Polyurethane compound, active energy ray-curable resin composition, cured product, and article

Abstract

The present invention relates to polyurethane compounds. The present invention addresses the problem of providing a material which can be photo-patterned, while maintaining basic characteristics such as solder resists such as high insulation properties and resistance to chemical treatments such as plating treatments, without impairing and being able to withstand heat resistance during substrate manufacturing such as soldering and element heat generation during long-term maintenance, and which has both flexibility and toughness. A polyurethane compound (A) according to the present invention is obtained by reacting an unsaturated epoxy carboxylic acid ester compound (c), a compound (d) having two hydroxyl groups and one or more carboxyl groups in one molecule, 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, the unsaturated epoxy carboxylate compound (c) is obtained by reacting a compound (b) having one or more ethylenically unsaturated groups and one carboxyl group in one molecule with an epoxy compound (a) having two epoxy groups in one molecule.

Description

[0001] This invention is a divisional application. The application number of the parent application is 201810049605.8, the application date is January 18, 2018, and the name of the invention is "Polyurethane compounds, active energy ray-curable resin compositions, cured products and articles". Technical Field

[0002] 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 an active energy ray-curable resin composition containing a polyurethane compound (A) and / or an acid-modified polyurethane compound (B), which is suitable for use as a resist material for flexible substrates, a color resist material for flexible displays, a spacer resist, and the like, and a cured product thereof. Background Art

[0003] In recent years, with the miniaturization of electronic information devices, the use of so-called flexible printed circuit boards has increased due to the requirements for circuit boards to be light, thin, and flexible.

[0004] Flexible printed circuit boards, as their name implies, are flexible. The materials used must be capable of photopatterning via alkaline development. They also possess essential properties such as high sensitivity, adhesion, scratch resistance, and high mechanical, thermal, and electrical strength. Furthermore, they are required to be able to form a strong film with the flexibility to conform to the flexible substrate.

[0005] Generally speaking, excellent properties such as sensitivity, curability, chemical resistance, and heat resistance are achieved by introducing more reactive groups into the rigid backbone, thereby imparting a high crosslinking density. Such resins are ideally used in applications such as conventional solder resists. However, this approach cannot impart the required flexibility to flexible substrates.

[0006] On the other hand, in order to impart flexibility, this is achieved by introducing a relatively small number of reactive groups into the flexible main chain, that is, by appropriately reducing the crosslinking density.

[0007] As mentioned above, these properties are contradictory, and solder resist materials for flexible substrates and other applications require materials that balance these properties at a high level. Previously, epoxy acrylate-based materials were primarily used. However, while these materials offer excellent chemical resistance and heat resistance, they lack sufficient flexibility. Therefore, it has been difficult to achieve a strong film that is both flexible and suitable for flexible substrates, and a more advanced film-forming material is desired.

[0008] As an attempt to solve these problems, Patent Document 1 describes a reactive urethane compound obtained by reacting a difunctional unsaturated epoxycarboxylate compound, a compound having two hydroxyl groups and one or more carboxyl groups in one molecule, and a diisocyanate compound.

[0009] The reactive urethane compound has good softness and heat resistance compared with conventional epoxy acrylate-based materials, but cannot exhibit higher softness required at present.

[0010] In addition, a method of simply using other diol compounds to constitute the reactive urethane compound, which is a general method of improving the softness of the urethane compound, can significantly reduce the heat resistance, and cannot obtain the heat resistance and hardening required for solder resist and other applications.

[0011] In addition, there is an attempt to add a rubber compound having two hydroxyl groups in the molecule for the purpose of imparting softness (Patent Document 2).

[0012] By this, although good softness can be exhibited, the rubber compound has poor compatibility with the reactive urethane compound, and if the rubber compound is used in an amount to exhibit sufficient softness, it becomes a phase separation state. Even when it is made into an active energy ray-hardening type resin composition in which other compounds are blended, a problem of compatibility occurs.

[0013] When a problem of compatibility occurs, adverse effects on developability occur, and specifically, development is difficult, fine patterning is difficult, and the like. In addition, with respect to heat resistance, it becomes difficult to exhibit satisfactory characteristics.

[0014] In addition to this, there is an attempt to use a non-reactive urethane compound 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 (Patent Document 3). However, the urethane compound does not have reactivity to active energy rays. Therefore, in order to obtain reactivity to active energy rays, that is, in order to obtain a resin composition that can be finely patterned by light drawing, other reactive compounds must be used, but it is not possible to exhibit reactivity to active energy rays and softness, heat resistance, and the like at a high level.

[0015] In addition, Patent Document 4 discloses a reactive polyurethane compound that has been imparted with reactivity to active energy rays, but the performance is not sufficient in terms of softness to 180°C bending, which is practically used for flexible printed boards.

[0016] [Related Art Documents]

[0017] [Patent Documents]

[0018] [Patent Document 1] Japanese Patent Application Laid-Open (JP A) No. 9-52925

[0019] [Patent Document 2] Japanese Patent Application Laid-Open (JP A) No. 2003-147043

[0020] [Patent Document 3] Japanese Patent Application Laid-Open No. 2006-124681

[0021] [Patent Document 4] Japanese Patent Application Laid-Open No. 2011-140624. Summary of the Invention

[0022] (Problems to be solved by the invention)

[0023] The present invention aims to provide a material that can be photopatterned without sacrificing the basic properties required of solder resists, such as heat resistance to withstand the heat of soldering during substrate manufacturing and the heat generated by components used on the substrate, reliability to maintain high insulation over a long period of time, and chemical resistance to chemical treatments such as plating, while also possessing the flexibility and toughness required for flexible substrates.

[0024] (Methods for solving the problem)

[0025] As a result of intensive research to address the aforementioned issues, the inventors discovered that polyurethane compounds obtained using ester diol compounds of dicarboxylic acids having specific structures, acid-modified compounds thereof, and resin compositions containing these compounds can address the aforementioned issues, leading to the completion of the present invention. Specifically, the present invention relates to the following:

[0026] [1] 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) of 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 one or more ethylenically unsaturated groups and one carboxyl group in one molecule with an epoxy compound (a) having two epoxy groups in one molecule;

[0027] [2] The polyurethane compound (A) according to [1], comprising sebacic acid polyester diol or dimer acid polyester diol as the polyester diol compound (e);

[0028] [3] An acid-modified polyurethane compound (B) obtained by reacting a polyacid anhydride (g) with the polyurethane compound (A);

[0029] [4] An active energy ray-curable resin composition comprising the polyurethane compound (A) described in [1] or [2] and / or the acid-modified polyurethane compound (B) described in [3];

[0030] [5] The active energy ray-curable resin composition according to [4], comprising a reactive compound (C) other than the polyurethane compound (A) and the acid-modified polyurethane compound (B);

[0031] [6] The active energy ray-curable resin composition according to [4] or [5] is a forming material;

[0032] [7] The active energy ray-curable resin composition according to [6] is a film-forming material;

[0033] [8] The active energy ray-curable resin composition according to any one of [4] to [7], which is a resist material;

[0034] [9] A cured product, which is the cured product of the active energy ray-curable resin composition according to any one of [4] to [8];

[0035]

[10] An article protectively covered with the hardened article described in [9].

