TW201827477A - Polyurethane compound, active energy ray curable resin composition containing the same and use thereof - Google Patents

Abstract

An objective of the present invention is to provide a material capable of optical patterning and, at the same time, having the flexibility and toughness of a flexible substrate at a high level but without compromising the heat resistance that can withstand the manufacturing of a substrate such as wielding and heat generation of an element, maintains high insulation for a long period of time, resistance to chemical treatment such as plating treatment, etc. The present invention provides a polyurethane compound (A) obtained by reacting an unsaturated epoxy carboxylate compound (c), a compound (d) having two hydroxyl groups and one or more carboxyl groups in one molecule, a polyester diol compound (e) having a dicarboxylic acid having 10 or more carbon atoms and a compound (f) having two isocyanate groups in one molecule, wherein the unsaturated epoxy carboxylate compound (c) is obtained by reacting a compound (b) having at least one ethylenically unsaturated group and one or more carboxyl groups in one molecule with an epoxy compound (a) having two epoxy groups in one molecule.

Description

   Polyurethane compound, active energy ray-curable resin composition containing the same, and use of the composition   

The present invention relates to an active energy ray-curable resin composition containing a polyurethane compound (A) and / or an acid-modified polyurethane compound (B), and a cured product thereof. In particular, the present invention relates to a polyurethane-containing compound (A) and / or an acid-modified polyurethane compound (B) suitable for use as a resist material such as a flexible substrate resist material, a color resist material for a flexible display, and a spacer resist. ) Of an active energy ray-curable resin composition, and a cured product thereof.

In recent years, with the miniaturization of electronic information equipment, the use of so-called flexible printed circuit boards has increased due to the characteristics of light, thin, and flexible circuit boards.

Flexible printed substrates are literally flexible, so the materials they use have the characteristics of photo-patterning by alkaline development, and also have high sensitivity, adhesion, scratch resistance, and high mechanical / thermal / It has the necessary characteristics such as electrical strength, and it is required to be capable of forming a tough film having high flexibility and following flexible substrates.

In general, excellent sensitivity, hardenability, chemical resistance, heat resistance and other characteristics are achieved by introducing more reactive groups into a main chain having a rigid skeleton and providing a high crosslinking density. This resin is suitably used in applications such as a general solder resist. However, this makes it impossible to impart the required flexibility to the flexible substrate.

On the other hand, in order to impart flexibility, it is achieved by introducing a small amount of a reactive group into the flexible main chain, that is, by appropriately reducing the crosslinking density.

As described above, these characteristics are opposite to each other. For solder resist materials such as flexible substrates, it is required to blend these characteristics at a high level. Conventionally, epoxy-based acrylate materials have been mainly used. However, although such materials are excellent in properties such as chemical resistance and heat resistance, they have insufficient flexibility. Therefore, it is difficult to obtain a tough film having both flexibility applicable to a flexible substrate, and a further film-forming material is desired.

In an attempt to solve these problems, Patent Document 1 describes that a difunctional unsaturated epoxy carboxylic acid ester compound, a compound having two hydroxyl groups and one or more carboxyl groups, and a diisocyanate compound are reacted in one molecule. The obtained reactive amine ester compound.

This reactive amine ester compound has better flexibility and heat resistance than conventional epoxy acrylate-based materials, but cannot exhibit the higher flexibility required to appear.

Furthermore, the simple method of improving the flexibility of amine ester compounds by simply using other diol compounds to constitute the reactive amine ester compound is a significant decrease in heat resistance, and the heat resistance required for applications such as solder resist cannot be obtained. Sclerosis.

In addition, an attempt has been made to add a rubber compound having two hydroxyl groups in a molecule for the purpose of imparting flexibility (Patent Document 2).

Thereby, although good flexibility can be exhibited, the rubber compound has poor compatibility with the reactive amine ester compound, and if a rubber compound is used in an amount to exhibit sufficient flexibility, it will be in a phase separation state. Even when an active energy ray-curable resin composition prepared with other compounds is prepared, compatibility problems still occur.

When the problem of compatibility is caused, it adversely affects the developability. Specifically, it is difficult to develop, and it is difficult to form a fine pattern. In addition, it is difficult to exhibit satisfactory characteristics in terms of heat resistance.

In addition, there are used non-reactive amine esters obtained by reacting a compound having two hydroxyl groups and one or more carboxyl groups in one molecule, a polyester-based or polycarbonate-based diol, and a diisocyanate compound. Attempts at compounds (Patent Document 3). However, the amine ester compound does not have reactivity to active energy rays. Therefore, in order to obtain reactivity to active energy rays, that is, to obtain a resin composition that can be finely patterned by light drawing, it is necessary to use other reactive compounds in combination, but it is not possible to exhibit high levels of activity with active energy rays. Reactivity, flexibility, heat resistance, etc.

Furthermore, Patent Document 4 discloses that a reactive polyurethane compound has been given reactivity to active energy rays, but the performance is not sufficient in terms of flexibility for bending printed boards at 180 ° C., which is actually used for flexible printed boards.

    [Prior technical literature]         [Patent Literature]    

[Patent Document 1] Japanese Patent Laid-Open No. 9-52925

[Patent Document 2] Japanese Patent Laid-Open No. 2003-147043

[Patent Document 3] Japanese Patent Laid-Open No. 2006-124681

[Patent Document 4] Japanese Patent Laid-Open No. 2011-140624

An object of the present invention is to provide a material capable of photo-patterning without damaging the heat resistance of the substrate used for the heat of soldering and the like and the heat generated by the elements used in the substrate, and maintaining high insulation for a long time. It has the basic characteristics required for solder resist, such as reliability, chemical resistance to plating and other chemical treatment, and has the flexibility and toughness required for flexible substrates.

As a result of intensive review in order to solve the aforementioned problems, the present inventors have found that a polyurethane compound obtained using an ester diol compound of a dicarboxylic acid having a specific structure, an acid-modified compound thereof, and a resin composition system containing the same The foregoing problem was solved, and the present invention was completed. That is, the present invention relates to the following: [1] A polyurethane compound (A), which is an unsaturated epoxy carboxylic acid ester compound (c), which has two hydroxyl groups and one or more carboxyl groups in one molecule. Compound (d), a polyester diol compound (e) of a dicarboxylic acid having 10 or more carbon atoms, and a compound (f) having two isocyanate groups in one molecule, which are obtained by reacting, The ester compound (c) is obtained by reacting a compound (b) having more than one ethylenically unsaturated group and one carboxyl group in one molecule with an epoxy compound (a) having two epoxy groups in one molecule; [ 2] The polyurethane compound (A) according to the above item [1], which contains sebacic acid polyester diol or dimer acid polyester diol as the polyester diol compound (e) [3] An acid-modified polyurethane compound (B), which is obtained by reacting a polybasic acid anhydride (g) with the aforementioned polyurethane compound (A); [4] an active energy ray-curable resin composition containing [5] The polyurethane compound (A) according to the above item [1] or [2], and / or the acid-modified polyurethane compound (B) according to the above item [3]; The active energy ray-curable resin composition according to item [4], which contains a reactive compound (C) other than the polyurethane compound (A) and the acid-modified polyurethane compound (B); [6] 4] or the active energy ray-curable resin composition described in [5], which is a material for forming; [7] the active energy ray-curable resin composition described in [6] above, which is a material for forming a film; [ 8] The active energy ray-curable resin composition according to any one of the foregoing items [4] to [7], which is a resist material; [9] A hardened material, which is any of the foregoing items [4] to [8] A hardened product of the active energy ray-curable resin composition according to one item; [10] An article which is protected and covered with the hardened product according to the above item [9].

