TW200920760A - Reactive carboxylate compound, active-energy-ray-curable resin composition utilizing the same, and use of the same - Google Patents

Abstract

To provide a resin composition which can be cured with an active energy ray such as ultraviolet ray or the like and enables to produce a rigid film or a molding material. Disclosed is a reactive compound derived from a phenolic epoxy resin containing a specific structure in the molecule, a compound having both of at least one polymerizable ethylenically unsaturated group and at least one carboxyl group in the molecule, and a compound having both of at least one hydroxyl group and at least one carboxyl group in the molecule. Also disclosed is a curable resin composition utilizing the reactive compound. A rigid cured article can be produced from the curable resin composition. The reactive compound has a good pigment-dispersing property.

Description

200920760 IX. Description of the Invention: [Technical Field] The present invention relates to a reactive epoxy carboxylate compound (A) and a reactive polycarboxylic acid compound (B) as an acid modifier thereof, the reactivity The epoxy carboxylic acid ester compound (A) is a phenolic epoxy resin (4) having a specific structure in a molecule, and a polymerizable ethylenically unsaturated group having both a polymer and a molecule represented by acrylic acid or the like. a compound having one or more carboxyl groups (a compound having one or more hydroxyl groups and one or more carboxyl groups in a knife (obtained by reacting with 0. The reactive epoxy carboxylate compound (A) and a reactive polycarboxylate) The acid compound (B) has a good affinity for the pigment, and a toughened cured product can be obtained from the resin composition containing the same. [Prior Art] In order to make the mobile device light and light or to increase its communication speed, a printed circuit is required. The board is highly precise and high-density. The requirements for the solder resist of the coated circuit itself are also increasing. Compared with the previous requirements, the printed circuit board is required to be further resistant to heat. It is thermally stable and can enhance the properties of substrate adhesion, high insulation, and non-electrical minerality. It is a material for beryllium forming materials with stronger physical properties. In the industry, it has been known to develop an epoxy resin containing a specific structure in a molecule, and a cured resin containing the same or a resin thereof, or an acid-modified J-phthalic acid ester resin thereof, is known in Patent Document 1 or Patent Document 2. An acid-modified epoxy acrylate having, for example, a phenol aralkyl type epoxy resin (for example, an iNc_3 〇〇〇 series manufactured by Nippon Chemical Co., Ltd., an nc 2 〇〇〇 series, etc.) as a basic skeleton is disclosed, and is generally known as 133740.doc 200920760 It is a material which exhibits a high degree of strongness after hardening, and has been studied as a solder resist. It is disclosed in Patent Document 3, which discloses that y 1 & another has a polycyclic hydrocarbon group as a basic skeleton. The acid-modified epoxy acrylate compound and its::曰= have been described as having relatively high kineticity after hardening. In addition, the comparative agent is also disclosed. However, although the solder resist has The reliability of 'but' does not satisfy the performance that can meet higher reliability with the electronicization of transmission equipment and the like in recent years. The electrons are also used as the acid preparation of these epoxy resins. The use of 暇 质 虱 虱 虱 虱 虱 尝试 尝试 尝试 尝试 尝试 分散 分散 分散 分散 分散 分散 分散 分散 分散 分散 分散 分散 分散 分散 分散 分散 分散 分散 分散 分散 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色 黑色Patent Document 5, No. 5, which discloses that the above-mentioned phenol aralkyl alkoxy oxy-resin is the basic skeleton of the acid-transfer ph ph ph acid-modified oxy-acid acrylate in the dispersion of carbon "color pigment" The application example of the black matrix photoresist t is also known. The following is also known as the following acid-modified ring of the epoxy tree having a polycyclic hydrocarbon group as the basic skeleton. The dispersion of carbon black in the enamel acrylate compound is applied as a black matrix photoresist. (Patent Document 6) However, in the case of a black matrix resist used in a liquid crystal display panel or the like, when a coloring pigment such as carbon black is blended in a nutrient manner, the pigment j is favorably dispersed in the tree month. Therefore, even if the high concentration of the pigment exhibits good developability, development without pigmentation can be achieved. The second...takes the pursuit of higher pigment concentration, that is, higher pigmentity. Although the previous acid-modified epoxy acrylate vines exhibited relatively good pigment dispersibility, there was a disadvantage of poor stability due to the false agglomeration in the pigment dispersion. On the other hand, it is known that a carboxylic acid ester compound obtained by reacting an acrylic acid and a carboxylic acid compound having a hydroxyl group with a common epoxy resin is a material having a low acid value and excellent developability. Further, Patent Document 7 It is disclosed that the compound has photoresist ink compatibility. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei No. Hei 5 No. Hei 5 No. 5, No. 5, No. 5, No. 5, No. 5, pp. [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei 2 No. Hei 2 No. Hei. [Patent Document 7] Japanese Laid-Open Patent Publication No. Hei 6-32449 No. [Invention] [Problems to be Solved by the Invention] Although the above-mentioned use molecule contains a specific structural composition, a hardened resin device of (4) strong epoxy resin can be obtained. Hardened material for extremely high reliability, but as a transmission

In view of the above problems, the inventors of the present invention have found that the molecule contains a specific structure and a coloring pigment dispersion resin composition which is not observed by the pigment dispersion liquid I33740.doc 200920760. An epoxy resin, a compound (b) having one or more polymerizable ethylenically unsaturated groups in the molecule and one or more hydroxyl groups and one or more carboxyl groups, and one or more hydroxyl groups and one or more The reactive epoxy carboxylate compound obtained by reacting the carboxyl group-containing compound (C), and the reactive polycarboxylate compound obtained by reacting the reactive epoxy carboxylate compound with the polybasic acid anhydride (d) have a special Excellent resin properties and resin properties as a cured product. Further, it has been found that the resin composition has a particularly good affinity with the coloring pigments, and it can be a photoresist material which has good developability even at a high pigment concentration. In other words, the present invention relates to a reactive epoxy carboxylic acid ester compound (A) which is an epoxy resin (a) represented by the following formula (1) and which is capable of being polymerized in one molecule or more. A compound (b) having a sulfonyl unsaturation group and one or more sulfo groups, and a compound (c) having one or more hydroxy groups and one or more carboxy groups in one molecule are obtained by reacting: [Chemical Formula 1]

133740.doc 200920760 (wherein '1 is the same or different, and represents a hydrogen atom, a halogen atom or a hydrocarbon group having a carbon number of 1 to 4; R·2 represents a divalent polycyclic hydrocarbon group having a carbon number of 7 to 16 or a carbon number of 7 to 18 of the exfoliating base; m represents an integer of 1 to 4, and η is an average value, indicating a positive number of 1 to 10). The present invention further relates to an epoxy resin (a) which is a reactive epoxy oxylate compound (A) of the formula (2):