[0036] (Effects of the Invention)

[0037] The polyurethane compound (A) of the present invention is a polyester diol compound using a dicarboxylic acid having 10 or more carbon atoms. Flexibility is enhanced by embedding a long-chain alkyl group. Therefore, the acid-modified polyurethane compound (B), an active energy ray-curable resin composition containing the same, and a cured product thereof can provide a material capable of photopatterning without compromising the basic properties required of solder resists, color resists, and the like, such as heat resistance to withstand the heat of soldering during substrate manufacturing and the heat generated by components used in the substrate, reliability in maintaining high insulation over a long period of time, and chemical resistance to chemical treatments such as plating. Furthermore, the material possesses the flexibility and toughness required for flexible substrates and the like, and is particularly suitable for use in film-forming materials requiring flexibility, such as solder resists for flexible substrates. DETAILED DESCRIPTION

[0038] Hereinafter, the present invention will be described in detail.

[0039] The polyurethane compound (A) of the present invention is obtained by reacting an unsaturated epoxycarboxylate compound (c), a compound (d) having two hydroxyl groups and one or more carboxyl groups in one molecule, 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. The unsaturated epoxycarboxylate compound (c) is obtained by reacting a compound (b) having one or more ethylenically unsaturated groups and one carboxyl group in one molecule with an epoxy compound (a) having two epoxy groups in one molecule.

[0040] Specifically, the polyurethane compound (A) of the present invention is produced in two reaction steps. First, an epoxy compound (a) having two epoxy groups per molecule is reacted with a compound (b) having one or more ethylenically unsaturated groups and one carboxyl group per molecule to produce an unsaturated epoxy carboxylate compound (c). In the present invention, this step is referred to as the carboxylation step.

[0041] Next, the unsaturated epoxycarboxylate compound (c) thus obtained, a compound (d) having two hydroxyl groups and one or more carboxyl groups in one molecule, 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 are reacted. In the present invention, this step is referred to as the urethanization step.

[0042] The unsaturated epoxy carboxylate compound (c) obtained in the carboxylation step is a carboxylate compound having two or more ethylenically unsaturated groups and two hydroxyl groups derived from the epoxy group of the epoxy compound (a) in one molecule.

[0043] In the subsequent urethanization step, two hydroxyl groups of the unsaturated epoxycarboxylate compound (c), two hydroxyl groups of the compound (d) having two hydroxyl groups and one or more carboxyl groups in one molecule, two hydroxyl groups of the 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 are reacted to obtain a polyurethane compound (A).

[0044] First, the carboxylation step will be described in detail.

[0045] The epoxy compound (a) having two epoxy groups per molecule (hereinafter referred to as "epoxy compound (a)") used in the production of the polyurethane compound (A) of the present invention is not particularly limited as long as it has two epoxy groups per molecule. Monofunctional epoxy compounds cannot adjust the molecular weight of the polyurethane compound (A) obtained in the urethanization step. Furthermore, trifunctional or higher-functional epoxy compounds form a multi-branched structure, making it difficult to obtain suitable physical properties of the cured product.

[0046] Examples of the epoxy compound (a) include bisphenol-based diglycidyl ethers such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and bisphenol fluorene diglycidyl ether; aromatic diglycidyl ether compounds such as biphenyl-based glycidyl ethers such as biphenol diglycidyl ether and tetramethylbiphenol glycidyl ether; alkyl glycol diglycidyl ethers such as hexanediol diglycidyl ether, alkyl glycol diglycidyl ethers such as polyethylene glycol diglycidyl ether, cycloalkyl glycol diglycidyl ethers such as cyclohexanediol diglycidyl ether and hydrogenated bisphenol A diglycidyl ether; 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate (CELLOXIDE manufactured by Daicel Chemical Co., Ltd.); 2021), 1,2,8,9-diepoxylimonene (CELLOXIDE 3000 manufactured by Daicel Chemical Co., Ltd.), and other so-called difunctional alicyclic epoxy compounds.

[0047] Among these, aromatic diglycidyl ether compounds are suitable because they have good heat resistance.

[0048] Furthermore, the epoxy compound (a) is preferably one without a hydroxyl group, because the unsaturated epoxy carboxylate compound (c) obtained in the epoxy carboxylation step becomes a trifunctional or higher-functional polyol compound, making it difficult to control the molecular weight of the polyurethane compound (A).

[0049] The compound (b) having both one or more ethylenically unsaturated groups and one carboxyl group per molecule (hereinafter referred to as "compound (b)") used in the production of the polyurethane compound (A) of the present invention has the purpose of introducing ethylenically unsaturated groups into the reactive polyurethane compound (A) and simultaneously converting the epoxy compound (a) into a diol compound reactive with an isocyanate group. The number of ethylenically unsaturated groups in the compound (b) is preferably 1 to 4.

[0050] Examples of the compound (b) include (meth)acrylic acids and crotonic acid, α-cyanocinnamic acid, cinnamic acid, or reaction products of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound other than monoglycidyl (meth)acrylate derivatives.

[0051] Examples of the (meth)acrylic acid include (meth)acrylic acid, β-styryl(meth)acrylic acid, β-furylmethyl(meth)acrylic acid, a reaction product of (meth)acrylic acid and ε-caprolactone, a (meth)acrylic acid dimer, half esters of an equivalent molar reaction product of a saturated or unsaturated dibasic acid anhydride and a (meth)acrylate derivative having one hydroxyl group per molecule, and half esters of an equivalent molar reaction product of a saturated or unsaturated dibasic acid and a monoglycidyl(meth)acrylate derivative.

[0052] Among these, (meth)acrylic acid, a reaction product of (meth)acrylic acid and ε-caprolactone, or cinnamic acid is more preferable in terms of sensitivity when prepared as an active energy ray-curable resin composition.

[0053] Furthermore, as the compound (b), a compound having no hydroxyl group is more preferred.

[0054] In the carboxylation step, the compound (b) is preferably 90 to 120 equivalents relative to 1 equivalent of the epoxy compound (a). Within this range, the resin can be produced under relatively stable conditions. When the feed amount of the compound (b) is greater than this range, the compound (b) having a carboxyl group will remain, which is not preferred. In addition, when the feed amount of the compound (b) is too small, unreacted epoxy compound (a) will remain, so the stability of the resin will be problematic.

[0055] The carboxylation step can be carried out without a solvent or by diluting the reaction with a solvent. When a solvent is used, it is not particularly limited as long as it is inert to the carboxylation reaction. In addition, it is more preferred to use a solvent that is inert in the subsequent urethanization step and the acid addition step described below, which may be used as needed.

[0056] When a solvent is used, its amount should be appropriately adjusted depending on the viscosity of the resulting resin and the intended use. It is preferably used to achieve a solids content of 99 to 30% by weight, more preferably 99 to 45% by weight. When the compound used in the reaction has a high viscosity, the viscosity is suppressed, allowing the reaction to proceed appropriately.

[0057] Examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene; aliphatic hydrocarbon solvents such as hexane, octane, and decane; and mixtures thereof such as petroleum ether, white gasoline, and solvent naphtha. In addition, ester solvents, ether solvents, and ketone solvents may also be used.