The polyurethane compound (A) of the present invention is a polyester diol compound using a dicarboxylic acid having a carbon number of 10 or more. By inserting a long-chain alkyl group, flexibility can be improved. Therefore, the acid-modified polyurethane compound (B), The active energy ray-curable resin composition containing the above and its hardened material can provide a material that can be patterned by light without damaging the heat of soldering and other components used on the substrate when the substrate is manufactured. Basic properties required for solder resist and color resist such as heat resistance for heat generation, long-term reliability with high insulation, chemical resistance to chemical treatment such as plating, and flexible substrates It has the required flexibility and toughness, and is particularly suitable for use in materials for film formation that require flexibility, such as solder resist for flexible substrates.

Hereinafter, the present invention will be described in detail.

The polyurethane compound (A) of the present invention is an unsaturated epoxy carboxylic acid ester compound (c), a compound (d) having two hydroxyl groups and one or more carboxyl groups in one molecule, and a dicarboxylic acid having 10 or more carbon atoms. An acidic polyester diol compound (e) and a compound (f) having two isocyanate groups in one molecule are obtained by reacting the unsaturated epoxy carboxylic acid ester compound (c) in one molecule. The compound (b) having one or more ethylenically unsaturated groups and one carboxyl group is obtained by reacting an epoxy compound (a) having two epoxy groups in one molecule.

That is, the polyurethane compound (A) of the present invention is produced in two reaction steps. First, an epoxy compound (a) having two epoxy groups in one molecule is reacted with a compound (b) having one or more ethylenically unsaturated groups and one carboxyl group in one molecule to obtain an unsaturated epoxy group. Step of carboxylic acid ester compound (c). In the present invention, this step is referred to as a carboxylic acid esterification step.

Next, the unsaturated epoxy carboxylic acid ester compound (c) thus obtained, a compound (d) having two hydroxyl groups and one or more carboxyl groups in one molecule, and a polyester of dicarboxylic acid having 10 or more carbon atoms A step of reacting a diol compound (e) and a compound (f) having two isocyanate groups in one molecule. In the present invention, this step is referred to as an amine esterification step.

The unsaturated epoxy carboxylic acid ester compound (c) obtained in the carboxylic acid esterification step has two or more ethylenically unsaturated groups and two hydroxyl groups derived from the epoxy group of the epoxy compound (a) in one molecule. Carboxylic acid ester compounds.

In the subsequent amine esterification step, two hydroxyl groups of the unsaturated epoxy carboxylic acid ester compound (c), two hydroxyl groups of the compound (d) having two hydroxyl groups and one or more carboxyl groups in one molecule, The two hydroxy groups of the polyester diol compound (e) of a dicarboxylic acid having 10 or more carbon atoms react with a compound (f) having two isocyanate groups in one molecule to obtain a polyurethane compound (A).

First, the carboxylic acid esterification step will be described in detail.

As far as the epoxy compound (a) having two epoxy groups in one molecule (hereinafter, also simply referred to as "epoxy compound (a)") is used in the production of the polyurethane compound (A) of the present invention, There are no particular restrictions on having two epoxy groups in one molecule. The monofunctional epoxy compound cannot adjust the molecular weight of the polyurethane compound (A) obtained in the amine esterification step, and since the trifunctional or more epoxy compound has a multi-branched structure, it is difficult to obtain suitable physical properties of the cured product.

Examples of the epoxy compound (a) include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and bisphenol fluorene bicyclo Bisphenol diglycidyl ethers such as oxypropyl ether, biphenyl diglycidyl ethers such as biphenol diglycidyl ether, tetramethyl diphenol glycidyl ether and other aromatic diphenylglycidyl ethers Glycidyl ether compounds; alkyl glycol diglycidyl ethers such as hexanediol diglycidyl ether, alkanediol diglycidyl ethers such as polyethylene glycol diglycidyl ether Type, saturated hydrocarbon-based diglycidyl ether compounds such as cycloalkyl glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and the like; 3 4,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate (CELLOXIDE 2021 manufactured by Daicel Chemical Co., Ltd.), 1, 2, 8, 9-diepoxy So-called bifunctional alicyclic epoxy compounds, such as methyl limonene (CELLOXIDE 3000 manufactured by Daicel Chemical Co., Ltd.).

Among these, an aromatic diglycidyl ether compound is suitable because it has good heat resistance.

The epoxy compound (a) is preferably one which does not have a hydroxyl group. This is because the unsaturated epoxy carboxylic acid ester compound (c) obtained in the esterification step of the epoxy carboxylic acid becomes a trifunctional or more functional polyol compound, and the control of the molecular weight of the polyurethane compound (A) becomes difficult. The reason.

A compound (b) (hereinafter, also simply referred to as "compound (b)") having one or more ethylenically unsaturated groups and one carboxyl group in one molecule used in the production of the polyurethane compound (A) of the present invention has The purpose of introducing an ethylenically unsaturated group into the reactive polyurethane compound (A), and simultaneously converting the epoxy compound (a) into a diol compound that can react with an isocyanate group. The number of ethylenically unsaturated groups in the compound (b) is preferably from 1 to 4.

Examples of the compound (b) include (meth) acrylic acid and crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a saturated or unsaturated dibasic acid and a monocyclic ring other than (meth) acrylic acid Reactants of unsaturated monoglycidyl compounds other than oxypropyl ester derivatives.

Examples of the (meth) acrylics include (meth) acrylic acid, β-styryl (meth) acrylic acid, β-furanmethyl (meth) acrylic acid, (meth) acrylic acid, and ε -Reaction product of caprolactone, (meth) acrylic acid dimer, equivalent of a mole reactant which is a saturated or unsaturated dibasic acid anhydride and a (meth) acrylic acid ester derivative having 1 hydroxyl group in one molecule Half-esters, half-esters that are equivalent Mohr reactants of saturated or unsaturated dibasic acids and (meth) acrylic acid monopropylene oxide derivatives.

Among these, in terms of sensitivity when an active energy ray-curable resin composition is produced, it is preferably a reaction product of (meth) acrylic acid, (meth) acrylic acid and ε-caprolactone, or cinnamic acid. .

The compound (b) is preferably one which does not have a hydroxyl group.

In the carboxylic acid esterification step, the compound (b) is preferably 90 to 120 equivalent% relative to 1 equivalent of the aforementioned epoxy compound (a). If it is in this range, it can be manufactured under relatively stable conditions. When the feed amount of the compound (b) is more than this range, the compound (b) having a carboxyl group remains, which is not preferable. When the amount of the compound (b) to be fed is too small, the unreacted epoxy compound (a) may remain, which may cause problems with the stability of the resin.

The carboxylic acid esterification step may be solvent-free or diluted and reacted with a solvent. When a solvent is used, it is not particularly limited as long as it is a solvent that is inert to the carboxylic acid esterification reaction. In addition, it is preferable to use an inert solvent in the acid addition step described later, if necessary, in the amine esterification step in the next step, if necessary.

When using a solvent, the amount of the solvent used should be appropriately adjusted according to the viscosity and use of the obtained resin, and it is preferably used so that the solid content content becomes 99 to 30% by weight, and more preferably 99. To 45% by weight. When the compound used in the reaction has a high viscosity, the viscosity is suppressed and the reaction proceeds appropriately.

Examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene; and aliphatic hydrocarbon solvents such as hexane, octane, and decane, and mixtures of these solvents. Petroleum ether, white gasoline, solvent oil, etc. In addition, an ester-based solvent, an ether-based solvent, and a ketone-based solvent may be used.

Examples of the ester-based solvent include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate; cyclic esters such as γ-butyrolactone; and ethylene glycol monomethyl ether monoacetic acid. Ester, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether mono Mono- or polyalkylene glycol monoalkyl ether monoacetates such as acetate, propylene glycol monomethyl ether monoacetate, butanediol monomethyl ether monoacetate, glutaric acid such as dimethyl glutarate, etc. Dialkyl succinates such as dialkyl succinates and dimethyl succinate; dialkyl dicarboxylic acids such as dialkyl adipates such as dimethyl adipate; and the like.

Examples of the ether-based solvent include alkyl ethers such as diethyl ether and ethyl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dipropylene glycol dimethyl ether. , Glycol ethers such as dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether; and cyclic ethers such as tetrahydrofuran.

Examples of the ketone-based solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

In addition, as long as it is inert to the reaction, the later-mentioned reactive compound (C) and the like may be used alone or in combination as a solvent. In this case, it can also be used as it is as a curable resin composition.

In the carboxylic acid esterification step, a catalyst is preferably used in order to promote the reaction. When the catalyst is used, the amount of the catalyst used is 0.1 to the reactant, that is, the total amount of the added solvent when the aforementioned epoxy compound (a), compound (b), and solvent are used. About 10% by weight. The reaction temperature at this time is 60 to 150 ° C, and the reaction time is preferably 5 to 60 hours.

Examples of the catalyst include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethylammonium iodide. , Triphenylphosphine, triphenylantimony, chromium octoate, zirconium octoate and other general alkaline catalysts.

In addition, a thermal polymerization inhibitor can be used. For the thermal polymerization inhibitor, for example, hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, and diphenyl are preferably used. Methylamine, 3,5-di-third-butyl-4-hydroxytoluene, and the like.

The carboxylic acid esterification step is based on the time point when the acid value of the sample becomes 5 mg ‧ KOH / g or less, and the end point is preferably the time point when the acid value of the sample becomes 5 mg ‧ KOH / g or less.

Next, the amine esterification step will be described in detail.

A compound (d) having two hydroxyl groups and one or more carboxyl groups in one molecule used in the production of the polyurethane compound (A) of the present invention (hereinafter, also simply referred to as "compound (d)") is a carboxyl group introduced into the polyurethane The compound (A) is soluble in an alkaline aqueous solution necessary for photo-patterning. The number of carboxyl groups in the compound (d) is preferably from 1 to 4.

The compound (d) is preferably dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolvaleric acid, etc. Among them, dimethylol is particularly preferred in consideration of obtaining raw materials. Propionic acid, dimethylol butyric acid.

By using a polyester diol compound (e) (hereinafter, also simply referred to as "polyester diol compound (e)") using a dicarboxylic acid having a carbon number of 10 or more in the production of the polyurethane compound (A) of the present invention, Can blend sensitivity, heat resistance, chemical resistance, and softness with a high level. The upper limit of the carbon number is preferably 100 or less.

This polyester diol compound (e) is characterized by having two hydroxyl groups in one molecule and having an ester bond in the main skeleton.

Examples of the polyester diol compound (e) include diol dicarboxylate diols in which a diol compound and a dicarboxylic acid are linked by an ester bond. The diol compound is not particularly limited as long as it is a compound having two hydroxyl groups other than the unsaturated epoxy carboxylic acid ester compound (c) and the compound (d).

Examples of diol dicarboxylic acid ester diols in which a diol compound and a dicarboxylic acid compound are connected by an ester bond include, for example, ethylene glycol sebacate polyester diol and propylene glycol sebacate polyester Glycol, butanediol sebacate polyester diol, neopentyl glycol sebacate polyester diol, methylpentanediol sebacate polyester diol, hexanediol sebacate polyester di Alcohol, ethylene glycol dimer acid polyester diol, propylene glycol dimer acid polyester diol, hexanediol dodecanedioate diol, ethylene glycol dodecanedioate diol, ethylene glycol Glycol dodecanoate glycol, etc.

Among these, the polyester diol compound (e) is particularly preferred because it exhibits suitable softness because it has suitable sebacic acid polyester diols and dimer acid polyester diols.

The aforementioned sebacic acid polyester diol is a reaction product obtained by reacting sebacic acid with a diol, and the dimer acid polyester diol is a reaction product obtained by reacting a dimer acid with a diol.

The above-mentioned dimer acid refers to a dibasic acid, and two monobasic fatty chains (usually 18 carbons) are dibasic acids having a molecular weight of two times obtained through a carbon-carbon covalent bond and two-molecule bonding. The representative compound is a dimer obtained by polymerizing unsaturated fatty acids such as linoleic acid, oleic acid, oleic acid, and pine oil fatty acid. In general, since the aforementioned unsaturated fatty acid having 18 carbon atoms is used as a raw material, the main component is a dicarboxylic acid having 36 carbon atoms.

Examples of the diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, and 1,2-butanediol , 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol , Neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,5-pentanediol, 2-ethyl-2-butylpropanediol, 1,9- Nonanediol, 2-methyloctanediol, 1,10-decanediol and the like.

A suitable molecular weight of the polyester diol compound (e) is preferably in the range of 250 to 5000, and more preferably 650 to 3000. When the molecular weight is smaller than this range, the effect of imparting flexibility is low, and when the molecular weight is larger than this range, the decrease in heat resistance becomes large.

The compound (f) having two isocyanate groups in one molecule (hereinafter, also simply referred to as "isocyanate compound (f)") used in the production of the polyurethane compound (A) of the present invention is used in combination with unsaturated epoxy carboxylic acid The amine esterification step of the hydroxyl group of the acid ester compound (c), the compound (d), and the polyester diol compound (e) imparts appropriate flexibility to the polyurethane compound (A).

Examples of the compound (f) include aliphatic linear diisocyanates, alicyclic diisocyanates, and aromatic isocyanates.

Examples of the aliphatic linear diisocyanates include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and the like.

Examples of the alicyclic diisocyanates include isophorone diisocyanate, norbornene diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated methylene bisphenylene diisocyanate.

Examples of the aromatic diisocyanates include toluene diisocyanate, xylylene diisocyanate, methylene bisphenylene diisocyanate, and the like.

Among these, in order to improve the flexibility, an aliphatic or alicyclic diisocyanate is preferred, and an aliphatic linear diisocyanate is particularly preferred.

The amine esterification step is a process of converting an unsaturated epoxy carboxylic acid ester compound (c), a compound (d) having two hydroxyl groups and one or more carboxyl groups in one molecule, and a dicarboxylic acid having 10 or more and 100 or less carbons. The mixture of the polyester diol compound (e) and the compound (f) having an isocyanate group is mixed.

In the production of the polyurethane compound (A), (the molar number of the unsaturated epoxy carboxylic acid ester compound (c) + the molar number of the compound (d) + the molar number of the polyester diol compound (e)) ÷ (mole number of isocyanate compound (f)), that is, the ratio of the hydroxyl group and the isocyanate group in the reaction system is preferably in the range of 1.05 to 2, and particularly preferably in the range of 1.15 to 1.6. That is, from the viewpoint of storage stability of the polyurethane compound (A), in the amine esterification step, it is fed with at least more hydroxyl groups than isocyanate groups so that isocyanate groups do not remain in the end.