(wherein & is the same or different from each other, and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms; 0 represents an integer of 1 to 4, and p is an average value, and represents a positive number of 1 to 10). The present invention further relates to an epoxy resin (a) which is a reactive epoxy oxy carboxylate compound of the formula (3): [Chemical 3]

133740.doc 200920760 (wherein R_4 are the same or different from each other' represents a hydrogen atom, a halogen atom or a hydrocarbon group having a carbon number of 1 to 4; q represents an integer of 1 to 4, and r is an average value, indicating a positive number of 1 to ίο ). The present invention further relates to an epoxy resin (a) which is a reactive epoxy oxy carboxylate compound of the formula (4): [Chem. 4]

(wherein Rs are the same or different from each other, and represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms; s represents an integer of 1 to 4, and t is an average value, and represents a positive number of 1 to 10). The present invention further relates to a reactive polycarboxylic acid compound (B) obtained by reacting the above-obtained reactive carboxylic acid ester compound (A) with a polybasic acid anhydride (d). Further, the present invention relates to an active energy ray-curable resin composition ‘characterized by containing the above-mentioned reactive carboxylic acid ester compound (A) and/or a reactive polycarboxylic acid compound. The present invention further relates to an active energy ray-curable resin composition' which contains a reactive compound (c) other than (A) and (B). The present invention further relates to an active energy ray-curable resin composition which contains a coloring pigment. 133740.doc 200920760 The present invention further relates to an active energy ray-curable resin composition containing a photopolymerization initiator. Further, the present invention relates to the above active energy ray-curable resin composition, which is a material for molding. Further, the present invention relates to the active energy ray-curable resin composition, which is a material for forming a film. Further, the present invention relates to the above active energy ray-curable resin composition, which is a photoresist material composition. 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 which is covered by the above active energy ray-curable resin composition. α [Effects of the Invention] The active energy ray-curable resin composition containing the epoxy resin having a specific structure in the molecule of the present invention can provide not only a toughened cured product but also a state in which it is dissolved. Excellent resin properties. The cured product obtained from the active energy ray-curable resin composition of the present invention can be preferably used as a material for forming a film which requires heat and mechanical strength. As a particularly preferable use, a solder resist for a printed circuit board, an interlayer insulating material for a multilayer printed wiring board, a solder resist for a flexible printed circuit board, a plating resist, a green light wave (four), and the like can be cited, and in particular, it can be used for higher requirements. In the use of special animals. Further, the obtained active energy ray-curable resin composition has high affinity with a coloring pigment such as carbon black, so that even at a high pigment concentration, 133740.doc 12 200920760 exhibits good pigment dispersibility and exhibits high affinity. Developability. Further, the pigment dispersion state of the color pigment dispersion can be maintained for a long period of time, thereby providing a resin composition capable of ensuring storage stability in the dispersion state of the ruthenium. Therefore, it is particularly useful as a photoresist for color resists and color filters, especially black matrix materials. [Embodiment] The reactive epoxy carboxylic acid ester compound of the present invention is a phenolic type of a characteristic skeleton represented by the following formula (〇) which is obtained by coupling a phenol epoxy group to a hydrocarbon group having a specific structure by imparting reactivity. The epoxy resin (a), the compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in the molecule, and one or more hydroxyl groups and one or more groups in one molecule The compound (C) is obtained by a reaction. Namely, the ethylenically unsaturated group and the hydroxyl group are simultaneously introduced into the molecular chain by esterification of the epoxy carboxylic acid to exhibit the characteristics of the present invention:

The epoxy resin (a) represented by the formula (1) used in the present invention is characterized in that it contains a phenolic epoxy group, and the carbon number represented by the heart is a "bivalent polycyclic ring" of the factory. a phenolic epoxy resin having a hydrocarbon group or a repeating skeleton of a hydrocarbon group having 7 to 18 carbon atoms. 133740.doc -13- 200920760 In the above formula, Ri is the same or different from each other and represents a hydrogen atom, a halogen atom or a carbon. The hydrocarbon group having a number of 1 to 4. Here, the halogen atom means a fluorine atom, a gas atom, a bromine atom, or a hard atom, and the hydrocarbon group having a carbon number of 1 to 4 represents a mercapto group, an ethyl group, a vinyl group, or the like. a saturated and unsaturated hydrocarbon group such as n-propyl, isopropyl, propenyl, n-butyl, isobutyl, t-butyl, tert-butyl or butenyl. R2 represents a valence of 2 to 16 carbon atoms. Polycyclic hydrocarbon group, or carbon number 7~18

Yan Fang from the base. Examples of the divalent polycyclic hydrocarbon group having a carbon number of 7 to 16 include: —裱[2,2,1]heptyldiyl, bicyclo[2,2,2]octyldiyl, octahydrocyclopentane Alkenyl decaindole, tetrahydrodicyclopentadienyl diyl, tetrahydrobicyclohexane dibasic. Among these, 'tetrahydrodicyclopentadienyl diyl can be preferably used. Further, examples of the exoaralkyl group having a carbon number of 7 to 18 include a stretched phenyl bismethylene group, a phenyl extended methyl group, a stretched phenyl bis methylene group, and a stretched phenyl double stretched ethyl group. A group, a naphthyl bismethylene group, a bis-methylene group, a phenymethylene group, a bis-methylene group, and the like. Among these, a phenyl bis-indenylene group and a phenyl bis-indenylene group can be preferably used. And in the general formula (1), m represents a "base number of 1 to 4. η is an average i' respectively represents a positive number of Η. Preferably, it is 1 匕 to 6. The value of η is less than 10, preferably. When it is less than 6, the epoxy tree 曰 (a) is in the appropriate viscosity range. The average value of R, which means that the money is heavy, can be used according to the use; suspected osmotic gas chromatography (Gpc) The measured value is calculated. As the towel-like epoxy resin (4), (IV) of the present invention is an epoxy resin having a characteristic biphenyl skeleton represented by the following general formula (2): 133740.doc -14- 200920760 [Chem. 6]

In the above formula, R3 is the same or π, and represents a hydrogen atom, a _ prime atom or a hydrocarbon group having 1 to 4 carbon atoms. The so-called dentinogen + represents a fluorine atom, a gas atom, a desert atom, and an atom. and then,. It represents an integer of Bu 4, and ρ is an average value, which respectively represents a positive number of 1 to 1 ,, preferably Bu 6 . When the value of ρ is less than 1 〇, preferably less than 6, the epoxy resin (4) is within a suitable viscosity range. In the epoxy resin (4) represented by the formula (7), all of them are nitrogen atoms, which are preferably obtained at low cost. Usually, it is available as a commercial product of the NC. 3000 series from this chemical. In the NC_3_ series, all of R3 in the above formula are strictly atoms, and P is an average value, and each represents a positive number of Ul. In the present invention, an appropriate one can be appropriately selected among the levels of the series. Further, as the epoxy resin (4) (4) in the invention (4), the aryl-based epoxy resin represented by the general formula (3) is used: 133740.doc 200920760 [Chemical 7] (3) , r4 are the same or different from each other, indicating a hydrogen atom,

