TW201102756A - Reactive urethane compound, actinic-energy-ray-curable resin composition containing same, and use thereof - Google Patents

Abstract

Provided are materials characterized by being capable of photopattering or by having flexibility required of flexible substrates, etc. and being less susceptible to alteration/discoloration even when exposed to high temperatures or light, while retaining heat resistance and long-lasting high insulating properties and retaining the intact basic properties of solder resists, color resists, or the like. One of the materials is a reactive polyurethane compound (A) obtained by reacting an epoxy carboxylate compound (a), a compound (b) having two hydroxy groups and one or more carboxy groups in the molecule, and a compound (c) containing no aromatic ring and having two isocyanate groups in the molecule, the compound (a) being obtained by reacting an epoxy resin (i) containing no aromatic ring and having two epoxy groups in the molecule with a compound (ii) having one or more polymerizable ethylenically unsaturated groups and one or more carboxy groups in the molecule. Others are a product of acid modification of the compound (A), an actinic-energy-ray-curable resin composition containing the compound (A) or the modification product, and a cured object formed from the composition.

Description

201102756 VI. Description of the Invention: [Technical Field] The present invention relates to a hardened film which is difficult to be modified or discolored by heat or light and which is strong but soft, and which can be developed by a lamp Photopatterned reactive polyamine phthalate compound σ product and active energy ray-curable resin composition containing the same, cured product thereof, and use thereof. [Pre-Technology] In order to achieve a reduction in the size and weight of the mobile device and an increase in the communication speed, it is required to increase the accuracy and density of the printed wiring board, and the requirements for the film forming material of the coated circuit, that is, the so-called solder resist. It is also getting higher and higher. Specifically, it is required to withstand the heat resistance of 70 pieces of heat generated during the manufacture of a substrate using solder or the like, the reliability of maintaining high insulation for a long period of time, and the performance of chemical treatment such as mineralization. More than the previous requirements, a material for forming a film having a more cured property was sought, but no material satisfying the properties was found. Further, in recent years, the use of flexible printed wiring boards such as flexible substrates has also expanded. In the case of a flexible substrate, the protection of the circuit is usually performed by laminating a so-called cover film, but there is a problem in productivity in terms of time consuming and the like. In response to this, an attempt has been made to use a developable solder resist type film forming material 'but it has not been found that the film is straight and can also follow the bending while satisfying other necessary characteristics. In addition, the LED (Light Emittmg is used as the light source), but in the printed wiring board on which the LED element is mounted, in order to more effectively illuminate the light, the 148718.doc 201102756 white is usually used on the mounting substrate. The film forming material, which is a material for forming a film, is desirably satisfying the above-mentioned characteristics required for the solder resist, and does not cause a change in coloring or the like during the component mounting process and long-term use, but has not been found to be practical. In addition, in the color resist used for manufacturing a color filter for a so-called liquid crystal display or an organic EL (Eleetr® Luminescence) display, as in the case of a printed wiring board, there is also a manufacturing process. Heat treatment at the time, or heat or light during use, resulting in deterioration or discoloration, resulting in deterioration of color reproducibility. Heart, requirement - a pattern that can be finely patterned by inhomogeneous development without discoloration Adhesive for adhesives. Further, for color filters, flexible color filters are required to obtain a flexible display. Therefore, the same flexibility as the flexible substrate is required. However, if an epoxy acrylate having an aromatic ring used in the conventional solder resist and color resist is used, heat treatment such as soldering during component mounting is required. Or the effect of heat or light generated by the LED element or the backlight when used as an actual substrate, the resist resin itself is deteriorated and discolored, and there is a problem in practical use. In order to solve the above various problems', Patent Document 1 In the case of 2, etc., attempts have been made to use an acrylic copolymer and a photoreactive compound as a composition, and to impart a graftability to a polymerizable ethylenically unsaturated group in order to impart reactivity to an acrylic copolymer. However, these materials are difficult to obtain sufficient sensitivity to light patterning, and do not have sufficient heat resistance, so heat resistance during heat treatment such as soldering of components and reliability of long-term insulation insulation are Insufficient. 148718.doc 201102756 In addition to this, an attempt was made to use an epoxy resin with an alicyclic structure to derive reactivity. An oxycarboxylate compound is used as a white solder resist (see Patent Document 3). However, this material lacks flexibility and is difficult to use for a flexible substrate. Patent Documents 4 and 5 and the like a reactive urethane acrylate compound containing a difunctional epoxy carboxylate compound containing an aromatic ring, a compound having two hydroxyl groups and one or more carboxyl groups in one molecule, and a diisocyanate compound is used for the solder resist, however The use of a reactive urethane compound derived from an epoxy resin containing no aromatic ring in a solder resist or the like is not described. [Prior Art Document] [Patent Document] [Patent Document 1] [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The case can be used for heat resistance which can withstand the heat generation of the substrate during the manufacture of the substrate such as solder, and the reliability of the long-term maintenance of high insulation, and the resistance to chemical treatment such as forging. Moreover, the material has the flexibility to be used for a flexible substrate, such as 148718.doc 201102756, and has the properties of being modified, discolored, or altered due to the color and the light. [Means for Solving the Problems] The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, (4) & an epoxy phenolic acid compound obtained by an epoxy resin containing no aromatic ring, and two molecules in the molecule a reactive polyurethane compound obtained from a compound having one or more slow groups and a compound having two isocyanate groups in the molecule, an acid-modified compound thereof, and an active energy ray-curable resin containing the same The composition, and the cured product thereof, complete the present invention. That is, the present invention relates to a reactive polyamine phthalate compound (A) obtained by reacting the following compound: an epoxy oxalate compound (a) which is free of an aromatic ring and has two in one molecule An epoxy group epoxy resin (oxime), which is obtained by reacting a compound (ii) having one or more polymerizable ethylenically unsaturated groups and one or more retarding groups in one molecule; and a compound having two in one molecule a hydroxyl group and more than one carboxyl group; and a compound (c) which does not contain an aromatic ring and has two isocyanate groups in one molecule. The present invention further relates to an acid-modified reactive polyurethane compound (B) which is obtained by reacting a polybasic acid anhydride (d) with the above-mentioned reactive polyurethane compound (A). The present invention further relates to an active energy ray-curable resin composition comprising the above reactive polyamine phthalate compound (A) and/or the above acid-modified reactive polyamine phthalate compound (B). Further, the present invention relates to the above active energy ray-curable resin composition containing the reactive compound (C) other than the compound (A) and the compound (B). 148718.doc 201102756 The present invention further relates to the above active energy ray-curable resin composition containing a coloring pigment. Further, the present invention relates to the above-mentioned active energy ray-curable resin composition which is a material for translucent molding. Further, the present invention relates to the above active energy ray-curable resin composition which is a material for forming a colored film. Further, the present invention relates to the above active energy ray-curable resin composition which is a material for forming a light-transmitting film. Further, the present invention relates to the above active energy ray-hardening resin composition which is a material for a resist. Further, the present invention relates to a cured product of the above active energy ray-curable resin composition. Further, the present invention relates to an article coated with a cured product of the above active energy ray-curable resin composition. [Effects of the Invention] The reactive polyurethane sulfonate compound of the present invention, the acid-modified compound thereof, and the active energy ray-curable resin composition containing the same, and the cured product thereof can be patterned into a calender, and can be used to have resistance &quot;Materials for solder resists that are made of solder-based substrate=2, heat resistance during component heating, long-term dimensionality (4) high insulation, and resistance to chemical treatment such as plating The far material has the properties of being able to be used for the flexibility and the discoloration of the flexible substrate and the like without impairing the basic characteristics of the color resist or the like. In addition, it is possible to provide a white solder resist 148718.doc 201102756 which can be colored even if it is used for a long period of time. For example, it can be suitably used as a solder resist for an LED mounting substrate or the like used as a light source. Further, it is also suitable for use as a resist adhesive for a color filter such as a liquid crystal display or an organic EL display, and an optical waveguide forming material, by making full use of the feature that is difficult to color. Further, since it is also flexible, it is possible to maximize the effects of the present invention by using it for a flexible substrate. [Embodiment] The reactive polyurethane compound (A) of the present invention is obtained by reacting the following compound: an epoxy carboxylate compound (a) which does not contain an aromatic ring and has two in one An epoxy group epoxy resin (i), which is obtained by reacting a compound (11) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule; and compound (b), which is in one molecule And having two hydroxyl groups and one or more carboxyl groups; and compound (c) which does not contain an aromatic ring and has two isocyanate groups in one molecule. That is, the reactive polyamine phthalate compound (A) of the present invention can be obtained by the following two reaction steps: an epoxy carboxylic acid esterification step of reacting the epoxy resin (i) with the compound (ii) to obtain a ring. An oxycarboxylate compound (a); and an urethanation step of the epoxy carboxylic acid ester compound (a), a compound (b) having two radicals and one or more carboxyl groups in one molecule, and The compound (c) having an aromatic ring and having two isocyanate groups in one molecule is reacted. The epoxy carboxylic acid ester compound (a) obtained by the epoxy carboxylic acid esterification step has two polymerizable ethylenically unsaturated groups in one molecule by reacting the epoxy resin (1) with the compound (ii). Two bases derived from epoxy resin (i). Then, in the amidoximation step, a compound having an isocyanate group 148718.doc 201102756 (C) 'p-oxycarboxylic acid ester compound (4), and a molecule having two hydroxyl groups and more than one carboxyl group The hydroxyl group of the compound (b) is subjected to carboxylic acid fortification to thereby obtain a reactive polyamine phthalate compound (A). The epoxy resin (1) which does not contain an aromatic ring and has two cyclic mercapto groups in one molecule used in the epoxy carboxylic acid esterification step is a characteristic constituent element of the present invention. Since aryl (4) is not contained, it is possible to suppress modification or discoloration of heat or light, and since it has two epoxy groups, it is possible to use a hydroxy group formed by esterification of an epoxy carboxylic acid. At this time, if a monofunctional epoxy compound is used, the molecular weight of the obtained reactive polyurethane compound (A) is not obtained, and if two or more epoxy compounds are used, a multi-branched structure is formed. Therefore, it is difficult to obtain a better hardened physical property. The epoxy resin (1) is preferably a compound represented by the formula (1). XRX (1) (wherein X represents a functional group having an epoxy group, R represents an organic residue directly bonded or not containing an aromatic ring) 乍 is a functional group having an epoxy group in the formula (I) For example, glycidol can be used, and an aliphatic substituent having an epoxy group such as A-»3 diglycidyl acetate; Ioxime% hexyl ether group, 3,4-epoxycyclohexylcarboxylate group An alicyclic substituent having a cyclic lacto group. s乍 is an organic residue which does not contain an aromatic ring in the formula (1), and is not particularly limited as long as it does not contain an aromatic compound. The compound represented by the formula (I) is, for example, a diol compound or a dicarboxylic acid 4 conjugate or the like: &amp; - epichlorohydrin, glycidol 'cyclohexene decanoic acid, cyclohexene 1487 丨 8 .d〇c 201102756 When the compound obtained by the reaction of the alcohol 4, R becomes a residue of the diol compound, the dicarboxylic acid compound or the like. Examples of the organic snail tomb that does not contain an aromatic ring include a linear hydrocarbon residue, a % hydrocarbon residue, a polyglycerol residue, a jujube ruthenium polyester diol residue, and a ring. Ether diol residue and the like. As a linear hydrocarbon residue, for example, an ethylene glycol residue, a propylene glycol residue, a butanediol residue, a pentane residue, a hexanediol residue, a heptanediol residue, and a bisphenol The alcohol residue, the decanediol residue, the decanediol residue, the adipic acid residue, the sebacic acid residue, and the like are preferably an organic residue having a carbon number of 2 to 3 Å, more preferably a carbon number (4). When the carbon number is less than the range, the cured product is insufficient in flexibility, and in many cases, the toughness is insufficient. As a % residue, for example, it can be listed as an example. </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; Cyclohexanediol residue, hydrogenated bisphenol A residue, "child touch a", Qingqing grave &amp; hydrogenated bisphenol F residue, hydrogenated biphenol residue, etc. 'preferably carbon number 2 to 3 〇, more It is better to have an organic residue of 6 to 18 in the opposite direction of the horse. When the carbon number is less than the range, the softness of the obtained hardened material is insufficient, and in many cases, the position of the substituted group is not strong. The substitution is not particularly limited. The polyglycerol residue may, for example, be a polyethylene glycol residue, a polypropylene glycol residue or a polytetramethylene glycol residue, and the like, 肀p _ ^ The number average molecular weight is preferably about 62 to about 30, more preferably about 5 (10) to about 10,000. When the number average molecular weight is less than the range, the softness of the obtained cured product is insufficient, and in many cases, the toughness is insufficient. The diol residue may, for example, be a poly(tetra)diol residue, 148718.doc •10·201102756 ethanol hexanol-oxime alcohol Residue, direct bond tobacco polyacetate diol residue, ring (tetra) polyglycol diol residue, etc., the number average molecular weight of the diol residue is preferably about 100~5000, more preferably 5〇〇~ When the number average molecular weight is less than the above range, the softening property of the obtained cured product is insufficient, and in many cases, the toughness is insufficient. Examples of the cyclic 1 alcohol residue are, for example, a spiro ring having a spiro structure. a second fermentation residue, a dioxane diol residue having an acetal ring structure, etc. Among these, 'in view of the heat resistance of the cured product, it is preferred to have a cyclohexane ring structure and a spiro ring structure in the molecule. a compound having a cyclic structure such as a ring-retaining structure, that is, a compound having an alicyclic structure or an epoxy group-containing functional group X having an alicyclic epoxy group. When the aliphatic alcohol is subjected to glycidyl etherification with epichlorohydrin to obtain the epoxy resin (1), chlorine derived from epichlorohydrin is likely to remain. When used for a solder resist or the like which requires long-term insulation, the gas is used. Will cause circuit wiring due to ion migration Open circuit or short circuit. It is preferred to use an epoxy resin which is purified by molecular steaming or the like without using epigas alcohol, or after the test is carried out by using epigas alcohol. A so-called nuclear hydrogenated epoxy resin in which an aromatic ring is selectively hydrogenated. The total gas content in the preferred gas-containing range 'epoxy resin (1) (using the measurement method according to JIS Κ 7243·3:2005) is 0 to 02 The weight %, more preferably 0 to 0.1% by weight. Further, in the case of the direct bonding of R, for example, 3, 4, epoxycyclohexylcarboxylic acid 3,4·epoxycyclohexylmethine (manufactured by Daielel Chemicals' (10). (4) 2021) et al. 1487I8.doc 201102756 One of the molecules used in the epoxy carboxylic acid esterification step, which has more than one polymerizable ethylenically unsaturated group and one or more slow-grouping compounds (丨丨) The epoxy resin (1) is introduced into the diol compound by an epoxy carboxylate reaction, and an ethylenically unsaturated group is introduced into the reactive polyurethane compound. The compound (u)' is preferably a compound having no hydroxyl group, and examples thereof include (fluorenyl)acrylic acid or crotonic acid, α-cyanocinnamic acid 'cinnamic acid, or a saturated or unsaturated dibasic acid. A reaction product of an unsaturated group-containing monoglycidyl compound or the like. Examples of the (fluorenyl)acrylic acid include (mercapto)acrylic acid, fluorenyl-styrylacrylic acid, β-mercaptoacrylic acid, (meth)acrylic acid dimer, (meth)acrylic acid, and ε-hexene. a reaction product of an ester, a half ester of a molar reactant such as a saturated or unsaturated dibasic acid anhydride and a (hydroxy) acrylate derivative having one hydroxyl group in one molecule, as a saturated or unsaturated dibasic acid A half ester of a molar reactant such as a (meth)acrylic acid monoglycidyl ester derivative. Among these, in terms of sensitivity in the case of producing an active energy ray-curable resin composition, a reaction product of (mercapto)acrylic acid, (mercapto)acrylic acid and caprolactone or cinnamic acid is preferred. In the epoxy carboxylic acid esterification step, it is preferred to use 1 〇 to 120 equivalent % of the compound (ii) with respect to 1 equivalent of the epoxy group of the epoxy resin (1). If it is in this range, it can be manufactured under relatively stable conditions. When the amount of the compound (Π) added is more than the above range, the excess carboxylic acid remains, which is not preferable. Further, if it is too small, an unreacted epoxy group remains, which causes a problem in the stability of the resin produced by J2 148718.doc 201102756. The epoxy carboxylate esterification step can be carried out in the absence of a solvent, or it can be reacted by dilution with a solvent. The solvent is not particularly limited as long as it is inert to the epoxy carboxylic acid esterification reaction, and is preferably a urethanization step in the next step and the following acid used as needed. An inert solvent is also used in the addition step. The amount of the solvent to be used should be appropriately adjusted depending on the viscosity or use of the obtained resin, and it is preferably 3 〇 to 1 〇〇 in terms of solid content.