Moreover, when it is larger than this range, the molecular weight of the obtained polyurethane compound (A) becomes too small, and it becomes difficult to obtain a tough hardened material. When the molecular weight is too small, the molecular weight of the obtained polyurethane compound (A) becomes too large. There may be adverse effects such as developability.

In the production of the polyurethane compound (A) of the present invention, the weight of the unsaturated epoxy carboxylic acid ester compound (c), the weight of the compound (d), the weight of the polyester diol compound (e), and the isocyanate compound (f) When the total weight of the resin composition is 100 parts, the unsaturated epoxy carboxylic acid ester compound (c) is 5 to 65 parts by weight, and the compound (d) is 5 to 25 parts by weight. The polyester diol compound (e) is 0.5 to 60 parts by weight, and the isocyanate compound (f) is 20 to 40 parts by weight. Within this range, a polyurethane compound (A) having developability by photo-patterning, an alkaline aqueous solution, and having properties suitable as a resist material can be obtained, and a particularly high level and high balance can be obtained. Heat-resistant, chemical-resistant, and excellent softened hardened material.

The amine esterification step may be solvent-free or diluted and reacted with a solvent. When a solvent is used, it is not particularly limited as long as it is a solvent that is inert to the amine esterification reaction.

When using a solvent, the amount used should be appropriately adjusted depending on the viscosity and application of the obtained resin, but it is preferably used so that the solid content content is 99 to 30% by weight, and more preferably, the solid content is used. It is used so that a content rate may become 90 to 45 weight%. Under the condition that the two steps are inert, the solvent used in the aforementioned carboxylic acid esterification step can also be used directly.

Examples of the solvent include the same solvents as those exemplified in the carboxylic acid esterification step. Moreover, as long as it is inert during a reaction, the reactive compound (C) etc. mentioned later can be used individually or in mixture as a solvent. In this case, it can also be used as it is as a hardening composition.

The amine esterification step may use a thermal polymerization inhibitor or the like, and the same compounds as those exemplified in the aforementioned carboxylic acid esterification step may be used.

The amine esterification step may be reacted substantially without a catalyst, but a catalyst may also be used to promote the reaction. When the catalyst is used, the amount of the catalyst used is about 0.01 to 1% by weight relative to the total amount of the reactants. Examples of the catalyst include general alkaline catalysts such as Lewis base catalysts such as tin ethylhexanoate.

The reaction temperature in the amine esterification step is preferably 40 to 150 ° C, and the reaction time is preferably 5 to 60 hours.

The reaction in the amine esterification step uses almost no residual isocyanate groups as the end point of the reaction. The determination of the end point of the reaction is performed by observing a peak near 2250 cm ^-1 derived from an isocyanate group by infrared absorption spectrometry or by a titration method shown in JIS K1556: 1968 and the like.

The preferred molecular weight range of the polyurethane compound (A) of the present invention thus obtained is a polystyrene-equivalent weight average molecular weight in the GPC range of 1,000 to 30,000, and more preferably a range of 3000 to 20,000. When the molecular weight is smaller than this, the toughness of the cured product cannot be sufficiently exhibited, or when the molecular weight is excessively larger, not only the viscosity becomes higher, but the application and the like become difficult, and the developability tends to decrease.

The present invention may also contain an acid-modified polyurethane compound (B) obtained by reacting a polybasic acid anhydride (g) with a reactive polyurethane compound (A), if necessary. Thereby, not only the compound (d) having two hydroxyl groups and one or more carboxyl groups in one molecule, but also the acid value required for alkaline development can be appropriately added in accordance with the characteristics of the required resin. In the present invention, this reaction step is referred to as an acid addition step.

Next, the acid addition step will be described in detail. The acid addition step is a step of reacting a polybasic acid anhydride (g) with a hydroxyl group remaining after the aforementioned amine esterification reaction, and introducing a carboxyl group through an ester bond. Therefore, it is not possible to perform acid addition at an equivalent amount of hydroxyl groups remaining after the amine esterification step is completed.

The polybasic acid anhydride (g) includes, for example, a compound having a cyclic anhydride structure in one molecule. From the viewpoint of developability, heat resistance, and hydrolysis resistance of an alkaline aqueous solution, succinic anhydride (SA), Phthalic anhydride (PAH), tetrahydrophthalic anhydride (THPA), hexahydrophthalic anhydride (HHPA), Ikon anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride Or maleic anhydride.

The acid addition step is performed by adding a polybasic acid anhydride (g) to the aforementioned polyurethane compound (A). The use amount of the polybasic acid anhydride (g) is appropriate according to the set value of the polyurethane compound (A), that is, based on the acid value derived from the compound (d), the amount of residual hydroxyl groups, and the acid value required for the polyurethane compound (A). Just change it.

When the polyurethane compound (A) and / or the acid-modified polyurethane compound (B) of the present invention is used as a basic developing-type inhibitor, it is preferable that the acid value of the solid content of the finally obtained polyurethane compound (based on JIS K5601- 2-1: 1999) is set to 30 to 120 mg‧KOH / g, and more preferably 40 to 105 mg‧KOH / g. When the solid component acid value is within this range, the active energy ray-curable resin composition of the present invention exhibits good developability due to an alkaline aqueous solution. That is, the balance between the good solubility of the active energy ray non-irradiated portion and the insolubility of the active energy ray irradiated portion can be achieved.

The acid addition step preferably uses a catalyst in order to promote the reaction, and the amount of the catalyst used is about 0.1 to 10% by weight relative to the total amount of the reactants. The reaction temperature at this time is 60 to 150 ° C, and the reaction time is preferably 5 to 60 hours.

Examples of the catalyst include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethylammonium iodide. , Triphenylphosphine, triphenylantimony, chromium octoate, zirconium octoate, etc.

The acid addition step may be solvent-free or diluted and reacted with a solvent. When a solvent is used, the solvent is not particularly limited as long as it is a solvent that is inert in the acid addition reaction. When the amine esterification step that belongs to the previous step is produced using a solvent, the acid addition reaction can be performed without removing the solvent as long as it is inert to both reactions.

The use amount of the solvent should be appropriately adjusted depending on the viscosity and use of the obtained resin, but it is preferably used so that the solid content content is 90 to 30% by weight, and more preferably the solid content is used. Used at a rate of 80 to 50% by weight.

The solvent may be the same as those exemplified in the carboxylic acid esterification reaction and the amine esterification step.

Moreover, as long as it is inert to a reaction, you may use the reactive compound (C) etc. mentioned later as a solvent individually or in mixture. In this case, it can also be used as it is as a hardening composition.

In the acid addition step, a thermal polymerization inhibitor or the like can be used, and the same compounds as those exemplified in the aforementioned carboxylic acid esterification step and the aforementioned amine esterification step can be used.

The reaction in the acid addition step is to set a point where the acid value of the reactant becomes a range of plus or minus 10% of the set acid value while sampling appropriately.

The active energy ray-curable resin composition of the present invention contains a polyurethane compound (A) and / or an acid-modified polyurethane compound (B). A resin composition containing a reactive compound (C) other than the component (A) and the component (B) is more preferable.

Examples of the reactive compound (C) include compounds such as radical-reactive acrylates, cation-reactive epoxy compounds, and vinyl compounds that induce both radicals and cations.

Examples of the radically reactive acrylates include monofunctional (meth) acrylates and polyfunctional (meth) acrylates.