Or a hydrocarbon group having a carbon number of 1 to 4. Further, q is an integer of '1' and 'eight', and an integral number of 1 to 4' and 1' is an average value, and represents a positive number of 1 to 10, respectively. Among the epoxy resins represented by the formula (3), it is preferred that all of them are a gas atom or a methyl group. The epoxy resin represented by the general formula (3) is usually obtained from the NC-2000 series. The Nc_2〇〇〇 series is all hydrogen atoms in the above formula, and the average value of 4 is 丨. Positive number. In the present invention, a suitable one can be appropriately selected among the grades of the series. ,

Further, as the epoxy resin (4) in the present invention, an epoxy resin having a polycyclic hydrocarbon group represented by the general formula (4) is preferred: [Chemical 8]

The wind atom and the dentate atom represent an integer of 1 to 4, and t is the above formula, R5 is the same or different from each other, or the hydrocarbon group having a stone inverse of 1 to 4, and s is a substitution number, 133740.doc -!6- 200920760 Average, representing a positive number from 1 to ίο. Wherein, R5 is a compound of a hydrogen atom or all of them are methyl groups.

The material can be obtained inexpensively and is preferred. Rs is all a hydrogen atom, and t is a flat S value, and a compound representing a positive number of W0 can be obtained as a XD_1000 series from a Japanese chemical (stock). In the towel of the present invention, a suitable compound can be appropriately selected from the range of the series.

The compound (b) having both _ or more polymerizable ethylenically unsaturated groups and a domain group in the molecule used in the present invention is imparted to the active energy ray. . Gan ¥ 1 d reverse response. The 4 is a monocarboxylic acid compound or a polycarboxylic acid compound.

Examples of the compound containing a single molecule in the molecule include, for example, (mercapto)acrylic acid or butyric acid, α-cyanocinnamic acid, cinnamic acid, or a saturated or unsaturated dibasic acid and A reaction of a non-fresh mono-glycidyl compound. In the above ten, examples of the acrylic acid include (mercapto)acrylic acid, β-styrene acrylic acid, ρ-glycosyl acrylic acid, and (meth)acrylic acid dimer, which are saturated or not. A saturated bis-anhydride and a half vinegar of a molar reaction of a (hydroxy) acrylate derivative having a hydroxyl group in a hydrazine molecule is a saturated or unsaturated 4 acid and (meth) acrylic acid monoglycidyl A half ester of a molar reactant such as an ester derivative. Further, examples of the polycarboxylic acid compound having a plurality of carboxyl groups in one molecule include a molar reactant having a plurality of (meth)pyropropionic acid derivative derivatives and a second 7C acid anhydride in a molecule. a semi-ester, a half-vinegar such as a saturated or unsaturated dibasic acid and a molar reactant such as a plurality of epoxy groups of glycidyl sulfonium S. 133740.doc -17- 200920760 ▲In terms of sensitivity when making an active energy ray-curable resin composition, the best of these is: (meth)acrylic acid, (meth)acrylic acid and £- The reaction product of the ester, or cinnamic acid. As the compound (9) having one or more polymerizable ethylenically unsaturated groups and one or more retarding groups in one molecule, it is preferred that the compound does not have a transbasic group. • The one used in the present invention is a combination of one or more mesogenic groups and one carboxylate-containing compound (4)' for introducing a hydroxyl group into a carboxylate compound. These include a compound having one hydroxyl group and one carboxyl group in one molecule, a compound having two or more hydroxyl groups and one carboxyl group in the molecule, and a compound having more than one meridional group and two or more groups in the molecule. The compound which has both a hydroxyl group and a carboxyl group in one molecule may, for example, be propylpropionic acid, butylbutyric acid or stearic acid. The compound r having two or more hydroxyl groups and one carboxyl group in the molecule may, for example, be dimethylol acetic acid, dimethylolpropionic acid or dimethylolbutanoic acid. The compound 'having one or more hydroxyl groups and two or more carboxyl groups in one molecule' may, for example, be hydroxyphthalic acid or the like. Among these, in view of the effects of the present invention, it is preferred to contain two or more bases in one molecule. Further, in view of the stability of the carboxylic acid esterification reaction, a preferred one molecule contains a carboxyl group. Most preferably, one molecule has two base groups and one carboxyl group. Particularly preferred are dimethylolpropionic acid and dimethylolbutanoic acid in view of the availability of raw materials. 133740.doc •18· 200920760 The compound (C) which is a compound of the above-mentioned base and one of the above-mentioned bases and (1) is preferably a polymerizable ethylenically unsaturated group. In the above, considering the reaction stability of the above epoxy resin (4) and the two kinds of tickic acid compounds (b) and (4), it is preferred that (8) and (4) are monodecanoic acid, and it is preferred that even (iv) mono-acid and In the case of a multi-m acid, the total mole amount of the mono/tetracarboxylic acid of the single (four) is also 15 or more.

The ratio of the ratio of the epoxy resin (4) to the total acid resistance of the acid-lowering compounds (b) and (4) in the reaction should be appropriately changed depending on the use. In other words, when all of the epoxy groups are acidified, the unreacted epoxy group does not remain, so the storage stability of the compound as a reactive component is high. In this case, only the reactivity brought about by the double bond of the person to be guided will be utilized. On the other hand, it is also possible to intentionally leave unreacted green in the finger by reducing the amount of the carboxylic acid compounds (b) and (C), and to store the unsaturated bond. The reaction, the reaction, and the reaction caused by the residual epoxy group, for example, a polymerization reaction or a thermal polymerization reaction caused by a photocationic catalyst. However, in this case, care must be taken when preserving reactive tartrate compounds and studying manufacturing conditions. / Residual reactive epoxy group reaction (IV) Oxygen (tetra) Cooling compound = the case 'It is preferred that the total amount of the cyclic lacto-based acid compounds (b) and (4) with respect to 1 equivalent of the above epoxy resin (4) is %~ Within the scope, it can be manufactured under the conditions of the relative 缰~々 attack from the right. When the carboxylic acid compound is more than this, it is not preferable. In the case where the remaining carboxylic acid compound is retained, 133740.doc -19- 200920760, in the case where the residual branched oxygen group is used, it is preferred that the total of the acid-lowering compounds (8) and (4) are relative to the above ring of lf4. The oxygen resin (4) is 2 Å to 1 column equivalent %. When the shape of the target is in the shape of the target, the effect of the composite hardening is weakened. Of course, in this case, sufficient attention must be paid to the gelation in the reaction and the stability of the (iv) vinegar compound (A) over time. In the case of the molar ratio of the carboxyl group, the use of the compound (b) having more than one polymerizable ethylenically unsaturated group and more than one county, and the compound (4) having more than one radical and one or more mercapto groups The ratio (b): (4) is preferably in the range of 9:...9, more preferably in the range of 4:6 to 8:2. If it is within this range, it is possible to prevent the sensitivity from being lowered when (b) is too small, and it is possible to prevent the effect of (c) from being weakened when (c) is too small. This rebellion can be reacted in the absence of a solvent, or it can be diluted with a solvent to carry out the reaction. The solvent which can be used herein is limited as long as it is inert to the acidification reaction. (4) The amount of the solvent to be used is adjusted according to the viscosity or use of the obtained resin. The solvent is preferably used in such a manner that the solid content is 9 G to 3 Qf%, more preferably 80 to 50% by mass. Specific examples of the solvent that can be used as the solvent include aromatic hydrocarbon solvents such as toluene, benzene, ethylbenzene, and tetraphenylene, and aliphatic hydrocarbon solvents such as hexamethylene and oxime. As a mixture of such a stone test, white gasoline, solvent petroleum brain and the like. Further, examples of the ester solvent include ethyl acetate, propyl acetate, and ethyl acetate, and the like; r-butane vinegar and the like; and ethylene glycol 133740.doc • 20· 200920760