Examples of the solvent of the hydrocarbon-based solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetradecylbenzene; and aliphatic hydrocarbon solvents such as hexane, octane, and decane; A mixture of petroleum ether, white gasoline, solvent naphtha, and the like. For example, ethyl acetate, acrylic acid

Mono- or polyalkylene glycol monoalkyl ether monoacetate such as monoacetate; pentane, as an ester solvent, a polyalkylene alkanoate such as a dialkyl adipate, a dialkyl succinate , base esters, etc.

Further, as the ketone solvent, for example, acetone, methyl ethyl hydrazine, hydrazine, and isophorone are exemplified as the ketone solvent. In addition to the above, the reactive compound (c) described later or the like may be used singly or in the form of a mixed organic talc. In this case, it can also be directly used as an active energy ray-curable resin composition. b In the epoxy m acid S step, in order to promote the reaction, it is preferred to use a catalyst which is used in an amount relative to the reactant, that is, the above-mentioned cyclosporine (1), compound (ii), The amount of the reactant such as the solvent as the case may be about 0.1 (7)% by weight. The reaction temperature is 60 to 150 t, and preferably between 5 and 60 hours. Examples of the catalyst include triethylamine, f-dimethylamine, ethylammonium chloride, trimethylammonium chloride, and trimethyliodide: ammonium: di-phosphoryl, Triphenylsulfonium, methyltriphenylphosphonium, chromic acid alkaline catalyst, and the like. Ning "mouth 4, as a thermal polymerization inhibitor, preferably used: hydroquinone monomethyl '2-methyl-p-benzoate' p-benzoate, diphenylamine, 3,5-di- The third butyl group is prepared by appropriately sampling the acid value of the sample to be 5 mg K〇H/g or less, preferably 2 mg K. The time point below 〇H/g is used as the end point. The urethanic acid acetalization step is used to react the compound (8) having two base groups and one or more enemy groups in one molecule to be used in the reactive polyurethane resin. It is deductible to make it soluble in the test liquid when performing photo patterning. 148718.doc •14· 201102756 As the compound (8), for example, dihydroxymercaptopropionic acid, dibasic butyric acid, and biphasic acid can be cited. Among them, in view of the fact that the raw material is preferably obtained as a light methyl propionic acid or a di-methyl butyric acid. The aromatic acid ring used in the urethanation step does not contain an aromatic ring and is in a molecule. And two compounds of the isoammonium sulphate (4)' are combined with the epoxy acid vinegar compound (a) and the two molecules in the molecule and the combination of two or more The transbasic group of (8) is subjected to a ureic acid s to produce a reactive polyurethane sulfonate compound (A), whereby a material having better flexibility can be obtained, and by eliminating the aromatic ring, heat can be suppressed. And the coloring/discoloration caused by light. As the compound (4), for example, a linear diisocyanate such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate may be mentioned. Aliphalone diisocyanate, sulfonate diisocyanate, benzoyl dimethyl diisocyanate, hydrogenated sub-f-bis-phenylene diisocyanate, etc. The ureic acid S is preferably a compound (c) having an isocyanate group mixed with a mixture of the compound (4) and the compound (b) in the epoxy acid retardation. The reactive polyurethane resin of the present invention is produced. In the case of (a), the molar number of the epoxy carboxylate compound (a) + the compound (the number of moles of V, the molar number of the compound (4) having an isocyanate group is the value in the reaction system The ratio of the hydroxyl group to the isocyanate group is preferably in the range of from 1 to 5, more preferably in the range of from 1.1 to 1.5. Therefore, the storage stability of the reactive polyurethane resin (A) is improved by making the isocyanate group the most in the acetalization reaction. When the ratio of the hydroxyl group to the isocyanate group in the reaction system is larger than the When the value is obtained, the molecule of the obtained reactive polyurethane compound 148718.doc •15-201102756 Jia becomes too small to obtain a toughened hardened material, and when it is less than this value, the molecular weight of the obtained resin is also changed. λ, the adverse effect of deterioration of developability, etc. Further, in the case of producing a reactive polyurethane compound (莫), the molar number of the epoxy carboxylate compound (3) / compound (b) The value of the molar number is better than the range of 0.1 to 4, which is particularly preferably in the range of 〇3 to 2. When the value is more than 4, the amount of the carboxyl group in the reactive polyurethane resin (A) is small, and it is difficult to impart desired developability. When the value is less than Q1, the reactive group in the reactive polyurethane resin (A) is small, and it is difficult to impart sensitivity or toughness of the coating film. The urethanation step can be carried out in the absence of a solvent, or it can be reacted by diluting the solvent into the bamboo. The solvent ' is not particularly limited as long as it is a solvent inert to the amidoxime reaction. The amount of the solvent to be used is appropriately adjusted in accordance with the viscosity or use of the known tree, and is preferably from 30 to 99% by weight, more preferably from 5 to 9 % by weight, based on the solid content. Further, in the case where the solvent is produced by using the solvent in the above step, the epoxy carboxylic acid esterification step, it is also inert to the two reactions, and it may be directly supplied to the next step, the amidoximation step, without removing the solvent. The solvent exemplified as the above-mentioned epoxy carboxylic acid esterification step can be exemplified. Further, as described above, the reactive compound described later may be used singly or in the form of a mixed organic solvent. In this case, it may be used as the active energy ray-curable resin composition as it is. The same compound as the above epoxy carboxylic acid esterification step can also be used as the heat t-inhibitor or the like. 148718.doc -16- 201102756 The urethanation step can also be carried out essentially in the absence of a catalyst, or a catalyst can be used to promote the reaction. In the case of using a catalyst, the amount of the reactants relative to the reactants, that is, the total amount of the reactants to which the above-mentioned carboxylate compound, compound (b), compound having an isocyanate group (c), and optionally a solvent are added are used. , is about 0 · 01 to 1% by weight. The reaction temperature is 40 to 150 ° C, and the reaction time is preferably 5 to 60 hours. As the catalyst, it is preferred to use a well-known general-purpose catalyst, for example, a Lewis base catalyst such as tin hexanoate or tin octylate. The amidoximeation step is the end point of the reaction in which the isocyanate group is hardly left. In order to determine the end point of the reaction, it is possible to use an observation of a rock near the 225 〇 cm·1 derived from an isocyanate group by infrared absorption spectroscopy or a titration method such as JIS K1556: 1968. With respect to the preferred molecular weight range of the reactive carboxylate compound (A) of the present invention thus obtained, the polystyrene conversion weight average molecular weight of GPC (gel permeatiation chromatography) is 1,000. ~3〇, the range of 〇〇〇 is better than the range of ^(9)~^(9). When the molecular weight is less than the molecular weight, the toughness of the cured product cannot be sufficiently exhibited, and when it is larger than the molecular weight, the viscosity becomes high, and coating or the like becomes difficult. When the reactive polyamine phthalate compound (A) of the present invention is used as an alkali developing resist, it is preferred to add the acid value of the solid component of the finally obtained reactive polyurethane compound (A). (According to JIS K56〇1_2 1 : 1999), the calculated value is 30 to 120 mg*KOH/g, more preferably 40 to 1〇5 mg.K〇H/g. 148718.doc 17 201102756 When the acid value of the solid component is in this range, the active energy ray-curable resin composition of the present invention exhibits good developability of an aqueous solution, which broadens the management of good patterning and overdevelopment. . The present invention also includes an acid-modified reactive polyamine phthalate compound (^) obtained by reacting a polybasic acid anhydride (4) with a reactive polyamine formate (A). By this, it is possible to add not only the compound (b) but also the acid value necessary for alkaline development in accordance with the desired tree property. In the present invention, the =哕 reaction step is referred to as an acid addition step. The hydrazine acid addition step is carried out by reacting the polybasic acid anhydride (4) with the radical group remaining in the reactive polyurethane octomerization product (4), and introducing the sulfhydryl group through a tie-bonding reaction. Therefore, it is not possible to add acid to the equivalent of the hydroxyl group remaining at the end of the above-mentioned carbamate hydration step. The polybasic acid needle (4) can be used as long as it is a compound having a cyclic acid trait structure in one molecule, and can provide an aqueous solution-developing compound having excellent heat resistance and chemical