[0058] Examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate; cyclic esters such as γ-butyrolactone; mono- or polyalkylene glycol monoalkyl ether monoacetates such as ethylene glycol monomethyl ether monoacetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, and butanediol monomethyl ether monoacetate; and polycarboxylic acid dialkyl esters such as dimethyl glutarate and other dialkyl succinates such as dimethyl succinate and dialkyl adipates such as dimethyl adipate.

[0059] Examples of the ether solvent include alkyl ethers such as diethyl ether and ethyl butyl ether; glycol 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.

[0060] Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

[0061] In addition, as long as it is inert to the reaction, a reactive compound (C) described later may be used alone or in combination as a solvent. In this case, it can be used as a curable resin composition as it is.

[0062] In the carboxylation step, a catalyst is preferably used to promote the reaction. When the catalyst is used, the amount of the catalyst used is approximately 0.1 to 10% by weight relative to the reactants, i.e., when the epoxy compound (a), the compound (b), and the solvent are used, relative to the total amount of the added solvent. The reaction temperature is preferably 60 to 150° C., and the reaction time is preferably 5 to 60 hours.

[0063] Examples of the catalyst include common basic catalysts such as triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylantimony, chromium octylate, and zirconium octylate.

[0064] Furthermore, a thermal polymerization inhibitor may be used. As the thermal polymerization inhibitor, for example, hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4-hydroxytoluene, and the like are preferably used.

[0065] The carboxylation step is terminated when the acid value of the sample becomes 5 mg·KOH / g or less, more preferably 2 mg·KOH / g or less, while sampling is performed appropriately.

[0066] Next, the urethanization step is described in detail.

[0067] The compound (d) having two hydroxyl groups and one or more carboxyl groups per molecule (hereinafter referred to as "compound (d)") used in the production of the polyurethane compound (A) of the present invention introduces carboxyl groups into the polyurethane compound (A) to render it soluble in the alkaline aqueous solution required for photopatterning. The number of carboxyl groups in compound (d) is preferably 1 to 4.

[0068] As the compound (d), dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolvaleric acid and the like are more preferred. Among them, dimethylolpropionic acid and dimethylolbutanoic acid are particularly preferred in view of the availability of raw materials.

[0069] By using a polyester diol compound (e) containing a dicarboxylic acid having 10 or more carbon atoms (hereinafter referred to simply as "polyester diol compound (e)") in the production of the polyurethane compound (A) of the present invention, it is possible to achieve a high balance between sensitivity, heat resistance, chemical resistance, and flexibility. The upper limit of the carbon number is preferably 100 or less.

[0070] The polyester diol compound (e) has two hydroxyl groups in one molecule and an ester bond in the main skeleton.

[0071] Examples of the polyester diol compound (e) include diol dicarboxylate diols formed by ester-bonding a diol compound and a dicarboxylic acid. The diol compound is not particularly limited as long as it has two hydroxyl groups other than the unsaturated epoxy carboxylate compound (c) and the compound (d).

[0072] Examples of the diol dicarboxylate diols in which a diol compound and a dicarboxylic acid compound are linked by an ester bond include ethylene glycol sebacic acid polyester diol, propylene glycol sebacic acid polyester diol, butanediol sebacic acid polyester diol, neopentyl glycol sebacic acid polyester diol, methylpentanediol sebacic acid polyester diol, hexanediol sebacic acid polyester diol, ethylene glycol dimer acid polyester diol, propylene glycol dimer acid polyester diol, hexanediol dodecanedioate diol, ethylene glycol dodecanedioate diol, and ethylene glycol dodecanedioate diol.

[0073] Among these, as the polyester diol compound (e), sebacic acid polyester diol and dimer acid polyester diol are particularly preferred because they exhibit suitable flexibility.

[0074] The sebacic acid polyester diol is a reaction product formed by reacting sebacic acid with a diol, and the dimer acid polyester diol is a reaction product formed by reacting a dimer acid with a diol.

[0075] Dimer acids are dibasic acids, consisting of two monobasic fatty chains (typically with 18 carbon atoms) bonded together via a carbon-carbon covalent bond, resulting in a dibasic acid with a molecular weight doubled. Typical compounds are dimers derived from the polymerization of unsaturated fatty acids such as linoleic acid, oleic acid, elaidic acid, and pine fatty acid. Generally, since these unsaturated fatty acids with 18 carbon atoms are used as raw materials, the main component is a dicarboxylic acid with 36 carbon atoms.

[0076] Examples of the diol include ethylene glycol, 1,2-propylene glycol, 1,3-propane diol, 2-methyl-1,3-propane diol, 1,2-butane diol, 1,3-butane diol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol, 3-methyl-1,5-pentane diol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,5-pentane diol, 2-ethyl-2-butylpropane diol, 1,9-nonane diol, 2-methyloctanediol, and 1,10-decane diol.

[0077] The 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 below this range, the effect of imparting flexibility is low, while when it is above this range, the decrease in heat resistance is significant.

[0078] The compound (f) having two isocyanate groups in one molecule (hereinafter also referred to as "isocyanate compound (f)") used in the production of the polyurethane compound (A) of the present invention is used in the urethanization step with the hydroxyl groups of the unsaturated epoxycarboxylate compound (c), the compound (d), and the polyester diol compound (e) to impart suitable flexibility to the polyurethane compound (A).

[0079] Examples of the compound (f) include aliphatic linear diisocyanates, alicyclic diisocyanates, and aromatic isocyanates.

[0080] Examples of the aliphatic linear diisocyanates include hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.

[0081] Examples of the alicyclic diisocyanates include isophorone diisocyanate, norbornene diisocyanate, hydrogenated xylylenediisocyanate, and hydrogenated methylenebisphenylene diisocyanate.

[0082] Examples of the aromatic diisocyanates include toluene diisocyanate, xylylene diisocyanate, and methylene bisphenylene diisocyanate.

[0083] Among these, when it is desired to improve flexibility, aliphatic or alicyclic diisocyanates are more preferred, and aliphatic linear diisocyanates are particularly preferred.

[0084] The urethanization step is carried out by mixing a mixture of an unsaturated epoxycarboxylate compound (c), a compound having two hydroxyl groups and one or more carboxyl groups in one molecule (d), a polyester diol compound (e) of a dicarboxylic acid having 10 to 100 carbon atoms, and a compound having an isocyanate group (f).

[0085] In the production of the polyurethane compound (A), the value represented by (the number of moles of the unsaturated epoxycarboxylate compound (c) + the number of moles of the compound (d) + the number of moles of the polyester diol compound (e)) ÷ (the number of moles of the isocyanate compound (f)), i.e., the ratio of hydroxyl groups to isocyanate groups 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. Specifically, from the perspective of storage stability of the polyurethane compound (A), the urethanization step is fed so that the number of hydroxyl groups is at least greater than that of isocyanate groups, so that no isocyanate groups remain in the end.

[0086] If the molecular weight is greater than this range, the molecular weight of the obtained polyurethane compound (A) becomes too small, making it difficult to obtain a tough cured product. If the molecular weight is too small, the molecular weight of the obtained polyurethane compound (A) becomes too large, which may adversely affect the developability and the like.