Monomethyl ether acetate, di r _ π M monoethyl epoxide per oxime ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene dioxime, early ether monoacetate, diethylene Alcohol monobutyl ether monoacetic acid series, rain-pain to -. - drunk early methyl acetate, butanediol monomethyl ether acetate, mono- or polyalkylene glycol monoalcoholic monoacetate; A polyalkyl carboxylate such as a dialkyl acid ester, a succinic acid, a succinic acid, or a polycarboxylic acid alkyl ester such as hexamethylene ketone. 'As an ether solvent, it can be enumerated. The alkyl esters such as diethyl ether and ethyl butyl ether, ethylene glycol, hexaerythritol, ethylene glycol, dipropylene glycol, dipropylene glycol, dipropylene glycol B shout, -- ο - alcohol monomethyl ether, triethylene glycol diethyl ether and other glycol ethers; tetrahydrofuran and other cyclic ethers. Further, examples of the 'solvent' include C-, methyl ethyl ketone, cyclohexanone, and isophorone. * Other than this, the reaction can be carried out in a separate or mixed organic solvent such as the reactive compound (c) other than (Α) or (Β) described later. In this case, it is preferred to use it as a composition when it is used as a hardening type composition. In the reaction, it is preferred to use a catalyst for promoting the reaction. The amount of the catalyst used is relative to the total amount of the reactants, that is, the above epoxy compound (4), compound (b) compound (c), and optionally added. The total amount of reactants such as solvent is 0, 〗 〖! 〇% by mass. The reaction temperature at this time is 6 Torr to 5 Torr, and the reaction time is preferably 5 to 6 G hours. Specific examples of the catalyst that can be used include, for example, ethylamine, dimethylbenzylamine, triethylammonium vapor, benzyltridecylsulfonylamine, benzylidenetrimethylphosphonium phenylphosphine, Known common organic catalysts such as triphenyl record, methyl triphenyl record, chromium octoate, and octanoic acid. Further, as the thermal polymerization inhibitor, it is preferred to use hydroquinone monoterpene 133740.doc -21 - 200920760 ether, 2-T-based hydroquinone, hydroquinone, diphenyl bitter, diphenyl Yisine, 3,5-di-tert-butyl perfluorotoluene, and the like. In the present reaction, sampling is suitably carried out to obtain an acid value of the sample of not more than $ mgKOH/g, preferably at a time of 2 mgK〇H/g or less. ... as a comparison of the reactive carboxylic acid ester compounds obtained in this way

In the preferred molecular weight range, the polystyrene-equivalent weight average molecular weight of GPC is in the range of 1, 〇〇〇 to 30,000, more preferably 丨^(10) to ❹(8). Yu j. In the case of a knife, the strongness of the cured product cannot be sufficiently exhibited. When the molecular weight is larger than the molecular weight, the viscosity is increased and coating is difficult. Hereinafter, the reactive polycarboxylic acid compound (B) of the present invention obtained by an acid addition step will be described. The acid addition step is carried out in order to obtain a reactive poly(tetra) compound (8) by introducing a retinyl group as required in the reactive carboxylate compound (A) obtained in the previous step. In the use of the resistive pattern, for example, it is necessary to impart solubility to the active energy ray non-irradiated portion in alkaline water, and to impart adhesion to metals, inorganic substances, and the like. Specifically, the carboxyl group is introduced via an ester bond by an addition reaction of a polybasic acid anhydride (d) to a radical formed by an epoxy group reaction. Specific examples of the polybasic acid anhydride (4) can be used, for example, in the case of a compound having an acid needle structure in one molecule, and particularly preferably an acid anhydride having excellent in aqueous solution developability, heat resistance, hydrolysis resistance, and the like. Phthalic anhydride, tetrahydro o-benzoic anhydride, hexahydrophthalic anhydride, itaconic acid 133740.doc -22- 200920760 needle, 3-mercaptotetrahydrophthalic anhydride, 4-methyl-6 Hydrogen phthalic anhydride, trimellitic anhydride, or maleic anhydride. The addition of the polybasic acid anhydride (d) can be carried out by adding a polybasic acid anhydride (d) to the above carboxylic acid esterification reaction liquid. The amount added should be changed as appropriate. However, when the polycarboxylic acid compound (B) of the present invention is to be used as an alkali-developing type photoresist, it is preferred to input a polybasic acid anhydride (d) of the following calculated value. The solid acid value of the obtained reactive polycarboxylic acid compound (according to JIS K5601-2-1: 1999) is 30 to 120 mg. KOH/g, more preferably 40 to 1 〇 5 11^.1 <: 〇 The calculated value of 11/§. When the acid value of the solid matter at this time is in the range, the alkaline aqueous solution developability of the active energy ray-curable resin composition of the present invention exhibits good developability. That is, the patterning property is good and the management range for overdevelopment is also wide, and no excess acid anhydride remains. Preferably, the catalyst is used in the reaction to promote the reaction, and the catalyst is used in a total amount relative to the reactants, that is, relative to the epoxy compound (a), the carboxylic acid compounds (b) and (c). The total amount of the obtained carboxylate compound (A), multi-π acid liver (4), and a solvent or the like added as needed is % by mass. The reaction temperature at this time is 604 5 (rc, and the reaction time is preferably 5 to 6 hours. Specific examples of the catalyst which can be used include, for example, triethylamine, dimethyl amide, and triethyl hydride. Ammonium chloride, benzyltrimethylammonium bromide, benzyl trimethyl sulfonamide, triphenylphosphine, triphenyl phthalate, methyltriphenyl sulfonium, chromium octoate, octanoic acid, etc. The reaction can be carried out in the absence of a solvent, or it can be reacted by diluting with a solvent. The solvent which can be used herein is a solvent which is inert with respect to the acid addition reaction. There is no particular limitation. It is the same as the one used in the lower esterification reaction of the previous step. When the carboxylic acid esterification reaction in the previous step is carried out using a solvent, it is also possible. As a condition of being inert with respect to the two reactions, the solvent is not removed and supplied directly to the next step, the acid addition reaction.