hydrolysis properties, for example, Listed: aromatic anhydrides such as phthalic anhydride and trimellitic anhydride, hydrogen phthalic anhydride, hexahydrophthalic anhydride, 3·fluorenyl-tetrahydrophthalic anhydride, 4-methyl- An alicyclic acid anhydride such as hexahydrophthalic anhydride; an aliphatic acid anhydride such as succinic anhydride, maleate (tetra) or itacon (tetra). Among them, in terms of coloring property, an aliphatic acid anhydride or an alicyclic acid anhydride is preferred. The acid addition step is carried out by adding a polybasic acid anhydride (4) to the above reactive polyurethane carboxylic acid compound (VIII). The amount of the "hepatic (4) money can be appropriately changed depending on the set value of the reaction polyurethane S compound (4), that is, the acid value derived from the compound (8), the amount of the remaining hydroxyl group, and the necessary acid value. J48718.doc 201102756 However, when the acid-modified reactive polyamine phthalic acid compound (B) of the present invention is used as an alkali-developing resist, the acid value of the solid component is added (according to JIS K5601-2) -1 : 1999) is a calculated amount of 30 to 120 mg.KOH/g, more preferably 40 to 105 mg, K〇H/g. When the acid value of the solid component is in this range, the active energy ray-curable resin composition of the present invention exhibits good developability of an alkaline aqueous solution. That is, the management range of good patterning and overdevelopment is widened. In the acid addition step, in order to promote the reaction, it is preferred to use a catalyst which is used in an amount relative to the reactant, that is, the above-mentioned reactive polyurethane compound (A) and polybasic acid anhydride (d) are added. The total enthalpy of the reactants such as the solvent of the case is about 0.1 to 1% by weight. The reaction temperature is 6 Torr to 15 (rc, and the reaction time is preferably 5 to 60 hours. Examples of the catalyst include triethylamine, benzyldimethylamine, triethylammonium chloride, and benzyl group. Tridecyl ammonium bromide, benzyl tridecyl ammonium iodide, diphenyl phosphine, triphenyl sulfonium, methyl triphenyl sulfonium, chromium octoate, bismuth octoate, etc. The acid addition step can be in a solvent-free state. The reaction may be carried out by diluting with a solvent. The solvent is not particularly limited as long as it is inert to the acid addition reaction. Further, the solvent is used in the amination step in the previous step. In the production, if it is inert to the two reactions, it may be directly supplied to the next step, the acid addition step, without removing the solvent. The amount of the solvent to be used is appropriately adjusted depending on the viscosity or use of the obtained resin, preferably The solid content is in the range of 30 to 90% by weight, more preferably 50 to 80% by weight. I48718.doc • 19· 201102756 As the solvent, for example, the above-mentioned epoxycarboxylic acid esterification step or amine citric acid can be used. The solvent having the same esterification step. Further, the reactivity described later can be used. When the compound (c) is used alone or in the form of a mixed organic solvent, it can be used as the active energy ray-curable resin composition as it is. The thermal polymerization inhibitor or the like can also be used in the esterification step with the above epoxy carboxylic acid. Or the same urethane esterification step. The acid addition step is carried out by appropriately sampling the acid value of the reactant by the above method, and the measured acid value is within a range of plus or minus 10% of the set acid value. The compound (A) and the reactive compound (c) other than the compound (B) which may be contained in the active energy ray-curable resin composition of the present invention may, for example, be a radical reactive type (fluorenyl group). a so-called reactive oligomer such as a acrylate, a cationically reactive epoxy compound, or a vinyl compound which is induced by the two. Examples of the radical reactive acrylate include monofunctional (A) Acrylates, polyfunctional (meth)acrylates, amine phthalic acid acrylates, polyesters, other epoxy (fluorenyl) An enoate or the like. Examples of the mono(g)(meth)acrylic acid class include, for example, methyl (meth) acrylate, ethyl (mercapto) acrylate, butyl (meth) acrylate, (methyl) ) lauryl acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate monoterpene ether, styrene ethyl (meth) acrylate, isobutyl ester (meth) acrylate, (fluorenyl) cyclohexyl acrylate, (mercapto) acrylate vinegar, (meth) methacrylate, etc. 148718.doc -20- 201102756 As polyfunctional (meth) acrylates, exemplified by Diol bis(indenyl) acrylate, hexanediol di(indenyl) acrylate, neopentyl glycol di(meth) acrylate, decanediol di(meth) acrylate, ethylene glycol bis(曱) Base) acrylate, diethylene glycol bis(indenyl) acrylate, polyethylene glycol di(meth) acrylate, tris(meth) propylene oxiranyl ethyl isocyanurate, polypropylene glycol bis ( Mercapto) acrylate, adipic acid epoxy di(meth) acrylate, bisphenol oxirane II曱-) acrylate, hydrogenated bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, hydroxypivalic acid neopentyl glycol ester ε-caprolactone adduct (Mercapto) acrylate, poly(meth) acrylate of dipentaerythritol and ε-caprolactone, dipentaerythritol poly(indenyl) acrylate, trishydroxypropyl propane tri(meth) acrylate, Trihydroxyethylpropane tri(meth) acrylate or its ethylene oxide adduct, pentaerythritol di(indenyl) acrylate vinegar or its ethylene oxide addition product, pentaerythritol tetra(meth) acrylate Dipentaerythritol hexa(indenyl) acrylate or an ethylene oxide adduct thereof. Further, an amine phthalate (meth) acrylate having both a functional group and a urethane bond reactive with an active energy ray in the same molecule, and a functional group reactive with an active energy ray in the same button may be mentioned. Polyester (meth) acrylate having a base and an ester bond, a compound derived from another epoxy resin and having a functional group reactive with an active energy ray in the same molecule, and an epoxy other than the compound (Β) (Mercapto) acrylate, and a reactive oligomer in which the bonds are present. The cation-reactive epoxy compound is not particularly limited as long as it has an epoxy group, and examples thereof include (meth)acrylic acid 148718.doc • 21 201102756 glycidyl ester, methyl glycidyl ether , ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylcarboxylic acid 3,4-epoxycyclohexyl decyl ester (manufactured by Union Carbide, Cyracure UVR -6110, etc., 3', 4'-epoxycyclohexylcarboxylic acid 3,4-epoxycyclohexylethane, diemulsified ethylenecyclohexene (manufactured by Union Carbide, elr_ 4206, etc.), limonene dioxide ( Manufactured by Daicei Chemical Industry Co., Ltd., Celloxide 3000, etc.), propylene dicyclohexene oxide, 3,4_epoxy_4_methylcyclohexyl-2-epoxypropane, 2-(3,4-epoxy ring Hexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexyl) adipate (manufactured by Uni〇n Carbide, Cyracure UVR- 6128, etc.), bis(3 4_epoxycyclohexyldecyl) adipic acid, bis(3,4-epoxycyclohexyl)ether, bis, 4-epoxycyclohexyldecyl)ether, (3,4-epoxycyclohexyl) diethyl siloxane silicon and the like. Examples of the vinyl compound include vinyl ethers, styrenes, and other ethylenic compounds. Examples of the vinyl ethers include ethyl vinyl ether, propyl vinyl bond, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of the phenethyl hydrazines include styrene, methyl stupidene, and ethyl strepethethylene. Examples of the other vinyl compound include triisopropenyl isocyanurate and trimethylallyl isocyanurate. Among these, as the reactive compound (c), a radical reactive type (fluorenyl) acrylate is particularly preferable. In the case of using a cationically reactive compound, it is necessary to form a two-liquid mixed type in such a manner that the carboxylic acid does not react with the epoxy group. The reactive polyurethane compound (A) of the present invention and/or the acid is modified by the anti-148718.doc -22- 201102756 functional polyurethane compound (B), and optionally the compound (A), The reactive energy ray-curable resin composition of the present invention can be obtained by mixing the reactive compound (C) other than the compound (B). In this case, other components may be appropriately added depending on the application. The active energy ray-curable resin composition of the present invention contains preferably from 5 to 97% by weight, particularly preferably from 10 to 87% by weight, of the reactive polyurethane compound (A) and/or acid modification reaction. a polyurethane compound (B), preferably containing 3 to 95% by weight, particularly preferably 3 to 90% by weight of a compound, or a reactive compound other than the compound (B). The active energy ray-curable resin composition of the present invention is easily cured by active ray radiation to provide a cured product. Here, as the active energy ray, ultraviolet rays are exemplified. Electromagnetic waves such as visible light, infrared rays, xenon rays, gamma rays, and laser rays; particle beams such as α-rays, β rays, and electron beams; etc. In view of the preferred use of the present invention, ultraviolet rays are preferred among them. Laser light, visible light, or electron beam. The coloring pigment which may be contained in the active energy ray-curable resin composition of the present invention is used for coloring the active energy ray-curable resin composition. The present invention is a material which is less colored by exposure to heat or light, and is therefore suitable for use as a material for coloring. Examples of the coloring pigment include phthalocyanine, azo, and quinone. An organic pigment such as a ketone ketone or an inorganic pigment such as carbon black or titanium oxide. Among these, it is particularly useful as a material which is colored in white, green, blue or the like which is sensitive to color change due to yellowing. 