[0087] In the production of the polyurethane compound (A) of the present invention, the preferred weight ratio of the unsaturated epoxycarboxylate compound (c), the compound (d), the polyester diol compound (e), and the isocyanate compound (f) is such that, based on 100 parts by weight of the total weight of the resin composition, the unsaturated epoxycarboxylate compound (c) is 5 to 65 parts by weight, 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 properties suitable for use as a resist material, which exhibits photopatterning and developability with alkaline aqueous solutions, can be obtained. Furthermore, a cured product having particularly high and well-balanced heat resistance, chemical resistance, and excellent flexibility can be obtained.

[0088] The urethanization step can be carried out without a solvent or by diluting the reaction with a solvent. When a solvent is used, it is not particularly limited as long as it is inert to the urethanization reaction.

[0089] When a solvent is used, its amount should be appropriately adjusted depending on the viscosity of the resulting resin and the intended use. It is preferably used so that the solids content is 99 to 30% by weight, and more preferably so that the solids content is 90 to 45% by weight. The solvent used in the carboxylation step may also be used as is, provided that the solvent is inert to both steps.

[0090] Examples of the solvent include the same solvents as those exemplified in the carboxylation step. Alternatively, the reactive compound (C) described below may be used alone or in combination as a solvent, as long as it is inert during the reaction. In this case, the curable composition may be used as is.

[0091] A thermal polymerization inhibitor or the like may also be used in the urethanization step, and the same compounds as those exemplified in the carboxylation step may be used.

[0092] The urethanization step can be carried out substantially without a catalyst, but a catalyst may be used to accelerate the reaction. When a catalyst is used, the amount of the catalyst used is approximately 0.01 to 1% by weight relative to the total weight of the reactants. Examples of such catalysts include common basic catalysts, such as Lewis base catalysts such as tin ethylhexanoate.

[0093] The reaction temperature of the urethanization step is more preferably 40 to 150° C., and the reaction time is more preferably 5 to 60 hours.

[0094] The urethanization step is terminated when almost no isocyanate groups remain. The endpoint is determined by observing the 2250 cm-1 wavelength of the isocyanate group using infrared absorption spectroscopy. -1 The peaks near the peak can be determined by titration according to JIS K1556:1968 or the like.

[0095] The polyurethane compound (A) of the present invention thus obtained preferably has a polystyrene-equivalent weight average molecular weight in GPC of 1,000 to 30,000, more preferably 3,000 to 20,000. If the molecular weight is less than this, the toughness of the cured product cannot be fully exhibited, while if the molecular weight is excessively greater than this, not only does the viscosity increase, making coating difficult, but also the developability tends to decrease.

[0096] Furthermore, the present invention may optionally contain an acid-modified polyurethane compound (B) obtained by reacting a polybasic acid anhydride (g) with a reactive polyurethane compound (A). This allows not only the compound (d) having two hydroxyl groups and one or more carboxyl groups per molecule, but also the acid value required for alkaline development to be appropriately added according to the desired resin properties. In the present invention, this reaction step is referred to as the acid addition step.

[0097] Next, the acid addition step is explained in detail. The acid addition step is a step of reacting the polybasic anhydride (g) with the hydroxyl group remaining after the urethanization reaction to introduce a carboxyl group via an ester bond. Therefore, the acid addition cannot be performed in an amount exceeding the equivalent of the hydroxyl group remaining after the urethanization step.

[0098] As the polybasic anhydride (g), a compound having a cyclic anhydride structure in one molecule can be exemplified, and from the viewpoints of alkali aqueous solution developability, heat resistance, hydrolysis resistance, and the like, succinic anhydride (SA), phthalic anhydride (PAH), tetrahydrophthalic anhydride (THPA), hexahydrophthalic anhydride (HHPA), itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride, or maleic anhydride is more preferable.

[0099] The acid addition step is performed by adding the polybasic anhydride (g) to the polyurethane compound (A). The amount of the polybasic anhydride (g) used can be appropriately changed depending on the set value of the polyurethane compound (A), that is, depending on the acid value derived from the compound (d), the amount of the remaining hydroxyl group, and the acid value required for the polyurethane compound (A).

[0100] When the polyurethane compound (A) and / or the acid-modified polyurethane compound (B) of the present application is used as a resist for an alkali developing type, the solid content acid value (according to JIS K5601-2-1:1999) of the finally obtained polyurethane compound is preferably set to 30 to 120 mg·KOH / g, and more preferably to 40 to 105 mg·KOH / g. When the solid content acid value is in this range, the active energy ray hardening type resin composition of the present application exhibits good developability by an alkali aqueous solution. That is, good solubility of the active energy ray non-irradiated portion and insolubility of the active energy ray irradiated portion can be balanced.

[0101] 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 with respect 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.

[0102] As the catalyst, triethylamine, benzyl dimethyl amine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, chromium octoate, zirconium octoate, and the like can be exemplified.

[0103] The acid addition step can be performed without a solvent or with a solvent diluted and reacted. When a solvent is used, the solvent is not particularly limited as long as it is inert in the acid addition reaction. In addition, when the urethanization step belonging to the previous step is performed using a solvent, the acid addition reaction can be performed without removing the solvent as long as it is inert to both reactions.

[0104] The amount of the solvent used should be appropriately adjusted depending on the viscosity and application of the resulting resin, but it is preferably used so that the solid content becomes 90 to 30% by weight, and is preferably used so that the solid content becomes 80 to 50% by weight.

[0105] The solvent may be the same solvent as exemplified in the carboxylation reaction and urethanization step.

[0106] Furthermore, as long as it is inert to the reaction, a reactive compound (C) described later may be used alone or in combination as a solvent. In this case, the composition may be used as it is as a curable composition.

[0107] In the acid addition step, a thermal polymerization inhibitor or the like may be used, and the same compounds as those exemplified in the carboxylation step and the urethanization step may be used.

[0108] The reaction in the acid addition step was terminated at a point where the acid value of the reactant fell within a range of plus or minus 10% of the set acid value while appropriately sampling.

[0109] The active energy ray-curable resin composition of the present invention contains a polyurethane compound (A) and / or an acid-modified polyurethane compound (B), and more preferably further contains a reactive compound (C) other than components (A) and (B).

[0110] Examples of the reactive compound (C) include radical-reactive acrylates, cation-reactive epoxy compounds, and vinyl compounds that are sensitive to both radicals and cations.

[0111] Examples of radical reaction type acrylates include monofunctional (meth)acrylates and polyfunctional (meth)acrylates.

[0112] 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, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and tetrahydrofuran (meth)acrylate.

[0113] Examples of the polyfunctional (meth)acrylates include butanediol di(meth)acrylate, hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(meth)acryloyloxyethyl isocyanate, polypropylene glycol di(meth)acrylate, epoxy adipate di(meth)acrylate, bisphenol ethylene oxide di(meth)acrylate, hydrogenated bisphenol ethylene oxide di(meth)acrylate, and the like. acrylate, bisphenol di(meth)acrylate, di(meth)acrylate of an ε-caprolactone adduct of hydroxypivalate neopentyl glycol, poly(meth)acrylate of a reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly(meth)acrylate, trimethylolpropane tri(meth)acrylate, triethylolpropane tri(meth)acrylate or its ethylene oxide adduct, pentaerythritol tri(meth)acrylate or its ethylene oxide adduct, pentaerythritol tetra(meth)acrylate or its ethylene oxide adduct, dipentaerythritol hexa(meth)acrylate or its ethylene oxide adduct, and the like.