The preferred amount of solvent to be used depends on the viscosity or use of the resin obtained. It is preferred to adjust the amount of the solid to a solid content of 90 to 30 mass. /〇, it is better to use the solvent in a manner of 80 to 50% by mass. In addition, it can be carried out by using the following reactive compound (c) or the like alone or in combination with organic solvents. In the case of the above (4), it is preferred to use it as a composition in the case of a hardening type composition. Further, it is preferred that the thermal polymerization inhibitor or the like be the same as the above-described carboxylic acid esterification reaction. In the present reaction, 'taken appropriately #, and the acid value of the reactant reached the range of the set acid value ± 1 G% as the end point. The difficult energy ray-curable resin composition of the present invention comprises an epoxy retinoic acid compound (4) and/or a polydecanoic acid compound (B). The epoxy retinoic acid compound (VIII) and/or the multiple (tetra) compound (8) are suitably used separately depending on the use thereof. In the case of the application of the P UI, the case where the pattern is formed by the printing method without developing, or the so-called solvent development type is washed out by the solvent 箄, Ψ, and the soil team J temple, the ring can be used. Oxygen-based compound (4), when it is developed by using water, can be acidified by ^m (8)^ I33740.doc •24- 200920760 _!, it is easy to make a fine pattern when it is an alkaline water developing type. And Lu, the use of 'Φ & Afc ^, and more use of polycarboxylic acid compounds (B). Of course, when the epoxy carboxylic acid & (A) is combined with the polycarboxylic acid compound (B), it does not produce any

The active energy ray-curable resin composition of the present invention may further contain a reactive compound (C) other than the oxime oxime compound (VIII) and the polycarboxylic acid compound (B). In the present invention, specific examples of the reactive compound (C) which can be used include a radical reaction type acrylate, a cationic reaction type other % oxygen compound, and a vinyl compound which induces the two. Reactive oligomers. Examples of the acrylates which can be used include monofunctional (fluorenyl)acrylic acid-based and polyfunctional (meth)acrylates, and examples thereof include epoxy acrylate vinegar, polyester acrylate, and acryl carboxylic acid. Ester and the like. Examples of the monofunctional (fluorenyl) acrylates include decyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) propylene 1 laurel vinegar, and polyethylene. Alcohol (mercapto) acrylic acid, polyethylene glycol (meth) acrylate monomethyl ether, (mercapto) phenyl ethyl acrylate, (fluorenyl) isobornyl (meth) acrylate, cyclohexyl (meth) acrylate Benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and the like. Examples of the polyfunctional (meth) acrylate include butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylic acid vinegar.壬diol di(indenyl)acrylic acid S, ethylene glycol di(indenyl) acrylate, diethylene glycol bis(indenyl) acrylate, polyethylene glycol bis (曱133740.doc -25- 200920760 base) acrylate, tris(methyl) propylene oxyethyl isocyanurate, polypropylene glycol di(meth) acrylate, adipic acid epoxide di(meth) acrylate, Bisphenol oxyethylene bis(indenyl) acrylate, hydrogenated bisphenol oxyethylene (meth) acrylate, bisphenol di(meth) acrylate, hydroxypivalic acid neopentyl glycol ε-caprolactone plus Poly(meth)acrylic acid vinegar, dipentaerythritol poly(fluorenyl) acrylate, trishydroxypropyl propane tris (meth) acrylate (dimercapto) acrylate, dipentaerythritol and ε-hexanol Acrylate, trishydroxyethylpropane tri(meth)acrylate and its ethylene oxide adduct, pentaerythritol III Yue-yl) acrylate, and ethylene oxide adduct, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and ethylene oxide adducts. Examples of the vinyl compound which can be used include vinyl ethers, styrenes, and other ethylene compounds. Examples of the ethylene test include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of the styrenes include styrene, methylstyrene, and ethylstyrene. Examples of the other vinyl compound include triallyl isocyanurate and trimethylallyl isocyanurate. Further, the term "reactive oligomer" includes an acrylamide-based carboxylic acid having both a functional group capable of inducing an active energy ray and a urethane bond in the same molecule; a polyester acrylate which senses a functional group of an active energy ray and an ester bond; and an epoxy acrylate which is derived from an epoxy resin and which has a functional group capable of inducing an active energy ray in the same molecule; A reactive oligomer or the like using these bonds is used. Further, the cationically reactive monomer is usually not particularly limited as long as it is a compound having an epoxy resin. For example, (meth)acrylic acid glycerin vinegar, methyl glycidol oxime, ethyl glycidol shrine, butyl glycidol shrine, bis bis diglycidyl ether, 3,4 epoxycyclohexyl 13,4·Epoxycyclohexylformate ("Carb UVR-6U" manufactured by Uni〇n Car·), 3,4-epoxycyclohexylethyl_3,4 _Epoxycyclohexylcarboxylic acid brewing, dioxane ethylene disulfide (ELR-4206 manufactured by Union Carbide Corporation, etc.), oxidized lemon dilute (Dasai Road (1) is called "Celloxide 3" manufactured by Chemical Industry Co., Ltd. 〇", etc.), propylene oxide hexene, 3,4-epoxy I methylcyclohexyl 2 propylene oxide, 2_(3,4_epoxy f hexyl-5,5-spiro-3, 4. Epoxy) cyclohexyl-m-dioxane, adipic acid bis(oxime. epoxycyclohexyl) ester ("Cyracure uvr_^28" manufactured by Union Carbide Co., Ltd.), adipic acid bis (3, 4) _Epoxycyclohexylmethyl) vinegar, double heart ring lactam hexyl) hydrazine, bis(3,4-epoxycyclohexylmethyl) shuang, bis(3,4-epoxycyclohexyl)diethyl oxime Alkane, etc. Among these, as the reactive compound, a radical-hardening acrylate is preferred. In the case of the cationic form, since the carboxylic acid reacts with the cyclic lactide group, it is necessary to prepare a two-liquid mixing type. By mixing the carboxylic acid ester compound (A) of the present invention and/or the reactive polycarboxylated D product (B), and optionally the reactive compound (C) other than (A) and (B), The active energy ray-curable resin composition of the present invention is obtained. 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 97 to 5 mass% in the composition. More preferably, it is a carboxylic acid ester compound of 133 740.doc • 27· 200920760 (A) and/or a reactive polycarboxylic acid compound (B), and contains 3 to 95% by mass, more preferably It is 3 to 90% by mass of the reactive compound (6) other than (8) and (B). Other ingredients with an upper limit of 7% can be included as needed.