Examples of the 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, phenylethyl (meth) acrylate, isoamyl (meth) acrylate, (meth) acrylic acid Cyclohexyl ester, benzyl (meth) acrylate, tetrahydrofuran methyl (meth) acrylate, and the like.

Examples of the polyfunctional (meth) acrylates include butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and neopentyl glycol di (meth) ) Acrylate, nonanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate , Trimeric isocyanate (meth) acrylfluorenyloxyethyl ester, polypropylene glycol di (meth) acrylate, adipic acid epoxy di (meth) acrylate, bisphenol ethylene oxide Di (meth) acrylate, hydrogenated bisphenol ethylene oxide di (meth) acrylate, bisphenol di (meth) acrylate, ε-caprolactone of hydroxytrimethylacetate neopentyl glycol plus Bis (meth) acrylates, poly (meth) acrylates of reactants of dipentaerythritol and ε-caprolactone, dipentaerythritol poly (meth) acrylates, trimethylol Propane tri (meth) acrylate, trihydroxyethylpropane tri (meth) acrylate or its ethylene oxide adduct, neopentyl tetraol tri (meth) acrylate or its ethylene oxide adduct Product, neopentaerythritol tetra (methyl) propane Esters or ethylene oxide adducts, two new dipentaerythritol hexa (meth) acrylate, or ethylene oxide adducts.

As for the cation-reactive epoxy compounds, the epoxy compound (a) is not particularly limited as long as it is a compound having an epoxy group, and examples thereof include propylene oxide (meth) acrylate and methyl epoxy. Propyl ether, ethylglycidyl ether, butylglycidyl ether, bisphenol-A diglycidyl ether, 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxy Cyclohexyl methyl ester ("CYRACURE UVR-6110", manufactured by Union Carbide, etc.), 3,4-epoxy cyclohexanecarboxylic acid 3,4-epoxy cyclohexyl ethyl ester, vinyl cyclohexene Oxide ("ELR-4206" manufactured by Union Carbide), limonene dioxide ("CELLOXIDE 3000" manufactured by Daicel Chemical Industries, etc.), allyl cyclohexene dioxide, 3,4-epoxy- 4-methylcyclohexyl-2-epoxypropane, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-di Alkane, bis (3,4-epoxycyclohexyl) adipate ("CYRACURE UVR-6128" manufactured by Union Carbide, etc.), bis (3,4-epoxycyclohexylmethyl) adipate , Bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane, etc. .

Examples of the vinyl compounds include vinyl ethers, styrenes, and other vinyl compounds.

Examples of the vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether.

Examples of the styrenes include styrene, methylstyrene, and ethylstyrene.

Examples of other vinyl compounds include triallyl isocyanate and trimethyl isocyanate. Allyl esters, etc.

In addition, the reactive compound (C) may be used: other than a polyurethane compound (A) and an acid-modified polyurethane compound (B), which have both a functional group capable of sensing an active energy ray and an amine ester bond in the same molecule. Polyurethane acrylates; polyester acrylates with functional groups and ester bonds that can also sense active energy rays in the same molecule; rings with functional groups derived from epoxy compounds that can sense active energy rays in the same molecule Oxyacrylates; oligomers and the like where such bonds are used compositely.

Among these, the reactive compound (C) is preferably a radical curing type acrylate. In the case of a cationic reaction type, since a carboxylic acid and an epoxy group react, it is necessary to make a two-liquid mixed type for preparation.

The active energy ray-curable resin composition of the present invention may have other components appropriately added depending on the application.

The active energy ray-curable resin composition of the present invention contains 97 to 5% by weight, preferably 87 to 10% by weight, of the polyurethane compound (A) and / or the acid addition-molded polyurethane compound (B) in the composition. And the reactive compound (C) other than the component (A) and the component (B) is 3 to 95% by weight, preferably 3 to 90% by weight. It may also be suitable for various purposes, and may contain other components with an upper limit of about 75% by weight as necessary.

Other components include a photopolymerization initiator, other additives, a pigment material, or a volatile solvent added for the purpose of adjusting the viscosity for the purpose of imparting coating suitability and the like.

Examples of the photopolymerization initiator that can be contained in the active energy ray-curable resin composition of the present invention include radical photopolymerization initiators and cationic photopolymerization initiators.

Examples of the radical photopolymerization initiator include benzene such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether. Marriages; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1- Ketone, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinyl-propane-1-one Isoacetophenones; anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, and 2-pentylanthraquinone; 2,4-diethylthioanthrone , 2-isopropylthioxanthone, 2-chlorothioxanthone and other thioanthrones; acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketals; benzophenone Ketones, 4-benzylidene-4'-methyldiphenyl sulfide, 4,4'-bismethylaminobenzophenone and other benzophenones; 2,4,6-trimethyl Phosphine oxides such as benzamidinediphenylphosphine oxide, bis (2,4,6-trimethylbenzyl) phenylphosphine oxide, and the like.

Examples of cationic photopolymerization initiators include diazonium salts of Lewis acids, phosphonium salts of Lewis acids, phosphonium salts of Lewis acids, phosphonium salts of Lewis acids, other halides, and Based initiators, borate based initiators, other photoacid generators, and the like.

Examples of the diazonium salt of Lewis acid include, for example, p-methoxyphenyldiazonium fluorophosphonic acid, N, N-diethylaminophenylphenyldiazonium hexafluorophosphonic acid (Sanxin Chemical Industry Co., Ltd. San-Aid SI-60L / SI-80L / SI-100L, etc.).

Examples of the phosphonium salt of a Lewis acid include diphenylphosphonium hexafluorophosphonate, diphenylphosphonium hexafluoroantimonate, and the like.

Examples of the phosphonium salt of Lewis acid include triphenylphosphonium hexafluorophosphonate (Cyracure UVI-6990 manufactured by Union Carbide, etc.) and triphenylphosphonium hexafluoroantimonate (Cyracure UVI-6974 manufactured by Union Carbide) and many more.

Examples of the phosphonium salt of a Lewis acid include triphenylphosphonium hexafluoroantimonate and the like.

Examples of other halides include 2,2,2-trichloro- [1-4 '-(dimethylethyl) phenyl] ethanone (Trigonal PI, etc., manufactured by AKZO), 2,2 -Dichloro-1- (4-phenoxyphenyl) ethanone (Sandray 1000, manufactured by Sandoz, etc.), α, α, α-tribromomethylphenylphosphonium (BMPS, etc. manufactured by Iron Chemicals Corporation), and the like.

Just three For the initiator, examples include: 2,4,6-ginseng (trichloromethyl) tri , 2,4-bis (trichloromethyl) -6- (4'-methoxyphenyl) tri (Triazine A, manufactured by Panchim, etc.), 2,4-bis (trichloromethyl) -6- (4'-methoxystyryl) tri (Triazine PMS, etc., manufactured by Panchim), 2,4-bis (trichloromethyl) -6-piperyltris (Triazine PP, etc., manufactured by Panchim), 2,4-bis (trichloromethyl) -6- (4'-methoxynaphthyl) tri (Triazine B, manufactured by Panchim, etc.), 2- [2 '-(5 ”-methylfuranyl) ethylene] -4,6-bis (trichloromethyl) -mesanthine (Manufactured by Sanwa Chemical Co., Ltd.), 2- (2'-furanylethylene) -4,6-bis (trichloromethyl) -mesan (By SANWA CHEMICAL).

Examples of the borate-based initiator include NK-3876 and NK-3881 (all of which are made by Japanese photosensitive dyes).

