), bisphenol ethylene oxide diacrylate as another reactive compound (F), 15G of tri (propylene glycol) diacrylate, 10G of amine ester acrylate (UX-5000, manufactured by Kakkiso Co., Ltd.), and 1.5G of IRGACURE 184 (manufactured by BASFJAPAN) as an active energy ray-reactive initiator (G) were charged and kneaded thoroughly until they became homogeneous, thereby preparing a curable composition.

The resulting composition was coated on a TFS substrate (tin-plated steel plate) with a wire bar coater #8, and the solvent was evaporated in an oven at 100 ℃ for 10 minutes. Thereafter, 500mJ/cm of irradiation was carried out²The ultraviolet ray of (2) is subjected to a curing reaction to obtain a cured film.

Evaluation of coating Material for Metal

< evaluation of curing Property >

The hardness of the coating film after hardening was evaluated in accordance with the pencil hardness test (JIS-K5600-5-4: 1999).

< evaluation of adhesion >

The adhesion to the metal substrate was evaluated according to the hundred-grid knife (cross-cut) peel test (JIS-K5600-5-6: 1999).

The evaluation criteria were also evaluated by the following classification in accordance with JIS-5600:

classification 0: no peeling off and good

Classification 1: slight peeling of the corner part only

And (4) classification 2: corner peeling

And (3) classification: less than half of the grid stripped

And 4, classification: more than half of the stripped grids

And (5) classification: almost all peeling was not preferred

< evaluation of impact resistance >

The impact resistance of the coating film was evaluated in accordance with the DuPont impact test (JIS-K5600-5-6: 1999). The weight was 500g, the impact die was 6.35mm, and the drop height was 250 mm.

○ no cracking

△ slight crack but no peeling

X: with peeling-off

[ Table 5]

In the table, abbreviation

HOA-HH: hydroxyethyl acrylate hexahydrophthalic acid monoester

TPGDA: tri (propylene glycol) diacrylate

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

[ industrial applicability ]

The carboxyl group-containing reactive compound (C) and the polyfunctional reactive compound (E) of the present invention are less discolored, have high resolution and high heat resistance. Therefore, the curable composition is particularly suitable for use as a coating film-forming material other than a solder resist material, and a curable material which is required to be colorless and transparent or colored, and is suitable for use in, for example: an active energy ray-curable coating material and a printing ink.

Further, since the carboxyl group-containing reactive compound (C) and the carboxyl group-containing polyfunctional reactive compound (E) of the present invention contain a carboxyl group in the molecule, they are also suitable for negative tone photopatterning by alkali development. Therefore, the present invention is suitable for use in resist materials and color resists requiring less coloring, particularly color resists for LCDs, black matrices, spacer resists, optical waveguide materials, and the like.

Claims

1. A carboxyl group-containing reactive compound is obtained by reacting a polyfunctional acid anhydride A obtained by reacting a polyhydric alcohol a having at least 3 or more hydroxyl groups in 1 molecule with a nuclear hydrogenated trimellitic anhydride acid halide B-1 or trimellitic anhydride acid halide B-2 with a compound B having 1 or more polymerizable ethylenically unsaturated groups and 1 or more hydroxyl groups in 1 molecule.

2. A carboxyl group-containing reactive compound obtained by reacting a polyfunctional acid anhydride A obtained by reacting a polyhydric alcohol a having at least 3 hydroxyl groups in 1 molecule with a nuclear hydrogenated trimellitic anhydride acid halide B-1 or trimellitic anhydride acid halide B-2 with a compound B having at least 1 polymerizable ethylenically unsaturated group and at least 1 hydroxyl group in 1 molecule, wherein the polyhydric alcohol a is a polyhydric alcohol a-1 having at least 3 hydroxyl groups in 1 molecule represented by the following general formula (1):

in the formula, R¹、R²、R³、R⁴、R⁵、R⁶Each independently of the other, R¹、R³、R⁴、R⁵、R⁶Represents a hydrogen atom, a hydroxyl group, a hydrocarbon group having 1 to 11 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms, R²Represents a hydroxyl group or a hydroxyalkyl group having 1 to 4 carbon atoms; l represents an integer of 0 to 11, and m and n each represent an integer of 1 to 11.

3. A carboxyl group-containing reactive compound obtained by reacting a polyfunctional acid anhydride A obtained by reacting a polyhydric alcohol a-2 having at least 3 or more hydroxyl groups in 1 molecule with a nuclear hydrogenated trimellitic anhydride acid halide B-1 or trimellitic anhydride acid halide B-2 with a compound B having 1 or more polymerizable ethylenically unsaturated groups and 1 or more hydroxyl groups in 1 molecule,

the polyol a-2 is obtained by reacting the polyol a described in claim 1 or 2 with 1 or more selected from the group consisting of alkylene oxides, cyclic ethers having 4 or more membered rings, and cyclic esters,

the alkylene oxide is a compound of a cyclic ether having a 3-membered ring.

4. A polyfunctional reactive compound obtained by reacting the reactive compound having a carboxyl group according to claim 1 or 2 with a compound D having 1 or more polymerizable ethylenically unsaturated groups and 1 or more epoxy groups in 1 molecule.

5. A polyfunctional reactive compound obtained by reacting the reactive compound having a carboxyl group according to claim 3 with a compound D having 1 or more polymerizable ethylenically unsaturated groups and 1 or more epoxy groups in 1 molecule.

6. An active energy ray-curable resin composition comprising the reactive compound of claim 1 or 2.

7. The active energy ray-curable resin composition according to claim 6, which is a coating film-forming material.

8. The active energy ray-curable resin composition according to claim 6, which is a drawing material by active energy rays.

9. An active energy ray-curable resin composition comprising the reactive compound of claim 3.

10. The active energy ray-curable resin composition according to claim 9, which is a coating film-forming material.

11. The active energy ray-curable resin composition according to claim 9, which is a drawing material by active energy rays.

12. An active energy ray-curable resin composition comprising the polyfunctional reactive compound of claim 4.

13. The active energy ray-curable resin composition according to claim 12, which is a coating film-forming material.

14. The active energy ray-curable resin composition according to claim 12, which is a drawing material by active energy rays.

15. An active energy ray-curable resin composition comprising the polyfunctional reactive compound of claim 5.

16. The active energy ray-curable resin composition according to claim 15, which is a drawing material by active energy rays.

17. The active energy ray-curable resin composition according to claim 15, which is a coating film-forming material.

18. A cured product of the active energy ray-curable resin composition according to claim 6.

19. A cured product of the active energy ray-curable resin composition according to claim 9.

20. A cured product of the active energy ray-curable resin composition according to claim 12.

21. A cured product of the active energy ray-curable resin composition according to claim 15.