The colored pigment which can be used in the present invention means that the active energy ray-curable resin composition of the present invention is used as a coloring material. The balance between the carboxylic acid vinegar compound (VIII) used in the present invention and the hydroxyl group of the reactive polycarboxylic acid compound (B) is within a specific range, so that it is particularly excellent in affinity with a pigment. Dispersibility. Although it is not clear about the mechanism, since the dispersion can be favorably performed, the pigment rolling degree is made rich, and in the composition which must be developed, a good patterning property can be exhibited due to a better dispersion state. Further, since the developing residue of the developing and dissolving portion is also small, it is preferable. Examples of the coloring pigment include organic pigments such as m-doped n-type (tetra), and inorganic pigments such as carbon black and titanium oxide. These medium carbon blacks have higher dispersion and are better. In order to efficiently and sufficiently harden, a photopolymerization initiator may be added to the active energy ray-curable resin composition of the present invention. The photopolymerization initiator "is a radical photopolymerization initiator "cationic photopolymerization initiator" and other polymerization initiators. Examples of the radical photopolymerization initiator include benzoin, benzoin, shampoo, benzoin, benzoin, benzoin, and the like; acetophenone, 2,2_diethoxy_ 2_Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, diacetophenone, 2_hydroxy-2-indole-based, small-propyl-, diethoxybenzene Ethyl ketone, K hydroxycyclohexyl phenyl ketone, 甲 133740.doc -28- 200920760 ke-W4-(methylthio)phenyl]_2 _ _ _ _ _ _ _ Stuffed, 2-tert-butyl...2-chlorinated onion, 2_pentyl, _please; 2'4-diethyloxosulfide, Yamaguchi, 2•iso-based _9_ oxysulfide Star, 2_chloro·9-oxathiazide, etc.-9-oxothiopurine; phenethyl dimethyl ketal, ketone dimethyl ketal and other ketals; diphenyl (4), 4_ Benzoinyl _4·_methyldiphenyl sulfonate, 4,4'-bismethylaminobenzophenone and other benzophenones 2 4 6_trimethylbenzimidyl diphenyl Phosphine oxide, bis(2, trimethyl benzhydryl)

A conventional radical type photoreaction initiator such as a phosphine oxide such as phenylphosphine oxide. Further, examples of the cationic photopolymerization initiator include a diazonium salt of a Lewis acid, a phosphonium salt of a Lewis acid, a nickel salt of a Lewis acid, a scale salt of a Lewis acid, other tooth compounds, and a three-spray initiator. "Initiatives and other photoacid generators, etc.. Examples of the diazonium salt of the Lewis acid include p-methoxyphenyldiazo (tetra)phosphonate, Ν'Ν·diethylaminophenyl. Nitrogen hexafluorophosphate (San-Aid SI-60L/SI-80L/SI-100L, etc. manufactured by Sanshin Chemical Industry Co., Ltd.); etc.; as a lock salt of a Lewis acid, diphenylphosphonium hexa(tetra) acid salt And diphenylsulfonium hexahydrophthalic acid; etc.; as a bismuth salt of a Lewis acid, a trisyl sulfonium hexafluorophosphonate (such as uv^6990 manufactured by Union Carbide Co., Ltd.), triphenylsulfonium hexafluoroantimonate Salt (Uni〇n~ manufactured by Heart Company)

Cy_re UVI-6974, etc.); and the scaly salt of a Lewis acid may, for example, be a triphenyl scaly hexafluoroantimonate. As other compounds, 2, 2, 2_three gas _ Π _ 4 Ι • (dimethyl ethyl) phenyl] ethyl ketone (Trig〇nal ρι, manufactured by ΑΚΖΟ company), 2, 2 _: gas - 133740 .doc -29- 200920760 1-heart (the present oxyphenyl) B _ (Sandray 1 000, etc.), α,α,α-tribromomethylphenyl sulfone (BMPS, manufactured by Titanic Chemical Co., Ltd.) and many more. As the starting agent of the three tillage system, 2,4,6-tris(trichloromethyl)-trisole, 2,4-trimethylmethyl-(4,-methoxyphenyl)_6_3 Plowing (Tdazine A, etc. manufactured by Panchim), 2,4-trichloromethyl_(4'·methoxystyryl)-6-three tillage (Triazine Pms manufactured by Panchim, etc.), 2,4- Tri-gas methyl-(Pepperyl)-6-three tillage (Triazine pp, manufactured by Panchim, etc.), 2,4_trimethylmethyl-(4'-methoxynaphthyl)-6-three tillage (Panchim Triazine B, etc. manufactured by the company, 2_[2,·(5"_methylfuranyl)ethylidene]_46_bis(trimethylmethyl)-all three tillage (manufactured by Sanwa Chemical Co., etc.), 2_( 2, _furanylethylidene)-4,6-bis(trichloromethyl)_all three ploughing (manufactured by Sanwa Chemical Co., Ltd.), etc. As a boric acid ester-based initiator, Japanese photosynthetic pigments can be cited as iNK_ 3876 and ΝΚ-388 1 and the like; as other photoacid generators, etc., 9-phenyl oxazole (biimidazole manufactured by Heijin Chemical Co., Ltd.), 2,2- azobis (2-amino-propane) Dihydrochloride (V5〇 manufactured by Wako Pure Chemical Co., Ltd.), 2,2_azobis[2_(imidazolin-2-yl) ) propane] dihydrochloride (such as va〇44 manufactured by Wako Pure Chemical Industries, Ltd.), [η·5·2_4·(cyclopentadecanyl) (1, 2, 3, 4, 5, 6 (methyl) Ethyl)-stupyl] iron (π) hexahydrophosphonate (produced by Ciba Geigy, chu _ 261, etc.), bis (y5-cyclopentadienyl) bis-difluoromethane Titanium (CGI_784, etc., manufactured by Ciba Geigy Co., Ltd.), etc. In addition to this, it is also possible to use azobisisobutane to protect oxygen and to guess azo-based initiators, and to pass the peroxides for the induction of heat.士士斯丨+切乐目 is based on a basic initiator. 'You can also use both free radicals and cations to make ten initiators. The initiator can be 133740.doc -30- 200920760 alone 1 In addition, the composition of the present invention may be used in combination with the above-mentioned amount of the wire-curable resin, and the resin component is the other component of the upper limit. Other ingredients: quality agent, pigment material, coloring material, and volatile viscosity added for human: addition, additivity, etc. to impart appropriate applicability to the coating. Others can be used as other additives, for example, a medium, a thixotropy imparting agent such as AerosU, a heat-hardening defoaming agent such as poly-coin, a benzoic acid, a para-benzene:, a fluorine-based leveling agent or an agent, Antioxidant, etc. I. A polymerization inhibitor such as a scale, which is stable and used as a material for other pigment materials. For example, it is also possible to use a pigment which is not intended for coloring. For example, ',, platinum, π-deficient 芈· π stone, barium sulfate, carbonated town, barium titanate, hydrazine hydroxide, stone stone, clay, and the like. In addition, it is also possible to use the same type of resin (the inert polymer which does not show reactivity).