。 148 718 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 The material to be used for the use of the uncured composition, such as a laser or the like, which is formed by hardening or forming a J-light, etc., that is, a sheet-like material 1 (4) Materials, so-called nano-printed materials which are finely processed by the micro-machining of "grip-making; ^ 厌 recognizing t ^ chess 孓" against the uncured composition, and especially the requirements of heat and light Light-emitting diode The use of a peripheral sealing material such as a photoelectric conversion element, etc. The material for forming a film according to the present invention refers to I for the purpose of coating the surface of the substrate. Examples include a gravure ink, a flexographic ink, and a silk. Ink materials such as mesh inks and lithographic inks; coating materials such as hard coats, top coats, overprint varnishes, clear coats, etc.; various adhesives such as lamination and optical discs or adhesives; adhesives, anti-etching For example, a resist material such as a resist for a micromachine or a resist is used. Further, a film for forming a film is temporarily applied onto a release substrate to form a film, and then bonded to a substrate which is originally intended. The so-called dry film forming the film also conforms to the film forming material. Among X # , it is also preferred that the reactive polyamine phthalate compound (A) and/or the acid-modified reactive urethane compound (B) are sufficient. It is used as an alkaline water developing type resist material composition by utilizing the characteristics of being soluble in alkaline water/gluten. In the present invention, the material for the resist refers to a film layer on which the composition is formed on a substrate, and the latter portion is irradiated with an active energy ray such as an ultraviolet ray, and is intended to be distinguished by the difference in physical properties between the illuminating unit and the A illuminating unit. Active energy ray-sensitive material. The material used for the purpose of removing the illuminating portion or the illuminating portion of the 148718.doc -24 - 201102756 j by a method such as a solvent or the like, or an alkali solution, etc., and removing it, and Draw. The material for the resist agent of the present invention, that is, the active energy ray-curable resin, can be used for various materials which can be patterned, for example, in particular, for: a flux material, an interlayer insulating material for a build-up method, and further, as an optical The waveguide is used for printing an electric, electronic, or optical substrate such as an optoelectronic substrate or an optical substrate. As a particularly preferable use, it is preferable to make use of a soldering agent which is soft and strong, and which is hard to be deteriorated or discolored by heat or light, and which is also a soldering agent for coloring purposes. The use of color resists for permanent resist applications, color calenders, etc. Further, the use of the flexible substrate for the required flexibility can maximize the effects of the present invention. The method for forming a film by using the active energy ray hard (tetra) resin composition of the present invention is not particularly limited, and a gravure printing method such as a gravure or the like, a relief printing method such as flexography, or a stencil printing method such as a screen can be used. Various coating methods such as a lithographic printing method such as a lithographic plate, a roll coater, a blade coater, a die coater, a curtain coater, and a spin coater. The cured product of the active energy ray-curable resin composition of the present invention which is irradiated with active energy rays and hardened is also included in the present invention. Further, in the active energy ray-curable resin composition of the present invention, other components may be added to the resin composition in an amount of 7% by weight based on the respective applications. Other components include photoinitiation polymerization, various additives, pigment materials, and adhesion to impart suitability for coating, etc. 148718.doc • 25· 201102756 degree adjustment volatile solvent. As the photopolymerization initiator, a radical photopolymerization initiator, a cationic photopolymerization initiator or the like can be used. Examples of the radical-type photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and the like, and the present ketone, 2,2-diethoxy-2- Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, ι,ι 2 diacetophenone, 2-hydroxyl-2-nonylphenylpropan-1-one, two Ethyl acetophenone, hydrazine-hydroxycyclohexyl phenyl ketone, 2-1-mercapto-1-[4-(indolylthio)phenyl]_2-mililine-propanone-buprole and the like; 2_ Ethyl hydrazine, 2-tert-butyl fluorene, 2-gas hydrazine, 2-pentyl hydrazine, etc.; 2,4-diethyl-9-oxopurine p-star, 2- Isopropyl _9_ oxysulfuron, 2 qi-9-oxopurine p star, etc. 9-oxo sulphur P mountain p star; acetophenone dimethyl ketal, stupid oxime didecyl ketal Ketones; benzophenones such as benzophenone, 4-benzylidene- 4,-methyldiphenyl sulfide, 4,4'-bis-decylaminobenzophenone; 2,4 Known general free radical photoreactions such as 6-trimercaptophenylphosphonium diphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, etc. Starting agent. Examples of the cationic photopolymerization initiator include a diazonium rust salt of a Lewis acid, a sulfonium salt of a Lewis acid, a sulfonium salt of a Lewis acid, a sulfonium salt of a Lewis acid, other halides, and a tri-grain starter. A borate initiator, other photoacid generator, and the like. Examples of the diazonium rust salt of the Lewis acid include p-methoxyphenyl diazonium rust fluorophosphonate and N,N-diethylaminophenyldiazonium hexafluorophosphonate (Sanshin Chemical Co., Ltd.) Manufactured by an industrial company, San_Aid SI_6〇L, San_Aid SI_ 148718.doc -26- 201102756 80L, San-Aid SI-100L, etc.). The more the cone of the Lewis acid is, the latter is exemplified by a diphenyl-terminated hexafluorophosphonic acid, a quinone-based hexahydrous acid salt, and the like. As a bismuth salt of a Lewis acid, for example, a magical hexafluorophosphonate (manufactured by Union Carbide, ρ 衣 知 · Cyracure UVI-6990, etc.), triphenyl sulfonium hexahydrate (Union Carbide) Company manufacturing, trace 6974, etc.). As the scaly salt of the Lewis acid, for example, triphenyl hexafluorophyllate can be mentioned. For other examples, for example, 2,2,2-trimethylethyl)phenyl]ethanone (manufactured by AKZ0, Trig〇nal ρι, etc.), 2,2_diox_1-[4-( Phenoxyphenyl)]ethyl ketone (manufactured by the company, - '1000, etc.), α, α, α-tribromomethyl phenyl sulfone (manufactured by Steel Chemical Co., Ltd., BMPS, etc.). Examples of the second-tillage starter include 2,4,6•tris(trichloromethyl)trinium, 2-dichloroindolyl-4-(4'-methoxyphenyl)_6_3 Plowing (manufactured by Panchim, Triazine A, etc.), 2-trimethylmethyl_4_(4,_decyloxystyryl) 6_ three tillage (manufactured by Panchim, Triazine pMS, etc.), 2 trigassulfonyl _4_ To 曰葵基-6-three tillage (manufactured by Panchim, THazine pp, etc.), 2_trimethylmethyl-4-(4-indolylmethyl)_6_three p well (manufactured by Panchim, Triazine B, etc. ), 2[2'(5&quot;-decylfuranyl)ethylidene]_46•bis (trioxanyl)-all three tillage (manufactured by Sanwa Chemical Co., Ltd.), 2_(2,·furanylethylene )_4,6_ bis(dichloroindenyl)-all three tillage (manufactured by Sanwa Chemical Co., Ltd.) and the like. Examples of the acid salt-based initiator include I48718.doc •27·201102756 NK-3876 and NK-388 1 manufactured by Japanese photosensitive pigments. Examples of the other photoacid generator include, for example, 9-phenyl acridine, 2,2'-bis(o-phenyl)-4,4',5,5'-tetraphenyl-linked m-wine (black gold). 2,2-azobis(2-aminopropane) dihydrochloride (manufactured by Wako Pure Chemical Industries Co., Ltd., 丨50, etc.), 2,2-azobis [2-() Imidazoline-2-yl)propane]dihydrochloride (manufactured by Wako Pure Chemical Industries, Ltd., 'VA044, etc.), [η-5-2-4-(cyclopentadecyl) (1,2,3,4,5 , 6,71)-(methylethyl)benzene]iron (11) hexafluorophosphonate (manufactured by Ciba Geigy Co., Ltd., Irgacure 261, etc.), bis(η5-cyclopentadienyl) bis [2,6- Difluoro-3-(1Η-pyrrol-1-yl)phenyl]titanium (manufactured by Ciba Geigy Co., Ltd., CGI-784, etc.) and the like. Further, in addition to the above, an azo-based initiator such as azobisisobutyronitrile or a peroxide-based radical initiator which is thermally induced by oxidized abbreviated formamidine may be used in combination. Further, a photopolymerization initiator of both a radical type and a cation type may be used in combination. 3 Xuan et al. The photopolymerization initiator may be used singly or in combination of two or more. The various additives may be exemplified by a thixotropic bond such as a melamine or a thermosetting contact, a poly 7 oxygen system or a hydrazine leveling agent. a polymerization inhibitor such as a phenol or a hydroquinone monomethyl ether, a stabilizer, a anti-rolling agent, etc. as a pigment material, can be listed as a pigment material