[0114] The cation-reactive epoxy compounds include epoxy compound (a) and are not particularly limited as long as they are compounds 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-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl ester (e.g., "CYRACURE UVR-6110" manufactured by Union Carbide), 3,4-epoxycyclohexylethyl 3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (e.g., "ELR-4206" manufactured by Union Carbide), limonene dioxide (e.g., "CELLOXIDE 3000", etc.), allylcyclohexene dioxide, 3,4-epoxy-4-methylcyclohexyl-2-epoxypropane, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, 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.

[0115] Examples of the vinyl compounds include vinyl ethers, styrenes, and other vinyl compounds.

[0116] As the vinyl ethers, for example, ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, and the like can be exemplified.

[0117] As the styrenes, for example, styrene, methylstyrene, ethylstyrene, and the like can be exemplified.

[0118] As the other vinyl compounds, for example, triallyl isocyanurate, trimethylallyl isocyanurate, and the like can be exemplified.

[0119] In addition, as the reactive compound (C), other urethane acrylates than the polyurethane compound (A), the acid-modified polyurethane compound (B) which have both a functional group which can be sensitized to an active energy ray and a urethane bond in the same molecule can be used, polyester acrylates which have both a functional group which can be sensitized to an active energy ray and an ester bond in the same molecule, epoxy acrylates which have a functional group derived from an epoxy compound and which can be sensitized to an active energy ray, oligomers in which these bonds are used in combination, and the like can be used.

[0120] Among these, as the reactive compound (C), acrylates of a radical hardening type are preferable. When it belongs to a cationic reaction type, since a carboxylic acid and an epoxy group react, it is necessary to be made into a 2-liquid mixed type which is prepared at the time of use.

[0121] The active energy ray hardening type resin composition of the present application can also be added with other components as appropriate depending on the application.

[0122] The active energy ray hardening type resin composition of the present application contains 97 to 5% by weight, more preferably 87 to 10% by weight, of the polyurethane compound (A) and / or the acid-addition type polyurethane compound (B), and 3 to 95% by weight, more preferably 3 to 90% by weight, of the reactive compound (C) other than the component (A) and the component (B). Other components can be contained as necessary up to about 75% by weight for the purpose of adapting to various applications.

[0123] As the other components, a photopolymerization initiator, other additives, a pigment material, or a volatile solvent added for the purpose of adjusting the viscosity so as to impart coating suitability, and the like can be exemplified.

[0124] As the photopolymerization initiator which can be contained in the active energy ray hardening type resin composition of the present application, a radical type photopolymerization initiator, a cationic type photopolymerization initiator, and the like can be exemplified.

[0125] As free radical photopolymerization initiators, for example, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenones such as acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-one; 2-ethylanthraquinone, 2 Anthraquinones such as tert-butylanthraquinone, 2-chloroanthraquinone, and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthonone, 2-isopropylthioxanthonone, and 2-chlorothioxanthonone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 4,4'-dimethylaminobenzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, etc.

[0126] Examples of the cationic photopolymerization initiator include diazonium salts of Lewis acids, iodonium salts of Lewis acids, sulfonium salts of Lewis acids, phosphonium salts of Lewis acids, other halides, triazine initiators, borate initiators, and other photoacid generators.

[0127] Examples of the diazonium salt of a Lewis acid include p-methoxyphenyldiazonium fluorophosphonate and N,N-diethylaminophenyldiazonium hexafluorophosphonate (San-Aid SI-60L / SI-80L / SI-100L manufactured by Sanshin Chemical Industry Co., Ltd.).

[0128] Examples of the iodonium salt of a Lewis acid include diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate.

[0129] Examples of the sulfonium salt of a Lewis acid include triphenylsulfonium hexafluorophosphonate (such as Cyracure UVI-6990 manufactured by Union Carbide Co., Ltd.) and triphenylsulfonium hexafluoroantimonate (such as Cyracure UVI-6974 manufactured by Union Carbide Co., Ltd.).

[0130] Examples of the phosphonium salt of a Lewis acid include triphenylphosphonium hexafluoroantimonate.

[0131] Examples of other halides include 2,2,2-trichloro-[1-4′-(dimethylethyl)phenyl]ethanone (Trigonal PI manufactured by AKZO, etc.), 2,2-dichloro-1-(4-phenoxyphenyl)ethanone (Sandray 1000 manufactured by Sandoz, etc.), and α,α,α-tribromomethylphenylsulfone (BMPS manufactured by Seishi Chemical Co., Ltd., etc.).

[0132] Examples of the triazine initiator include 2,4,6-tris(trichloromethyl)triazine, 2,4-bis(trichloromethyl)-6-(4'-methoxyphenyl)triazine (Triazine A manufactured by Panchim Co., Ltd., etc.), 2,4-bis(trichloromethyl)-6-(4'-methoxyphenyl)triazine (Triazine PMS manufactured by Panchim Co., Ltd., etc.), 2,4-bis(trichloromethyl)-6-piperidyltriazine (Triazine PP manufactured by Panchim Co., Ltd., etc.), 2,4-bis(trichloromethyl)-6-(4'-methoxynaphthyl)triazine (Triazine B manufactured by Panchim Co., Ltd., etc.), 2-[2'-(5"-methylfuryl)ethylidene]-4,6-bis(trichloromethyl)-s-triazine (SANWA Chemical Co., Ltd.), 2-(2'-furylidene)-4,6-bis(trichloromethyl)-s-triazine (Sanwa Chemical Co., Ltd.), and the like.

[0133] Examples of borate-based initiators include NK-3876 and NK-3881 (all manufactured by Japan Photochromic Co., Ltd.).

[0134] Examples of other photoacid generators include 9-phenylacridine, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2-biimidazole (biimidazole manufactured by Kurokin Chemicals, etc.), 2,2-azobis(2-amino-propane) dihydrochloride (V50 manufactured by Wako Pure Chemical Industries, Ltd., etc.), 2,2-azobis[2-(imidazolin-2-yl)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)phenyl] iron (II) (Irgacure 261 manufactured by Ciba Geigy, etc.), bis(η-5-cyclopentadienyl)bis[2,6-difluoro-3-(1H-pyridin-1-yl)phenyl]titanium (Ciba Geigy CGI-784, etc.

[0135] In addition, azo initiators such as azobisisobutyronitrile, heat-sensitive peroxide-based free radical initiators such as benzoyl peroxide, etc. can also be used in combination. In addition, both free radical and cationic initiators can be used in combination, and one type of each initiator can be used alone or in combination of two or more types.

[0136] Among these, in consideration of the properties of the polyurethane compound (A) of the present invention, a radical photopolymerization initiator is particularly preferred.

[0137] The active energy ray-curable resin composition of the present invention may contain a curing agent as appropriate depending on the intended use. This curing agent is used, particularly in materials intended for electrical insulation, to obtain a strong cured film by reacting with the acidic groups contained therein.

[0138] Examples of the curing agent include epoxy compounds other than the reactive compound (C). Among them, epoxy compounds containing two or more epoxy groups per molecule are particularly preferred. This is because they can produce a stronger cured product compared to using monofunctional epoxy compounds. Furthermore, the epoxy equivalent weight 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. If the epoxy equivalent weight is below this range, the resulting cured product tends to be brittle, while if it is above this range, the resulting cured product tends to be weak due to the reduced number of crosslinking sites.