Examples of other photoacid generators include 9-phenylacridine, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1, 2-biimidazole (biimidazole manufactured by Heijing Kasei Co., Ltd.), 2,2-azobis (2-amino-propane) dihydrochloride (V50 manufactured by Wako Pure Chemical Industries, Ltd.), 2,2-azobis [2- (imidazoline-2yl) propane] dihydrochloride (VA044, manufactured by Wako Pure Chemical Industries, Ltd., etc.), hexafluorophosphonic acid [η-5-2-4- (cyclopentadecyl) (1,2, 3,4,5,6, η)-(methylethyl) benzene] iron (II) (Irgacure 261 manufactured by Ciba Geigy, etc.), bis (η-5-cyclopentadienyl) bis [2,6 -Difluoro-3- (1H-pyridin-1-yl) phenyl] titanium (CGI-784 manufactured by Ciba Geigy, etc.) and the like.

Furthermore, an azo-based initiator such as azobisisobutyronitrile, a peroxide-based radical initiator such as benzyl peroxide, and the like may be used in combination. In addition, both a radical-based and a cationic-based initiator may be used in combination, or one type may be used alone or two or more types may be used in combination.

Among these, in consideration of the properties of the polyurethane compound (A) of the present invention, a radical photopolymerization initiator is particularly preferred.

Furthermore, the active energy ray-curable resin composition of the present invention may contain a curing agent as appropriate depending on the application. This hardener is used for obtaining the hardened film | membrane which is strong by the reaction with the acidic group contained especially in the material for the purpose of electrical insulation.

Examples of the curing agent include epoxy compounds other than the reactive compound (C), and among them, epoxy compounds containing two or more epoxy groups in one molecule are preferred. This is because, compared with the use of a monofunctional epoxy compound, a harder hardened product can be obtained. The epoxy equivalent of these epoxy compounds is preferably in the range of 150 to 450 g / eq, and more preferably in the range of 180 to 350 g / eq. When the epoxy equivalent is less than this range, the obtained hardened product is liable to become fragile, and when it is larger than this range, the crosslinked sites are reduced, so the obtained hardened product is liable to become weak.

This epoxy compound can be arbitrarily selected according to the purpose of use of a hardened | cured material, and the required characteristic, A well-known general epoxy compound can be used arbitrarily.

Examples of the monofunctional epoxy compound include phenyl glycidyl ether and glycidyl (meth) acrylate.

Examples of the epoxy compound having two or more epoxy groups in the molecule include phenol novolac epoxy resin, cresol novolac epoxy resin, hydroxyphenylmethane epoxy resin, and Cyclopentadiene phenol epoxy resin, bisphenol-A epoxy resin, bisphenol-F epoxy resin, biphenol epoxy resin, bisphenol-A novolac epoxy resin, Epoxy resin, glyoxal epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, etc.

Examples of the phenol novolak epoxy resin include EPICLON N-770 (manufactured by DIC Corporation), DEN438 (manufactured by Dow Chemical Co.), jER154 (manufactured by Japan epoxy resin Co., Ltd.), and EPPN- 201, RE-306 (all manufactured by Nippon Kayaku Co., Ltd.), etc.

Examples of the cresol novolac epoxy resin include EPICLON N-695 (manufactured by DIC Corporation), EOCN-102S, EOCN-103S, and EOCN-104S (all manufactured by Nippon Kayaku Co., Ltd.) ), UVR-6650 (manufactured by Union Carbide), ESCN-195 (manufactured by Sumitomo Chemical Industries, Ltd.), etc.

Examples of the hydroxyphenylmethane type epoxy resin include EPPN-503, EPPN-502H, EPPN-501H (all manufactured by Nippon Kayaku Co., Ltd.), and TACTIX-742 (made by Dow Chemical) , JER E1032H60 (manufactured by Japan epoxy resin Co., Ltd.) and the like.

Examples of the dicyclopentadiene phenol type epoxy resin include EPICLON EXA-7200 (manufactured by DIC Corporation) and TACTIX-556 (manufactured by Dow Chemical Co., Ltd.).

Examples of the bisphenol epoxy resin include jER828, jER1001 (all manufactured by Japan epoxy resin Co., Ltd.), UVR-6410 (made by Union Carbide), DER-331 (made by Dow Chemical), YD-8125 (manufactured by Toto Chemical Co., Ltd.), NER-1202, NER-1302 (all manufactured by Nippon Kayaku Co., Ltd.) and other bisphenol-A epoxy resins, UVR-6490 (manufactured by Union Carbide), Bisphenol-F epoxy resins such as YDF-8170 (manufactured by Tohto Chemical Co., Ltd.), NER-7403, and NER-7604 (all manufactured by Nippon Kayaku Co., Ltd.).

Examples of the biphenol type epoxy resin include biphenol type epoxy resins such as NC-3000, NC-3000-H, and NC-3000-L (all manufactured by Nippon Kayaku Co., Ltd.), YX, and the like. -4000 (manufactured by Japan epoxy resin Co., Ltd.), xylenol-type epoxy resin, YL-6121 (manufactured by Japan epoxy resin Co., Ltd.), and the like.

Examples of the bisphenol A novolac epoxy resin include EPICLON N-880 (manufactured by DIC Corporation), jER E157S75 (manufactured by Japan epoxy resin Corporation), and the like.

Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (manufactured by Nippon Kayaku Co., Ltd.) and EXA-4750 (manufactured by DIC Co., Ltd.).

Examples of the glyoxal-type epoxy resin include GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.).

Examples of the alicyclic epoxy resin include EHPE-3150 (manufactured by Daicel Chemical Industry Co., Ltd.).

Examples of the heterocyclic epoxy resin include TEPIC (manufactured by Nissan Chemical Industries, Ltd.).

Among these, biphenol-type epoxy resins are particularly effective in terms of flexibility, and particularly preferred are NC-3000, NC-3000-H, NC-3000-L, and the like.

When the epoxy compound is contained, a suitable blending amount thereof is about 5 to 80% by weight, more preferably about 10 to 70% by weight, of the solid content of the active energy ray-curable resin composition of the present invention. When the blending amount is less than the above amount, the hardened product obtained is likely to become weak, and when the blending amount is too large, the balance with the epoxy-based hardener described below may adversely affect the hardenability and the like.

Examples of the other additives that may be contained in the active energy ray-curable resin composition of the present invention include, for example, a thermosetting catalyst such as melamine, a shake-imparting agent such as Aerosil, a silicone or fluorine-based leveling agent, or Antifoaming agents, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, stabilizers, antioxidants, or flame retardants for imparting flame retardancy.

In particular, when a film-forming material for the purpose of electrical insulation is used, a flame retardant is preferably used in combination. As a preferable flame retardant, a publicly known one can be used, and a halogen-based flame retardant such as a brominated epoxy resin, bromodiphenyl ether, or the like, a phosphazene resin, or a triphenyl phosphate can be suitably used. And other phosphate ester resins, organic hydrogen flame retardants such as dihydro-9-oxa-phosphaphenanthrene-10-oxide derivatives, metal hydroxide flame retardants such as magnesium hydroxide, red phosphorus, and antimony trioxide And other inorganic flame retardants.

Examples of the pigment material that can be contained in the active energy ray-curable resin composition of the present invention include coloring pigments for coloring purposes and extender pigments for non-coloring purposes.

Examples of the colored pigment include organic pigments such as phthalocyanin-based, azo-based, and quinacridone-based, and inorganic pigments such as carbon black and titanium oxide.