Ut] , N is an extender pigment for the purpose of color, such as talc, barium sulfate - 驮 驮 calcium, magnesium carbonate, barium titanate, aluminum hydroxide, cerium oxide, clay, and the like. Emulsification and 'can also use the active energy (so-called inert poly-manufactured by the resin), such as the resin per oxy-resin, phenolic resin, amine 曱 148718.doc -28 - 201102756 Ester resin, polyester resin, ketone-formaldehyde resin, cresol resin, xylene tree ruthenium, diallyl phthalate resin, styrene resin, guanamine resin, natural or synthetic rubber, acrylic resin, Polyolefin resin' or such modified material. Preferably, the succinct is used in the resin composition in a range of up to 4% by weight. In particular, when a resin composition containing an acid-modified reactive polyurethane compound (B) is used in a solder resist application, it is preferred to use a known epoxy resin as a reaction to active energy rays. Resin type. The carboxyl group derived from the compound (b) remains after being hardened by the active energy ray, and the cured product tends to have poor water resistance and hydrolysis property, but is made of an epoxy resin which is not reactive with active energy rays. The residual carboxyl group is further reacted to form a strong crosslinked structure, which improves performance. The volatile solvent for viscosity adjustment may be added to the resin composition in an amount of up to 50% by weight, more preferably up to 35% by weight. [Examples] The examples are not limited to the examples. Also, the number of parts indicates the parts by weight. Hereinafter, the present invention will be described in more detail by way of examples. However, in the examples of the present invention, the measurement was carried out under the following conditions without any special softening point and epoxy equivalent. (1) Epoxy equivalent: measured by the method according to jIS K7236: • 2001