[0139] The epoxy compound can be arbitrarily selected depending on the intended use and required properties of the cured product, and any known epoxy compound can be used.

[0140] Examples of the monofunctional epoxy compound include phenyl glycidyl ether and glycidyl (meth)acrylate.

[0141] Examples of epoxy compounds having two or more epoxy groups in the molecule include phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, trishydroxyphenylmethane-type epoxy resins, dicyclopentadienephenol-type epoxy resins, bisphenol-A-type epoxy resins, bisphenol-F-type epoxy resins, biphenol-type epoxy resins, bisphenol-A novolac-type epoxy resins, naphthalene-skeleton-containing epoxy resins, glyoxal-type epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, and the like.

[0142] Examples of the phenol novolac epoxy resin include EPICLON N-770 (manufactured by DIC Corporation), DEN438 (manufactured by Dow Chemical Corporation), jER154 (manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-201, and RE-306 (all manufactured by Nippon Kayaku Co., Ltd.).

[0143] 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 Co., Ltd.), and ESCN-195 (manufactured by Sumitomo Chemical Industries, Ltd.).

[0144] Examples of the trishydroxyphenylmethane epoxy resin include EPPN-503, EPPN-502H, and EPPN-501H (all manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Co., Ltd.), and jER E1032H60 (manufactured by Japan Epoxy Resin Co., Ltd.).

[0145] As this dicyclopentadienephenol type epoxy resin, EPICLON EXA-7200 (made by DIC Corporation) and TACTIX-556 (made by Dow Chemical Company) etc. are mentioned, for example.

[0146] Examples of the bisphenol-type epoxy resin include bisphenol-A epoxy resins such as jER828 and jER1001 (all manufactured by Japan Epoxyresin Co., Ltd.), UVR-6410 (manufactured by Union Carbide Co., Ltd.), DER-331 (manufactured by Dow Chemical Co., Ltd.), YD-8125 (manufactured by Tohto Kasei Co., Ltd.), NER-1202, and NER-1302 (all manufactured by Nippon Kayaku Co., Ltd.); and bisphenol-F epoxy resins such as UVR-6490 (manufactured by Union Carbide Co., Ltd.), YDF-8170 (manufactured by Tohto Kasei Co., Ltd.), NER-7403, and NER-7604 (all manufactured by Nippon Kayaku Co., Ltd.).

[0147] 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.), bixylenol type epoxy resins such as YX-4000 (manufactured by Japan Epoxy Resin Co., Ltd.), and YL-6121 (manufactured by Japan Epoxy Resin Co., Ltd.).

[0148] Examples of the bisphenol A novolac-type epoxy resin include EPICLON N-880 (manufactured by DIC Corporation) and jER E157S75 (manufactured by Japan Epoxy Resin Co., Ltd.).

[0149] Examples of the naphthalene skeleton-containing epoxy resin include NC-7000 (manufactured by Nippon Kayaku Co., Ltd.) and EXA-4750 (manufactured by DIC Corporation).

[0150] Examples of the glyoxal-type epoxy resin include GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.).

[0151] As this alicyclic epoxy resin, EHPE-3150 (made by Daicel Chemical Industries, Ltd.) etc. are mentioned, for example.

[0152] Examples of the heterocyclic epoxy resin include TEPIC (manufactured by Nissan Chemical Industries, Ltd.).

[0153] Among them, biphenol-type epoxy resins are particularly effective in terms of flexibility, and examples thereof include NC-3000, NC-3000-H, and NC-3000-L.

[0154] When the epoxy compound is included, its suitable blending amount is approximately 5 to 80% by weight, more preferably approximately 10 to 70% by weight, of the solids content of the active energy ray-curable resin composition of the present invention. A blending amount less than this may result in a weak cured product. A blending amount exceeding this amount may adversely affect curability due to balance issues with the epoxy curing agent described below.

[0155] Examples of other additives that may be contained in the active energy ray-curable resin composition of the present invention include heat-curing catalysts such as melamine, thixotropy-imparting agents such as aerosil, silicone-based or fluorine-based leveling agents or defoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, stabilizers, antioxidants, and flame retardants for imparting flame retardancy.

[0156] In particular, when used as a film-forming material for electrical insulation, it is more preferred to use a flame retardant in combination. Preferred flame retardants include commonly known flame retardants, and suitable examples include brominated epoxy resins, bromodiphenyl ether and other halogen-based flame retardants, phosphazene resins, triphenyl phosphate and other phosphate resins, dihydro-9-oxa-phosphaphenanthrene-10-oxide derivatives and other organic phosphorus-based flame retardants, magnesium hydroxide and other metal hydroxide-based flame retardants, and red phosphorus, antimony trioxide and other inorganic flame retardants.

[0157] Examples of the pigment material that may be contained in the active energy ray-curable resin composition of the present invention include coloring pigments for the purpose of coloring and extender pigments not for the purpose of coloring.

[0158] Examples of the coloring pigment include organic pigments such as phthalocyanine-based, azo-based, and quinacridone-based pigments, and inorganic pigments such as carbon black and titanium oxide.

[0159] Examples of the extender pigment include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silicon oxide, and clay.

[0160] Furthermore, resins that are unreactive to active energy rays (so-called inert polymers) may be included. Examples of such resins that may be included in the active energy ray-curable resin composition of the present invention include epoxy resins other than the epoxy resin used as the curing agent, phenol resins, polyurethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, styrene resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified forms thereof. These resins are preferably used in an amount of up to 40% by weight in the active energy ray-curable resin composition.

[0161] In particular, when the polyurethane compound (A) and / or the acid-modified polyurethane compound (B) are used in solder resist applications, they are preferably used in combination with an epoxy resin. The carboxyl groups remaining after curing by active energy rays are further carboxylated to form a strong crosslinked structure, resulting in excellent water resistance and hydrolysis resistance of the cured product.

[0162] The active energy ray-curable resin composition of the present invention may contain a volatile solvent in an amount up to 50% by weight (more preferably 35% by weight) in the resin composition for the purpose of adjusting the viscosity according to the intended use.

[0163] The active energy ray-curable resin composition of the present invention is readily cured by active energy rays. Examples of active energy rays include electromagnetic waves such as ultraviolet rays, visible light, infrared rays, X-rays, gamma rays, and laser beams, and particle rays such as alpha rays, beta rays, and electron beams. Considering the preferred applications of the present invention, ultraviolet rays, laser beams, visible light, and electron beams are particularly preferred.

[0164] The present invention includes using the active energy ray-curable resin composition as a film-forming material for coating a substrate surface. Specifically, the film-forming material includes, for example, ink materials such as gravure inks, flexographic inks, screen inks, and overprint inks; coating materials such as hard coats, top coats, overprint varnishes, and clear coats; adhesive materials such as adhesives or pressure-sensitive adhesives for lamination or optical discs; and resist materials such as solder resists, etch resists, and micromachining resists.

[0165] The film-forming material is also a so-called dry film in which the film-forming material is temporarily applied to a releasable substrate to form a film, and then bonded to the original target substrate to form a film.