Examples of the extender pigment include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, and clay.

Furthermore, it may contain resins (so-called inert polymers) which do not show reactivity with active energy rays. This resin can contain, for example, other epoxy resins, phenol resins, amine ester resins, and polyester resins other than the epoxy resins as the hardener in the active energy ray-curable resin composition of the present invention. Ketone-formaldehyde resin, cresol resin, xylene resin, diallyl phthalate resin, styrene resin, guanamine resin, natural and synthetic rubber, acrylic resin, polyolefin resin, and other modified products. These are preferably used in the active energy ray-curable resin composition in a range up to 40% by weight.

In particular, when the polyurethane compound (A) and / or the acid-modified polyurethane compound (B) is used for a solder resist application, an epoxy resin is preferably used in combination. The carboxyl group remaining after hardening by the active energy ray is further carboxylic acidified to form a strong cross-linked structure, so that the cured product is excellent in water resistance and hydrolysis resistance.

The volatile solvent that can be contained in the active energy ray-curable resin composition of the present invention, for the purpose of adjusting the viscosity according to the purpose of use, as long as it is 50% by weight (more preferably 35% by weight) in the resin composition. Just add the range.

The active energy ray-curable resin composition of the present invention is easily hardened by the active energy ray. Examples of active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, and laser rays, and particle rays such as alpha rays, beta rays, and electron rays. In consideration of a suitable application of the present invention, among them, ultraviolet rays, laser rays, visible rays, or electron rays are preferred.

The present invention includes using the aforementioned active energy ray-curable resin composition as a film-forming material for the purpose of coating the surface of a substrate. That is, the film-forming material is, for example, printing ink materials such as gravure printing ink, flexographic printing ink, screen printing ink, overprint printing ink, hard coating, top coating, overprint varnish, clear coating, etc. Coating materials, adhesives for pressure-sensitive adhesives such as laminates or optical discs, solder resists, etching resists, and resist materials such as micromechanical resists.

The film-forming material is also a so-called dry film in which a film-forming material is temporarily applied to a peelable substrate and formed into a film, and then the substrate is bonded to the original substrate to form a film.

The present invention also includes using the aforementioned active energy ray-curable resin composition as a film-forming material for the purpose of electrical insulation. That is, the material for film formation is a material that requires electrical insulation, such as a solder resist material for a circuit board, an insulating mold material, an interlayer insulation material, a semiconductor protective film material, and a wiring covering material.

The present invention also includes using the aforementioned active energy ray-curable resin composition as an active energy ray sensing type resist material. The active energy ray sensing type resist material is such that a film layer of the composition is formed on a substrate, and then A part is irradiated with active energy rays such as ultraviolet rays to draw using the difference in physical properties between the irradiated part and the unirradiated part. That is, it is used for the purpose of removing the irradiated portion or the unirradiated portion by a method such as dissolving in a solvent or the like, an alkaline solution, or the like, and drawing it.

The present invention also includes the aforementioned active energy ray-curable resin composition for use in a permanent resist. Permanent resist refers to the user of the above-mentioned resist materials, which is not based on the premise of peeling after drawing, but does not peel until it is actually used by the person who is the base material, and continues to maintain its purpose and function.

The active energy ray-curable resin composition for a resist of the present invention can be applied to various materials to be patterned. Among them, it is particularly used for a solder resist material, an interlayer insulating material for a build-up method, and the like. As optical waveguides, electrical / electronic / optical substrates such as printed circuit boards, optoelectronic substrates, and optical substrates are used.

For particularly suitable applications, it can make use of the characteristics of good heat resistance and developability, and is used in insulating films such as photosensitive films, photosensitive films with a support, and prepregs, circuit boards (multilayer board applications, multilayer Printed circuit board applications, etc.), solder masks, underfill materials, die bonding materials, semiconductor packaging materials, plugging resins, parts embedding resins and other applications that require resin compositions. Among them, a resin composition for an insulating layer of a multilayer printed circuit board (a multilayer printed circuit board using a cured product of a photosensitive resin composition as an insulating layer), a resin composition for an interlayer insulating layer (a photosensitive The hardened material of the resin composition is used as an interlayer insulating layer of a multilayer printed wiring board), and the resin composition for forming a plating film (a multilayer printed circuit board with a plated film formed on a cured material of the photosensitive resin composition).

Furthermore, it can exhibit good developability in high pigment concentration, and can be suitably used as a color resist, a resist material for a color filter, and particularly suitable for a black matrix material.

In addition, the soft and strong hardened material can be used in a flexible manner, and when it is used for an insulating material for a flexible substrate that requires flexibility, the effect of the present invention can be exerted to the maximum, and it is a suitable application.

There is no particular limitation on the method of film formation, and gravure printing methods such as gravure, letterpress printing methods such as flexography, stencil printing methods such as screen printing, lithographic printing methods such as register, roll coater, knife Coating methods, such as coating machines, mold coaters, curtain coaters, and spin coaters.

The present invention also includes a hardened product obtained by irradiating the active energy ray-curable resin composition with an active energy ray to harden it.

[Example]

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to these examples. In the examples, unless otherwise specified,% means% by weight.

The softening point and epoxy equivalent were measured under the following conditions.

1) Epoxy equivalent (WPE): measured by a method according to JIS K 7236: 2001.

2) Total chlorine: measured by a method in accordance with JIS K 7243-3: 2005.

3) Acid value: Measured in accordance with JIS K 0070: 1992.

4) The measurement conditions of GPC are as follows.

Model: TOSOH HLC-8220GPC

Tubing: TSKGEL Super HZM-N

Eluate: THF (tetrahydrofuran); 0.35ml / min, temperature 40 ° C

Detector: Differential refractometer

Molecular weight standard: polystyrene

    (Synthesis Example 1): Preparation of unsaturated epoxy carboxylic acid ester compound (c) (carboxylic acid esterification step)    

1840 g of bisphenol A epoxy resin (RE-310S, WPE = 184g / eq, manufactured by Nippon Kayaku Co., Ltd.) as the epoxy compound (a), and acrylic acid (referred to as AA, Mw = 72) 720 g, 30 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate (abbreviated as PGMAc) as a solvent are added so that the solid content content is 80%, and reacted at 100 ° C for 24 hours A solution of the unsaturated epoxy carboxylic acid ester compound (c) was obtained.

The reaction was completed at the time when the solid content converted acid value was 1.8 mg‧KOH / g. This acid value measurement is converted into the acid value of the solid content measured in the reaction solution. The epoxy value was measured and found to be 13000 g / eq. It was also confirmed that the epoxy group was sufficiently reacted.

    (Example 1): Preparation of polyurethane compound (A) (amine esterification step)    

In the reaction tank, the unsaturated epoxy carboxylic acid ester compound (c) solution obtained in Synthesis Example 1 was added in the amount described in Table 1 (recorded value is a solid content conversion value) as the dihydroxymethyl compound (d). Propylene glycol was added in the amount described in Table 1, and the polyester diol described in Table 1 as the polyester diol compound (e) was added in the amount described in Table 1, as a solvent of propylene glycol monomethyl ether acetic acid. An ester (abbreviated as PGMAc) was added with 47.5 g so that the solid content of the polyurethane compound (A) became 50%, and the mixture was dissolved by stirring.