(4) The measurement conditions of GPC are as follows. 148718.doc -29· 201102756

Column: TSKGEL Super HZM-N

Dissolution: THF (tetrahydrofuran), 0.3 5 ml/min, temperature 40 ° C Detector: differential refractometer molecular weight standard: synthesis of polystyrene synthesis example 1 epoxy carboxylate compound (a) (epoxy carboxylate) The epoxy resin (1) epoxy group 1 mole (the same g number as the epoxy equivalent (WPE, g/eq)), and the acrylic acid (abbreviated as AA) of the compound (ii) Propylene glycol monoterpene ether monoacetate (PGMAc), which is a solvent, has a molecular weight of 72) 1 mol (72 g) and 3 g of triphenylphosphine as a catalyst, and the solid content is 80%. The epoxy carboxylate compound (a) solution was obtained by reacting at 100 ° C for 24 hours. The reaction end point is determined by the solid component acid value (AV, mg KOH/g). The acid value of the solid component is converted from the acid value of the solution measured in the reaction system. Synthesis Example 2: Synthesis of epoxy carboxylic acid ester compound having an aromatic ring The reaction was carried out in the same manner as in Synthesis Example 1, except that the amount of the bisphenol A type epoxy resin described in Table 1 was used as the epoxy resin. [Table 1] Synthesis Example Epoxy Resin XR WPE TC1 (%) AV Synthesis Example 1-1 HDDEP GEth HD 115 0.08 0.8 Synthesis Example 1-2 PTMGEP GEth PTMG650 430 0.09 1.2 Synthesis Example 1-3 PCDLEP GEth PCDL800 530 0.09 2.1 Synthesis Example 1-4 CHDMEP GEth CHDM 165 0.08 1.4 Synthesis Example 1-5 HBAEP GEth H-BisA 199 2.3 2.4 Synthesis Example 1-6 HBAEP-LC GEth H-BisA 205 0.05 1.7 Synthesis Example 1-7 HDDCE CEst HD 210 Trace 1.9 Synthesis Example 1-8 TCDCE CEst TCD 240 Trace 1.8 Synthesis Example 1-9 DOGCE CEst DOG 255 Trace 1.6 Synthesis Example 1-10 ECMECC CEst/CEth none 135 Trace 1.6 Synthesis Example 2 BPAEP GEth Bis-A 180 0.05 1.9 148718.doc -30 - 201102756 Abbreviation WPE as described in Table 1 : Epoxy equivalent (g/eq) TC1 : Total gas (%) AV : Solution acid value in the reaction system, mg KOH / g X : Epoxy in the formula (I) Type of base and its bonding form GEth : glycidyl ether CEst : 3,4-epoxycyclohexyl decanoate CEth : 3,4-epoxycyclohexyl ether R: two of the formula (I) Alcohol residue HD: hexanediol residue (linear hydrocarbon residue) PTMG650: polybutanediol residue (polyalkylene glycol residue, average molecular weight "ο) PCDL800: poly Carbonate diol residue (polyester diol residue, average molecular weight 800) is CHDM: cyclohexanedikecanol residue (cyclic hydrocarbon residue) H-BisA: hydrogenated bisphenol A residue (ring Hydrocarbon residue) TCD _bicyclodecane dimethanol residue (cyclic hydrocarbon residue) DOG. dioxane diol residue (cyclic ether diol residue) N〇ne : no bond group (direct Bonding)