[0166] The present application also includes the use of the active energy ray-curable resin composition as a film-forming material for the purpose of electrical insulation. That is, the film-forming material is a material such as a solder resist material for a circuit board, an insulating mold material, an interlayer insulating material, a semiconductor protective film material, a wiring covering material, and the like, which requires electrical insulation.

[0167] The present application also includes the use of the active energy ray-curable resin composition as an active energy ray-sensitive resist material, which is a material in which a film layer of the composition is formed on a substrate, and then, a portion thereof is irradiated with an active energy ray such as ultraviolet rays, to perform drawing using the difference in properties between the irradiated portion and the non-irradiated portion. That is, the irradiated portion or the non-irradiated portion is removed by some method, such as dissolution with a solvent or an alkaline solution, and the like, and drawing is performed.

[0168] The present application also includes the use of the active energy ray-curable resin composition for a permanent resist. The permanent resist is a resist material that is not used on the premise that it is peeled off after drawing, but is continuously maintained for its purpose and function until it is actually used as a substrate.

[0169] The active energy ray-curable resin composition of the present application for a resist can be applied to various materials that must be patterned, among which there are particularly a solder resist material, an interlayer insulating material for a build-up method, and the like, and can be further utilized as an optical waveguide for electric / electronic / optical substrates such as printed circuit boards, optoelectronic substrates, and optical substrates, and the like.

[0170] For particularly suitable uses, the characteristics of heat resistance and good developability can be utilized, and the composition can be used for a wide range of uses requiring a resin composition, such as a photosensitive film, a photosensitive film with a support, an insulating resin sheet such as a prepreg, a circuit board (for a build-up board, for a multilayer printed circuit board, and the like), a solder resist, an underfill material, a die bonding material, a semiconductor packaging material, a via resin, a part embedding resin, and the like. Among these, the composition is more preferably used as a resin composition for an insulating layer of a multilayer printed circuit board (a multilayer printed circuit board in which a hardened product of a photosensitive resin composition is used as an insulating layer), a resin composition for an interlayer insulating layer (a multilayer printed circuit board in which a hardened product of a photosensitive resin composition is used as an interlayer insulating layer), and a resin composition for plating film formation (a multilayer printed circuit board in which a plating film is formed on a hardened product of a photosensitive resin composition).

[0171] In addition, the composition can exhibit good developability even in a high pigment concentration, and can be suitably used for a color resist, a resist material for a color filter, and particularly a black matrix material and the like.

[0172] Furthermore, by utilizing the property of obtaining a soft and tough cured product, the effects of the present invention can be maximized when used in applications where flexibility is required, such as insulating materials for flexible substrates. This is a suitable application.

[0173] There are no particular restrictions on the method for forming the film, and various coating methods such as gravure printing such as gravure, relief printing such as flexographic printing, stencil printing such as screen printing, offset printing such as lithography, roll coater, knife coater, die coater, curtain coater, and spin coater can be arbitrarily used.

[0174] The present invention also includes a cured product obtained by curing the active energy ray-curable resin composition by irradiating it with active energy rays.

[0175] [Example]

[0176] The present invention will be described in more detail below with reference to the following examples, but the present invention is not limited to these examples. In the examples, unless otherwise specified, % represents weight %.

[0177] The softening point and epoxy equivalent are measured under the following conditions.

[0178] 1) Epoxy equivalent (WPE): measured by a method in accordance with JIS K 7236:2001.

[0179] 2) Total chlorine content: measured by a method in accordance with JIS K 7243-3:2005.

[0180] 3) Acid value: measured by a method in accordance with JIS K 0070:1992.

[0181] 4) The measurement conditions of GPC are as follows.

[0182] Instrument: TOSOH HLC-8220GPC

[0183] Column: TSKGEL Super HZM-N

[0184] Mobile phase: THF (tetrahydrofuran); 0.35 ml / min, temperature 40°C

[0185] Detector: Differential refractometer

[0186] Molecular weight standard: polystyrene

[0187] (Synthesis Example 1): Preparation of unsaturated epoxy carboxylate compound (c) (carboxylic acid esterification step)

[0188] 1840 g of bisphenol A-type epoxy resin (RE-310S, WPE = 184 g / eq, manufactured by Nippon Kayaku Co., Ltd.) as the epoxy compound (a), 720 g of acrylic acid (abbreviated as AA, Mw = 72) as the compound (b), 30 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate (abbreviated as PGMAc) as a solvent were added so as to give a solid content of 80%, and the mixture was reacted at 100°C for 24 hours to obtain a solution of an unsaturated epoxy carboxylate compound (c).

[0189] The reaction was completed when the acid value, calculated as solids, reached 1.8 mg·KOH / g. This acid value was converted to the acid value of the solids measured in the reaction solution. The epoxy value was also measured and found to be 13,000 g / eq, confirming that the epoxy groups had fully reacted.

[0190] (Example 1): Preparation of polyurethane compound (A) (urethanization step)

[0191] To a reaction vessel, the unsaturated epoxycarboxylate compound (c) solution obtained in Synthesis Example 1 was added in the amount listed in Table 1 (the listed values ​​are solid content conversion values), dimethylolpropionic acid as compound (d) was added in the amount listed in Table 1, the polyester diol listed in Table 1 as polyester diol compound (e) was added in the amount listed in Table 1, and 47.5 g of propylene glycol monomethyl ether acetate (abbreviated as PGMAc) as a solvent was added so that the solid content of the polyurethane compound (A) would be 50%, and the mixture was stirred and dissolved.

[0192] Separately, 0.5 g of tin octylate as a catalyst and 0.1 g of hydroquinone as a thermal polymerization inhibitor were added, and the mixture was heated to 100°C. Subsequently, hexamethylene diisocyanate, as the isocyanate compound (f) in the amount listed in Table 1, was added using a dropping funnel to allow the reaction to proceed. After the addition was complete, the reaction was continued for 10 hours. Infrared absorption spectroscopy confirmed the absence of an absorption peak derived from an isocyanate group, thereby obtaining a polyurethane compound (A).

[0193] (Comparative Example 1): Preparation of a comparative polyurethane compound

[0194] The polyurethane compounds listed in Table 1 were prepared in the same manner as in Example 1 using the carboxylate compound (c) prepared in Synthesis Example 1.

[0195] Example (c) (d) (e) (f) (c+d+e) / f Example 1-1 15.2g 9.8g URIC SE-2013C 28.6g 18.1g 1.3 Example 1-2 21.2g 9.4g URIC-3091U 19.9g 20.8g 1.3 Examples 1-3 14.7g 9.3g PRIPLAST XL 101 29.3g 17.9g 1.3 Comparative Example 1-1 21.3g 9.4g PCDLT-6001 19.7g 20.8g 1.3

[0196] Abbreviations in the table:

[0197] (c+d+e) / f: the ratio of the total molar number of hydroxyl groups to the total molar number of isocyanate groups in the reaction system

[0198] URIC SE-2013C: Sebacic acid polyester polyol (manufactured by Ito Oil Manufacturing Co., Ltd.) with an average molecular weight of 2000

[0199] URIC-3091U: Sebacic acid polyester polyol (manufactured by Ito Oil Manufacturing Co., Ltd.) with an average molecular weight of 1000

[0200] PRIPLAST XL 101: Dimer acid polyester polyol (manufactured by CRODA Co., Ltd.) with an average molecular weight of 2200

[0201] PCDLT-6001: Polycarbonate diol (manufactured by Asahi Kasei Co., Ltd.) with an average molecular weight of 1000

[0202] (Example 2): Preparation of acid-modified polyurethane compound (B) (acid addition step)

[0203] To a reaction vessel, the polyurethane compound (A) obtained in Example 1 and the PGMAc solution were added in the amounts listed in Table 2. Furthermore, the polyanhydride (g) listed in Table 2 was added in the amounts listed in Table 2 (calculated to give a solids acid value of 90 mg·KOH / g). PGMAc was added as a solvent to achieve a final solids content of 50%, i.e., an equal weight of PGMAc and anhydride was added. 0.2 g of triethylamine was added as a catalyst and stirred to dissolve the mixture.