In addition, 0.5 g of tin octoate as a catalyst and 0.1 g of hydroquinone as a thermal polymerization inhibitor were added and heated to 100 ° C. Thereafter, the amount of the hexamethylene diisocyanate as the isocyanate compound (f) as described in Table 1 was added using a dropping funnel to perform a reaction. After completion of the dropping, the reaction was continued for 10 hours, and it was confirmed by an infrared absorption spectrum that there was no absorption spectrum peak derived from an isocyanate group, and a polyurethane compound (A) was obtained.

    (Comparative Example 1): Preparation of Comparative Polyurethane Compound    

Using the carboxylic acid ester compound (c) prepared in Synthesis Example 1, the polyurethane compounds in Table 1 were prepared in the same manner as in Example 1.

Shorthand in the table:

(c + d + e) / f: the ratio of the total molar number of hydroxyl groups contained in the reaction system to the total molar number of isocyanate groups

URIC SE-2013C: Sebacic acid polyester polyol (made by Ito Oil Co., Ltd.) average molecular weight 2000

URIC-3091U: Sebacic acid polyester polyol (made by Ito Oil Co., Ltd.) average molecular weight 1000

PRIPLAST XL 101: Dimer acid polyester polyol (CRODA Co., Ltd.) average molecular weight 2200

PCDLT-6001: Polycarbonate diol (manufactured by Asahi Kasei Corporation) with an average molecular weight of 1,000

    (Example 2): Preparation of acid-modified polyurethane compound (B) (acid addition step)    

In the reaction tank, the PGMAc solution of the polyurethane compound (A) obtained in Example 1 was added in the amount shown in Table 2, and the acid anhydride described in Table 2 as the polybasic acid anhydride (g) was added in the amount shown in Table 2. (Calculated value of the acid value of the solid content as 90 mg · KOH / g) was added. Further, PGMAc is added as a solvent so that the final solid content content becomes 50%, that is, PGMAc is added as a solvent with the same weight as the acid anhydride. Add 0.2 g of triethylamine as a catalyst and stir to dissolve.

After being dissolved, the mixture was heated to 100 ° C. with stirring and allowed to react for 50 hours to obtain an acid-modified polyurethane compound (B). After completion of the reaction, an acid value measurement was performed to confirm completion of the reaction.

    (Comparative Example 2): Preparation of a comparative acid-modified polyurethane compound    

Using the polyurethane compound prepared in Comparative Example 1, an amine esterification step was performed in the same manner as in Example 2 to prepare an acid-modified amine ester compound.

Shorthand in the table:

AV: Solid content acid value (mg‧KOH / g): The measurement is performed as a solution and converted to a value in solid content.

Mw: weight-average molecular weight measured by gel permeation chromatography (standard conversion value of polystyrene)

SA: Succinic anhydride (manufactured by New Japan Physicochemical Co., Ltd.)

    (Example 3) Adjustment and evaluation of solder resist material composition for flexible substrate    

6.0 g of the acid-modified polyurethane compound (B) obtained in Example 2 and 1.2 g of DPCA-20 (trade name: manufactured by Nippon Kayaku Co., Ltd.) as a reactive compound (C) were added as a photopolymerization initiator 0.27 g of IRGACURE 907 (manufactured by Ciba Specialty Chemicals) and 0.01 g of KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.), 0.01 g of TPP as a thermosetting catalyst, and diethylene glycol monomethyl as a concentration adjustment solvent Ether monoacetate, the solid content concentration was adjusted to 60%. Thereafter, the resist material resin composition was obtained by uniformly dispersing.

Details of the evaluation items.

Evaluation of roll bending resistance (abbreviated in the table: softness)

A bisphenol A type epoxy resin (trade name: YD-134, manufactured by Nippon Steel & Sumikin Co., Ltd.) as a curing component is added to the resist material composition so as to be 120% with respect to the carboxyl group. The obtained composition was applied to a polyimide film KAPTON 100H (manufactured by DU PONT-TORAY) so that the thickness became 20 μm using an applicator, and the coating film was dried using a hot air dryer at 80 ° C. for 60 minutes.

Next, ultraviolet rays were irradiated with an energy of 500 mJ / cm ² using an ultraviolet irradiator (manufactured by GS YUASA: CS 30L-1). Then, it hardened in the oven at 150 degreeC for 30 minutes.

This cured film was subjected to a 180-degree roll-bending test, and the number of times until cracking of the cured film was evaluated was evaluated.

Evaluation of developability (abbreviated in the table: developability)

The developability is that the coating film before ultraviolet irradiation is spray-developed using a 1% sodium carbonate aqueous solution as a developing solution. The development time (unit: second) is evaluated by the time until the coating film is completely dissolved, which is the so-called break time.

× ‧‧Swelling and peeling

Evaluation of welding heat resistance (abbreviated in the table: heat resistance)

The test according to JIS C-5016 10.3: 1994 was performed. Using a patterned film formed with a hardened film of a resist, the immersion was repeated three times in a heated solder bath. After the immersion, the peeling condition was evaluated by a checkerboard peeling test on the flexible substrate.

Welding bath temperature: 260 ° C

One dipping time: 60 seconds

Evaluation criteria: The aforementioned checkerboard grid number (100) is used as the denominator, and the remaining grid number is used as the numerator.

From the above results, it can be judged that the active energy ray-curable resin composition using the acid-modified polyurethane compound (B) of the present invention can obtain a good cured film in roll bending resistance.

In view of such characteristics, it has been found that the active energy ray-curable resin composition containing the acid-modified polyurethane compound (B) of the present invention can be particularly suitably used as a solder resist for flexible substrates.

    (Industrial availability)    

The polyurethane compound (A) of the present invention, a composition containing the polyurethane compound (A), and a cured product thereof are materials having good flexibility, and can be suitably used as a resist material for a flexible substrate or a flexible display. Resistors such as color resists and spacer resists.

Claims (10)

    A polyurethane compound (A) is an unsaturated epoxy carboxylic acid ester compound (c), a compound (d) having two hydroxyl groups and one or more carboxyl groups in one molecule, and a dicarboxylic acid having 10 or more carbon atoms A polyester diol compound (e) and a compound (f) having two isocyanate groups in one molecule, wherein the unsaturated epoxy carboxylic acid ester compound (c) has one or more molecules in one molecule. The compound (b) having an ethylenically unsaturated group and one carboxyl group is obtained by reacting an epoxy compound (a) having two epoxy groups in one molecule.         The polyurethane compound (A) according to item 1 of the scope of the patent application contains a sebacic acid polyester diol or a dimer acid polyester diol as the polyester diol compound (e).         An acid-modified polyurethane compound (B) is obtained by reacting a polybasic acid anhydride (g) with the polyurethane compound (A) described in item 1 or 2 of the scope of patent application.         An active energy ray-curable resin composition containing the polyurethane compound (A) described in item 1 or 2 of the patent application scope, or the polyurethane compound (B) described in item 3 of the patent application scope.         The active energy ray-curable resin composition according to item 4 of the scope of application for a patent, further contains a reactive compound (C) other than the polyurethane compound (A) and the acid-modified polyurethane compound (B).         The active energy ray-curable resin composition according to item 4 or item 5 of the scope of patent application is a material for forming.         The active energy ray-curable resin composition according to item 6 of the scope of patent application is a material for forming a film.         The active energy ray-curable resin composition according to any one of claims 4 to 7 of the scope of application for a patent, which is a resist material.         A hardened product is a hardened product of the active energy ray-curable resin composition described in any one of claims 4 to 8 of the scope of patent application.         An article is protected with a hardened body as described in item 9 of the scope of patent application.