Xie furnace, 1 such as other epoxy resin, phenol resin, amine ester tree glutinous rice, polyester resin, _J type ψ α M r '赦 " ah type of cheese resin, cresol resin, xylene tree 曰 本 本 甲酸Di-propyl ester correction # 曰 secret moon 曰, styrene resin, guanamine resin, natural and synthetic rubber, propylene eucalyptus, polyolefin resin, and these modified substances. These resins are used. In the range of 〇 mass %, if it is to be used in the case where the reactive polyphthalic acid compound is used as a solder resist, it is preferred to use it as a common one which does not exhibit a reactive oxime for the active energy ray. Epoxy resin. The reason is that after reacting and hardening using the 133740.doc •31 - 200920760 performance line, the carboxyl group derived from (b) will remain, resulting in water resistance or hydrolysis of the cured product. Therefore, by using an epoxy resin, the remaining carboxyl group is further carboxylated to form a stronger crosslinked structure. It can also be used for the purpose of adjusting the viscosity according to the use of (4). Better yet, 35 mass% is Add volatile dissolved solution

The present invention relates to an active energy ray-curable resin composition which is a molding material and a film forming material composition. Or U in the present invention, the term "forming material" means an uncured composition = a mold, or a (4) mold to form an object, and then formed by active energy == reaction; or unhardened The material used in the composition. The use of the towel to cause the hardening reaction to be formed: the use of the body 'is exemplified by the following preferred uses: forming a planar shape, protecting the sealing material of the component, and microfabricating the "module to the unhardened combination" On the object, the micro-mica die-casting material is further carried out, and in particular, the following: (4) "The 舻, the umbrella wire a T,,,, the 囟 囟 之 之 之 之 之 周边 周边 周边 周边 周边 周边 周边 周边 周边Sealing materials, etc. In the present invention, it is used as a material for forming a medium. As a specific application, gravure ink, convex=based ink, plate ink, black... Earth ink, ink, etc., hard coating, overcoat, overprint, lacquer, clear coating, etc., lamination Use: agent, adhesive, etc., followed by material discs with 4 kinds of receiver blocking agents, etching resists, micro-mechanical light I33740.doc -32- 200920760 resistance and other anti-surname materials are equivalent. Further, the so-called dry film in which the film forming material is temporarily applied to the release substrate and then bonded to the original target substrate to form a film also corresponds to the film material. It is preferred to use (4) to improve the adhesion to the substrate, and therefore it is preferably used in applications for coating a plastic substrate or a metal substrate. Properties: Two: It is also preferred to use the unreacted reactive polycarboxylic acid compound (B) in a basic aqueous solution to become a soluble composition. In the present invention, the term "photoresist material composition" means a film layer on which a β-mite composition is formed on a substrate, and then partially irradiates an active energy ray such as ultraviolet rays, and the illuminating portion is used. An activity-line-inductive type composition in which the physical properties of the green temple are different, and specifically, the composition uses a method such as a solvent or the like. Sexual dissolution = dissolution of the irradiated portion or the unirradiated portion, and the active energy ray-curable resin r::: hardened by the invention. Here, as the active energy ray: ?, infrared, x-ray" The preferred use of the invention such as ray, thunder ray, etc., ❹, etc. If you consider this light or electron beam. Among the preferred materials of 4, ultraviolet rays, lightning rays, and various materials which can be used in the active energy ray hardening (IV) of the present invention, such as J, can be used as a solder resist material, and a layering method 133740.doc * 33 - 200920760 "Interlayer insulating material, and can also be used as an optical waveguide for printing electrical, electronic, optical substrates, etc., such as reflective electronic substrates or optical substrates. As a particularly good use, it can be fully utilized. It is used for permanent photoresists such as solder resists, and it is used for color resists such as printing inks and color calenders, especially for permanent photoresists such as solder resists. The use of a photoresist for a black matrix. In addition to this, it can also be particularly preferably used for dry film applications, which requires mechanical strength of the hardening reaction using the / tongue performance s line. That is, due to the present invention: The balance of the base group and the epoxy group of the epoxy resin (4) is in a specific range, so that although the reactive phthalate compound of the present invention has a relatively high molecular weight, it can also exert a good display. The method of forming the bedding is not particularly limited, and the following methods can be used arbitrarily: a concave i printing method such as a gravure, a letterpress printing method such as a letterpress, a stencil printing method such as a screen, a lithographic printing method such as a plate printing, and a roll coating method. Various coating methods such as knife coating, die coating, curtain coating, and spin coating. The cured product of the active energy ray-curable resin composition of the present invention means the active energy ray-curable resin of the present invention for use in the above-mentioned use. The composition is irradiated with an active energy ray to harden it. It is understood that the material covered by the active energy ray-curable resin composition of the present invention means that the active energy ray-curable type of the present invention is formed on a suitable substrate. The film layer of the resin composition is partially irradiated with an active energy ray such as ultraviolet rays to obtain a film hardened layer formed on the substrate. In this case, the cured product of the resin composition can be uniformly formed on the substrate. The article of the hardened layer 133740.doc -34- 200920760 The article which is formed to form the film hardened layer may be a resist pattern product, and is not particularly limited. u >, the present invention is by way of example, but the present invention is not limited to the examples. In the examples, unless otherwise indicated, the parts represent parts by mass.

The softening point, epoxy equivalent, and the like were measured under the following conditions. υEpoxy equivalent: measured according to the method according to JISK 7236: 2_. 2) Softening point: The measurement was carried out in accordance with the method according to JIS K 7234: 1986. 3) Acid value: The measurement was carried out in accordance with the method according to JIS K〇〇7〇: 1992. 4) The measurement conditions of GPC are as follows.