[0204] After dissolution, the mixture was heated to 100° C. while stirring and reacted for 50 hours to obtain an acid-modified polyurethane compound (B). After completion of the reaction, the acid value was measured to confirm the completion of the reaction.

[0205] (Comparative Example 2): Preparation of an acid-modified polyurethane compound for comparison

[0206] Using the polyurethane compound prepared in Comparative Example 1, a urethanization step was performed in the same manner as in Example 2 to prepare an acid-modified urethane compound.

[0207] Example (A) (g) AV Mw(k) Example 2-1 Example 1-1 71.7 gg SA 0.7g 60 9.8 Example 2-2 Example 1-2 71.3g SA 0.7g 60 9.5 Example 2-3 Example 1-3 71.22g SA 0.7g 60 10.2 Comparative Example 2-1 Comparative Example 1-1 71.22 g SA 0.7g 60 10.7

[0208] Abbreviations in the table:

[0209] AV: Acid value of solid content (mg·KOH / g): The measurement is performed as a solution and converted to a value of solid content.

[0210] Mw: weight average molecular weight measured using gel permeation chromatography (polystyrene standard conversion value)

[0211] SA: Succinic anhydride (manufactured by Shin Nippon Chemical Co., Ltd.)

[0212] (Example 3): Adjustment and evaluation of solder resist material composition for flexible substrates

[0213] 6.0 g of the acid-modified polyurethane compound (B) obtained in Example 2, 1.2 g of DPCA-20 (trade name: Nippon Kayaku Co., Ltd.) as a reactive compound (C), 0.27 g of IRGACURE 907 (Ciba Specialty Chemicals) and 0.01 g of KAYACURE DETX-S (Nippon Kayaku Co., Ltd.) as photopolymerization initiators, 0.01 g of TPP as a thermal curing catalyst, and diethylene glycol monomethyl ether monoacetate as a concentration adjustment solvent were added to adjust the solid content concentration to 60%. The mixture was then uniformly dispersed to obtain a resist material resin composition.

[0214] Describe in detail each item of the assessment project.

[0215] Sealing bending resistance evaluation (abbreviated as: softness in the table)

[0216] A bisphenol A epoxy resin (trade name: YD-134, manufactured by Nippon Steel & Sumitomo Metal Corporation) was added to the resist material composition as a curing component to a ratio of 120% relative to the carboxyl group. The resulting composition was applied to a polyimide film, KAPTON 100H (manufactured by DU PONT-TORAY), using an applicator to a thickness of 20 μm. The film was then dried in a hot air dryer at 80°C for 60 minutes.

[0217] Next, an ultraviolet irradiator (GS YUASA: CS 30L-1) was used to irradiate the sample at 500 mJ / cm 2 Then, it was cured in an oven at 150°C for 30 minutes.

[0218] The cured film was subjected to a 180-degree roll-seal bending test, and the number of times cracks were generated in the cured film was evaluated.

[0219] Evaluation of development properties (abbreviated as development properties in the table)

[0220] The developing property was evaluated by spray developing the coating film before ultraviolet irradiation using a 1% sodium carbonate aqueous solution as a developer (unit: seconds) based on the time required for the coating film to completely dissolve, i.e., the so-called break time.

[0221] ×··Swelling and peeling

[0222] Welding heat resistance evaluation (abbreviated as: heat resistance in the table)

[0223] The test was conducted in accordance with JIS C-5016 10.3: 1994. A patterned film with a resist-cured film was dipped three times in a heated solder bath. After immersion, the flexible substrate was subjected to a cross-cut peel test to evaluate peeling.

[0224] Soldering bath temperature: 260°C

[0225] One dipping time: 60 seconds

[0226] Evaluation criteria: The number of chessboard squares (100) is used as the denominator, and the number of remaining squares is used as the numerator.

[0227] [Table 3]

[0228] Example Compound (A) Softness Developability Heat resistance Example 3-1 Example 2-1 27 10 100100 Example 3-2 Example 2-2 20 10 100 / 100 Example 3-3 Example 2-3 23 20 100 / 100 Comparative Example 3-1 Comparative Example 2-1 12 × 100 / 100

[0229] From these results, it was found that the active energy ray-curable resin composition using the acid-modified polyurethane compound (B) of the present invention can provide a cured film excellent in curling and folding resistance.

[0230] In view of such characteristics, it was 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.

[0231] (Industrial Applicability)

[0232] The polyurethane compound (A) of the present invention, the composition containing the polyurethane compound (A), and the cured product thereof are materials having excellent flexibility and can be suitably used as resist materials such as resist materials for flexible substrates, color resists for flexible displays, and spacer resists.

Claims

1. 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) which is a dimer acid polyester diol, 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 one or more ethylenically unsaturated groups and one carboxyl group in one molecule with an epoxy compound (a) having two epoxy groups in one molecule.

2. An acid-modified polyurethane compound (B) obtained by reacting a polybasic acid anhydride (g) with the polyurethane compound (A) according to claim 1. 3 . An active energy ray-curable resin composition comprising the polyurethane compound (A) according to claim 1 or the polyurethane compound (B) according to claim 2 . 4 . The active energy ray-curable resin composition according to claim 3 , further comprising 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 claim 3 or 4, which is a forming material. 6 . The active energy ray-curable resin composition according to claim 5 , which is a film-forming material. 7 . The active energy ray-curable resin composition according to claim 3 , which is a resist material. 8 . A cured product comprising the active energy ray-curable resin composition according to claim 3 .

9. An article protectively covered with the hardened article according to claim 8.

10. A resin composition comprising a polyurethane compound (B) and a reactive compound (C), wherein: The reactive compound (C) is a multifunctional (meth)acrylate.

11. A resin composition comprising a polyurethane compound (A) and a reactive compound (C), wherein: The polyurethane compound (A) is obtained by reacting an unsaturated epoxycarboxylate compound (c), a compound (d) having two hydroxyl groups and one or more carboxyl groups in one molecule, an ethylene glycol dimer acid polyester diol or a propylene glycol dimer acid polyester diol (e), and a compound (f) having two isocyanate groups in one molecule. The unsaturated epoxycarboxylate compound (c) is obtained by reacting a compound (b) having one or more ethylenically unsaturated groups and one carboxyl group in one molecule with an epoxy compound (a) having two epoxy groups in one molecule. When the total weight of the resin composition is set to 100 parts, the isocyanate compound (f) is 20 to 40 parts by weight, The reactive compound (C) is a multifunctional (meth)acrylate.