Bis-A. Bisphenol A residue (bisphenol A residue with aromatic ring) Example 1 Preparation of 'Reactive Polyurethane Compound (A) (Aminic Acid. Esterification Step); In the case of the reactive polyurethane compound (A), the amount of the solid squeegee was 50%, and the amount (the solid content conversion value) described in Table 2 was added to the compound of Example 1 to form α; The compound (4) solution, as described in Table 2, as a solvent, a compound having two base groups and more than one thiol group 148718.doc •31 · 201102756 (b) Propylene glycol monoterpene ether acetate (PGMAc for short) is stirred and dissolved. Further, 1 g of tin octylate as a catalyst was added and heated to 100 ° C. Then, the diisocyanate described in Table 2 was added as a compound (c) having no aromatic ring and having two isocyanate groups in one molecule, and the reaction was carried out using a dropping funnel. After the completion of the dropwise addition, the reaction was continued for 2 hours, and the absorption peak derived from the isocyanate group was confirmed by infrared absorption spectrum to obtain a reactive polyurethane compound (A). Comparative Example 1: Production of a reactive polyamine phthalate compound having an aromatic ring Comparative Example 1-1 was produced by using the epoxy carboxylic acid ester compound synthesized in Synthesis Example 2 in the same manner as in Example 1 to produce an aromatic ring. Reactive polyurethane compound. Comparative Example 1 - 2 A reactive polyamine phthalate compound having an aromatic ring was produced in the same manner as in Example 1 except that a compound having an aromatic ring and having two isocyanate groups was used. [Table 2] Example Compound (a) Compound (b) Compound (c) (a+b)/ca/b AV Example 1-1 Synthesis Example 1-1 53.4 g DMPA 14.3 g HMDI 32.3 g 1.30 1.33 59 Implementation Example 1-2 Synthesis Example 1-2 63.6 g DMPA 14.3 g HMDI 22.0 g 1.30 0.59 60 Example 1-3 Synthesis Example 1-3 64.9 g DMPA 14.3 g HMDI 20.8 g 1.30 0.50 60 Synthesis Example 1-4 Synthesis Example 1-4 56.5 g DMPA 14.3 g HMDI 29.2 g 1.30 1.11 59 Example 1-5 Synthesis Example 1-5 58.0 g DMPA 14.3 g HMDI 27.7 g 1.30 1.00 58 Ridge Example 1-6 Synthesis Example 1-6 58.3 g DMPA 14.3 g HMDI 27.4 g 1.30 0.98 59 Example 1-7 Synthesis Example 1-7 58.5 g DMPA 14.3 g HMDI 27.2 g 1.30 0.97 60 Example 1-8 Synthesis Example 1-8 59.5 g DMPA 14.3 g HMDI 26.2 g 1.30 0.89 61 EXAMPLES 1-9 Synthesis Example 1-9 60.0 g DMPA 14.3 g HMDI 25.7 g 1.30 0.86 59 Example 1-10 Synthesis Example 1-10 54.4 g DMPA 14.3 g HMDI 31.2 g 1.30 1.26 60 Example 1-11 Synthesis Example 1-8 64.8 g DMPA 14.3 g HMDI 20.8 g 1.7 0.97 61 Example 1-12 Synthesis Example 1-8 54.6 g DMPA 14.3 g HMDI 31.1 g 1.05 0.82 59 Example 1-13 Synthesis Example 1-8 54.3 g DMPA 14.3 g TMDI 31.4 g 1.30 0.81 59 Example 1-14 Synthesis Example 1-8 52.9 g DMPA 14.3 g IPDI 32.8 g 1.30 0.79 60 Example 1-15 Synthesis Example 1-8 73.1 g DMPA 6.0 g HMDI 20.9 g 1.30 2.63 26 Example 1-16 Synthesis Example 1 -8 44.0 g DMPA 23.9 g HMDI 32.1 g 1.30 0.40 97 Comparative Example 1-1 Synthesis Example 2 57.4 g DMPA 14.3 g TMDI 28.3 g 1.30 1.04 59 Comparative Example 1-2 Synthesis Example 1-8 58.7 g DMPA 14.3 g TDI 27.0 g 1.30 0.88 59 148718.doc -32- 201102756 The abbreviation DMPA described in Table 2: dimethylolpropionic acid HMDI: hexamethylene diisocyanate TMDI: trimethylhexamethylene diisocyanate IPDI: isophorone II Isocyanate, TDI: toluene diisocyanate (aromatic) (a+b)/C : (molar number of compound (4) + molar number of compound (8) / molar number of compound (c) a/b·· The number of moles of the compound (&amp;)/the number of moles of the compound (b) AV. The acid value at the end of the reaction (converted solid content), Example 2: acid-modified reactive polyurethane compound (b) Production (acid addition step) The reactive polymerization produced in Example 1 was added to the reaction tank in the amount (solid content conversion value) described in Table 3 To the solution of the amine phthalate compound (A), the acid anhydride described in Table 3 was added, and propylene glycol monomethyl ether acetate was added as a solvent so that the acid-modified reactive polyamine phthalate compound became 50% by solid content. The ester (referred to as PGMAc) is stirred and dissolved. The solution was heated at 8 ° C for 10 hours, and the acid value was measured to confirm the completion of the reaction. *Comparative Example 2: Production of acid-modified reactive urethane compound having an aromatic ring (acid addition step) Using the reactive polyurethane compound produced in Comparative Example 1 in a reaction vessel An acid-modified reactive urethane compound having an aromatic ring was produced in the same manner as in Example 2. 148718.doc •33· 201102756 [Table 3] Example Compound (A) Compound (d) AV (Compound (A)) AV (Compound (B)) Example 2-1 Example 1-8 93.5 g THPA 6.5 g 60 80 Example 2-2 Example 1-15 93.5 g SA 6.5 g 26 61 Comparative Example 2-1 Comparative Example 1-1 93.5 g THPA 6.5 g 60 82 The abbreviation THPA described in Table 3: tetrahydrophthalic acid Acid anhydride SA: succinic anhydride AV (compound (Λ)): acid value (solid content conversion value) of the compound (Λ) which is a raw material, mgKOH/g AV (compound (B)): acid of the compound (B) produced Value (solid content conversion value), mg KOH/g Example 3: Preparation and evaluation of a white solder resist composition for a flexible substrate The reactive polyamine phthalate compound (A) obtained in Example 1 was formulated or carried out. 54 g of the acid-modified reactive amine phthalate compound (B) obtained in Example 2, HX-220 (trade name, manufactured by Nippon Kayaku Co., Ltd., diacrylate monomer) as the reactive compound (C) 3.5 g, Lucirin TPO (manufactured by BASF) 5 g as a photopolymerization initiator, alicyclic diepoxide resin as a hardening component (Celloxide 2021P, Daic) 15 g, melamine as thermal hardening catalyst, 1 g of methyl ethyl steel as a concentration adjusting solvent, and titanium oxide (Tipaque A-1 00: manufactured by Ishihara Sangyo) 30 g as a coloring pigment, After premixing, the mixture was kneaded by a three-roll mill to uniformly disperse it to obtain a resist resin composition. The obtained resist resin composition was applied onto a copper-laminated polyimide film by a screen method so that the film thickness after drying was approximately 20 μm. 148718.doc -34- 201102756 The coated substrate was heated in an electric oven for 8 minutes at 80 ° C for solvent drying. Then, using an ultraviolet exposure apparatus (OAK Co., Ltd., model HMW-680GW), 5〇〇mJ/ was irradiated by drawing a mask with a circuit pattern and a stage exposure meter N〇2 manufactured by Kodak for estimating the sensitivity. Ultraviolet light of cm2. Thereafter, the film was developed by a 1% sodium carbonate aqueous solution to remove the resin of the ultraviolet non-irradiated portion. Wash and dry, to

The printed substrate was heated and hardened by an electric oven at 150 ° C for 6 minutes to obtain a hardened film. X Sensitivity Evaluation The sensitivity is determined by the concentration portion of the first stage of the staged exposure meter that is obtained by passing through the stage exposure meter. The larger the number of segments, the higher the sensitivity (unit: segment). Development property evaluation The development property is evaluated as the developability (unit: second) when the exposure portion obtained by the transmission pattern mask is developed in accordance with the time until the pattern shape portion is completely developed, that is, the image formation time &amp; Preferably, it is 20 to 50 seconds 2 == shadow: when it is shorter than the time, the development is too early and the problem is easy to occur on the snail. Also, in the case of too long, there will be 4 problems of productivity. 3 Evaluation of hardenability The evaluation of the hardenability was carried out. The hardness of the hardened film after heating and the beam was evaluated. The evaluation method is based on mK5_-5_4:1999. Heat resistance evaluation 148718.doc 201102756 After the heat evaluation system was smelted, it was immersed in a 26 〇t solder bath for 1 minute, taken out, washed with water, air dried, and subjected to adhesion test (jis K5600-2-6 : 1999) and evaluated. 〇: no peeling Δ: slight peeling x: peeling Evaluation of coloring property The obtained substrate was exposed to Super UV Tester (manufactured by Iwasaki Electric Co., Ltd. for 24 hours) to visually evaluate the coloring. 〇: almost no color change Δ: slight discoloration x: severe yellowing, and it is substantially impossible to use a flexographic evaluation to form a polyimine printed substrate having a resist cured film on the side of the cured film. Use your fingers to fully flatten the bend. The bent portion was restored to its shape, and the resist film was observed with an optical microscope. It will be bent once and there is no question. «The sample of Ε is repeatedly bent and bent 5 times in the same part." The optical display is used to observe the crack of the anti-money film of the bent portion. ◎: No cracks after repeated five times: No cracks when bent once Δ: Fine cracks were observed once bent X: Peeling 148718.doc -36- 201102756 [Table 4] Example compound (B) Sensitivity developability hardenability, heat-stainability, folding property Example 3-1 Example 1-1 8 43 4H Δ Δ 〇 Example 3-2 Example 1-2 6 55 2H Δ Δ ◎ Example 3-3 Implementation Example 1-3 5 48 3H 〇Δ ◎ Example 3-4 Example 1-4 8 35 4H 〇Δ 〇 Example 3-5 Example 1-5 7 23 3H 〇Δ 〇 Example 3-6 Example 1 -6 7 28 3H 〇Δ 〇 Example 3-7 Example 1-7 8 35 3H Δ 〇〇 Example 3-8 Example 1-8 8 33 3H 〇〇〇 Example 3-9 Example 1-9 9 27 4H 〇〇〇Example 3-10 Example 1-10 9 29 4H 〇〇Δ Example 3-11 Example 1-11 6 18 3H Δ 〇Δ Example 3-12 Example 1-12 11 85 4H Δ 〇 ◎ Example 3-13 Example 1-13 8 43 4H 〇〇〇 Example 3-14 Example 1-14 7 38 4H 〇〇〇 Example 3-15 Example 1-15 Unable to develop 4H 〇 〇Δ Example 3-16 Example 1-16 5 15 4H Δ 〇 ◎ Example 3-17 Example 2-1 7 25 4H 〇〇〇 Example 3-18 Example 2-2 9 18 4H 〇〇〇 Comparative Example 3-1 Comparative Example 1-1 6 24 3H 〇X Δ Comparative Example 3-2 Comparative Example 1-2 8 35 4H 〇X Δ Comparative Example 3-3 Comparative Example 2-1 8 35 2H Δ X Δ or more, based on the evaluation result as a white solder resist, a reactive polyamine phthalate compound containing an aromatic ring and containing In the evaluation of the coloring property, the acid-modified reactive polyamine phthalate compound of the aromatic ring showed a strong coloration which was substantially unusable. On the other hand, the reactive polyurethane compound (A) and the acid-modified reactive polyamine phthalate (B) of the present application which do not contain an aromatic ring exhibited excellent properties in each test. Further, it is understood that the acidity can be adjusted from the compound (A) to the compound (B), and the balance of developability or other characteristics can be adjusted, and the acid modification is preferably 148718.doc -37 - 201102756. Example 4: Long-term insulation evaluation of the composition for a white solder resist The composition for a solder resist produced in Example 3 was applied to a line having a film thickness after drying to a thickness of about 20 μm by a wire mesh method. On a BT resin printed circuit board having a comb pattern with a gap of 100 μm. The coated substrate was heated at 80 ° C for 60 minutes in an electric oven to carry out solvent drying. Then, an ultraviolet ray of 500 mJ/cm2 was irradiated by an ultraviolet ray exposure apparatus, and then the printed substrate was heated and hardened by an electric oven at 150 ° C for 60 minutes to obtain a cured film. The lead wire was connected to the obtained substrate, and a voltage of 100 volts was applied thereto, and the resistance value was observed under an environment temperature of 85 ° C and a relative humidity of 85%. Measure until the resistance is below 1 megaohm. ◎: Maintain the resistance value for more than 2000 hours 〇: Maintain the resistance value for more than 1000 hours, less than 2000 hours Δ: Maintain the resistance value for more than 500 hours, less than 1000 hours X: less than 500 hours, the resistance value becomes 10 megohms The following [Table 5] Example Resist composition R TCI AV Insulation Example 4-1 Example 3-1 HD 0.08 59 0 Example 4-2 Example 3-2 PTMG650 0.09 60 Δ Example 4-3 Implementation Example 3-4 CHDM 0.08 59 ◎ Example 4-4 Example 3-5 H-BisA 2.3 58 X Example 4-5 Example 3-6 H-BisA 0.05 59 ◎ Example 4-6 Example 3-7 HD Trace 60 〇 Example 4-7 Example 3-8 TCD Trace 61 ◎ Example 4-8 Example 3-10 None Trace 60 Δ Example 4-9 Example 3-17 TCD Trace 80 〇 Example 4- 10 Example 3-18 TCD Trace 61 Δ 148718.doc -38- 201102756 The abbreviation TC1 described in Table 5: total gas (%) AV: the acid value of the solid component of compound (A) or compound (B) (called K〇) H/g) R: diol residue in the formula (I) HD: hexanediol residue (linear hydrocarbon residue) PTMG650: polybutanediol residue (polyalkylene glycol residue, average molecular weight) 65〇) CHDM: Hexanediyl Yue alcohol residue (a cyclic hydrocarbon residue) H-BisA: hydrogenated bisphenol A residue (cyclic hydrocarbon residue) TCD: tricyclodecane dimethanol residue (cyclic hydrocarbon residue)

None : no bond group (direct bond) According to the above results, the example of the higher total gas (Example 4_4) shows a decrease in long-term insulation performance compared with the example of the low chloride having the same skeleton (Example 4_5). The tendency. x, those with an alicyclic skeleton in the skeleton show a southerly insulation. It can be understood from the above test results that the reactive polyamine vinegar compound (4) or the acid-modified reactive polyurethane urethane compound (8) of the present invention has the basic characteristics as a solder resist and has less discoloration. The adaptability and long-term insulation properties. [Industrial Applicability] The active energy ray-curable resin composition of the present invention is excellent as a material having both hardness, softness, and difficulty in coloring, and is also excellent in reproducibility. Coloring resistance (4) Performance (4) Effect of the use of this property, for example; · Ray hardening printing ink, color anti-synthesis agent', especially as a material 148718.doc.39- 201102756 It is used for color anti-agents and lens materials for LCD (Liquid Crystal Display), and flexible displays. 148718.doc -40-

Claims (1)

201102756 VII. Patent application scope: ι_ A reactive polyurethane compound (A) obtained by reacting the following compounds: an epoxy carboxylate compound (a) which is free of aromatic rings and is in a molecule An epoxy resin (i) having two epoxy groups, reacting with a compound (1) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule; and compound (b), wherein The molecule has two hydroxyl groups and one or more carboxyl groups; and the compound 'which does not contain an aromatic ring and has two isocyanate groups in one molecule. 2. An acid-modified reactive polyurethane compound (B) obtained by reacting a polybasic acid if (d) with a reactive polyamine phthalate compound (a) as claimed in claim 1. 3. An active energy ray-curable resin composition comprising a reactive polyurethane compound (A) and/or an acid-modified reactive polyamine phthalate compound (B) 〇 4. As claimed in claim 3 The active energy ray-curable resin composition further contains a reactive compound (c) other than the compound (A) and the compound (B). 5. The active energy ray-curable resin composition of claim 3, which comprises a coloring pigment. 6. The active energy ray-curable resin composition according to any one of claims 3 to 5, which is a material for translucent molding. The active energy ray-curable resin composition as set forth in any one of claims 3 to 5, which is a material for forming a colored film. 8. The active energy ray-curable resin composition 148718.doc 201102756 according to any one of claims 3 to 5, which is a material for forming a light-transmitting film. 9. 10. 11. The active energy ray-curable resin composition as claimed in claims 3 to 5 is a material for a resist. The hardened material is a cured product of the active energy ray-curable resin composition according to any one of claims 3 to 5. An article which is coated with a cured product of the active energy ray-curable resin composition of claim 10. 148718.doc 201102756 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: (none) 148718.doc