Equipment type: TOSOH HLC-8220GPC

Column: TSKGEL Super HZM-N Dissolve · · THF 〇 Hydrogen Furan); 0.35 mi per minute, 4 〇〇 c Detector: Differential Refractometer Molecular Weight Standard: Polystyrene Solid Example 1. With General Formula (2) Preparation of the carboxylate compound (a) of the epoxy resin indicated by adding 288 g of NC-3000H as an epoxy resin (a) (manufactured by Nippon Kayaku Co., Ltd., softening point: 70 ° C, epoxy equivalent: 288 g /eq, all of R3 shown in the formula (2) is a hydrogen atom 'p is an average value, and the amount described in Table 1 is one or more polymerizable ethylenically unsaturated groups in the molecule. Acrylic acid of one or more carboxyl groups (b) (abbreviated as Aa, Mw = 72), and the amount described in Table 1 as a compound having one or more hydroxyl groups and one or more carboxyl groups in the molecule] 33740.doc -35· 200920760 c) Dihydroxymethyl propionic acid (abbreviated as DMPA, Mw == ι34). The input equivalent ratio of each AA and DMPA to the epoxy group is described in terms of molar ratio. 3 g of triphenylphosphine as a catalyst was added, and propylene glycol monomethyl ether monoacetate as a solvent was added so that the solid content became 80% by mass, and the reaction was carried out for 24 hours at rc to obtain the carboxy group of the present invention. The acid ester compound solution (AV; 1^^: 〇^§) was used to determine the end point of the reaction, and the measured values are shown in Table 1. The acid value was measured in the reaction solution and then converted into a solid form. The acid value of the product. Example 2: Preparation of a carboxylate compound of the epoxy resin represented by the general formula (3): 230 g of NC 2 oxime (epoxy resin (4)) was added, and the product was softened. The point is 6 (TC, epoxy equivalent is 230 g/eq, R4 shown in the general formula (3) is a hydrogen atom, r is an average value, is 5), and the amount described in Table 1 is a compound (b). Acrylic acid and dimethylolpropionic acid as compound (c). The equivalent ratio of each AA and DMPA to epoxy group is described by molar ratio. 3 g of triphenylphosphine as a catalyst is added and added. As a solvent, propylene glycol monomethicone is called monoacetic acid vinegar so that the solid matter becomes 8 〇 mass% of the reaction liquid at 1 〇〇 ° C The reaction was carried out for 24 hours to obtain a solution of the carboxylate compound (A). The end point of the reaction was determined by the acid value of the solid (AV; mgKOH/g), and the measured values are shown in Table 1. The acid value was measured in the reaction solution. And then converted to the acid value of the solid matter. Example 3: Production of the epoxy carboxylic acid ester compound (A) of the epoxy resin represented by the general formula (4) 133740.doc • 36· 200920760 , plus 250 g XD-1 000 (manufactured by Nippon Chemical Co., Ltd.) has a softening point of 7 (TC, epoxy equivalent of 25 〇g/eq, and all of them are represented by the formula (4) as a hydrogen atom, 1 The average value is the amount of the glyco-acid (b) as the chemical substance (b) and the methylpropionic acid as the compound (c) in the amounts described in Table 3) and Table 1. The relative AA and DMpA are described in terms of molar ratio. The equivalent ratio of the epoxy group was used. 3 g of triphenylphosphine was used as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent was added to make the solid matter 8% by mass, and reacted at 1 hour for 24 hours. , obtaining a solution of the epoxy carboxylate compound (A)" using the solid acid value (AV; mgK〇H / g) to determine the reaction 'end point, will be determined It is described in Table 1. The acid value was measured in the reaction solution and converted to the acid value of the solid. Comparative Example 1: Preparation of a comparative carboxylic acid ester compound, NC-3000H 288 g was added as a compound) Acrylic acid 72 § (Morby: 1.0), 3 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent was added so that the solid content became 80% by mass. The reaction was carried out for 24 hours to obtain a carboxylate compound solution. The end point of the reaction was determined by the solid acid value (AV; mgKOH/g), and the measured values are shown in Table 1. The acid value is measured in the reaction solution and then converted to the acid value of the solid. Comparative Example 2: Preparation of a comparative carboxylic acid ester compound: 230 g of NC-2000, acrylic acid as a compound (b) "molar ratio: 1.0", 3 g of triphenylphosphine as a catalyst, and added as a solvent The propylene glycol monomethyl ether monoacetate was reacted at 80 ° C for 24 hours to obtain a carboxylate compound solution. The solid matter acid value was obtained by reacting the solid matter at 8% by mass of the reaction liquid at 133740.doc -37 to 200920760 at 100 ° C. (AV; mgKOH/g) was used to determine the end point of the reaction, and the measured values are shown in Table 1. The acid value was measured in the reaction solution and then converted to the acid value of the solid. Comparative Example 3: Comparative epoxy carboxylate The ester compound is prepared by adding XD-1000 250 g, as the compound (b), the acrylic acid 72 is in molar ratio: 1.0), and as a catalyst, triphenylphosphine 3 §, adding propylene glycol monomethyl ether as a solvent The acid ester was reacted at 丄(10) for 24 hours to obtain a solution of the epoxy phthalate compound. The acid value (AV; mgKOH/g) was used to determine the end point of the reaction, and the measured value was recorded. In Table 1. The acid value is measured in the reaction solution. And then converted to the acid value of the solid. Comparative Example 4-1: Preparation of the comparative carboxylic acid ester compound Addition of the phenolic phenolic-type epoxy resin EOCN-103S (manufactured by Nippon Kayaku Co., Ltd., softening point is 80 ° C, ring An oxygen equivalent of 200 g/eq) 200 g, 36 g of acrylic acid as a compound (b) having more than one polymerizable ethylenically unsaturated group and more than one carboxyl group in the molecule (mole ratio: 〇.5) And 67 g (molar ratio: 0.5) of dimethylolpropionic acid which is a compound (c) having one or more hydroxyl groups and one or more carboxyl groups in the molecule. 3 g of triphenylphosphine as a catalyst is added and added The propylene glycol monomethyl ether monoacetate as a solvent was reacted at 8% by mass for 24 hours to obtain a comparative carboxylic acid ester compound solution. The solid acid value (AV; mgKOH/g) was used. The end point of the reaction was determined, and the measured values are shown in Table 1. The acid value was measured in the reaction solution, and 133740.doc -38 - 200920760 was then converted into the acid value of the solid. Comparative Example 4-2: Comparison Preparation of acid ester compound with cresol novolac type epoxy resin jER-1002 (Japan Manufactured by Oxygen Resin Co., Ltd., having an epoxy equivalent of 400 g/eq) 200 g, 18 g of acrylic acid as (b) (mole ratio: 0.5), and 34 g of dimethylolpropionic acid as compound (c) Ratio: 0.5). Add 3 g of triphenylphosphine as a catalyst, and add propylene glycol monoterpene ether monoacetate as a solvent to make the solid matter 80% by mass of the reaction liquid, at (.' 1 〇〇 The reaction was carried out at ° C for 24 hours to obtain a comparative carboxylic acid ester compound solution. The acid value of the solid (AV; mgKOH/g) was used to determine the end point of the reaction, and the measured values are shown in Table 1. The acid value is measured in the reaction solution and then converted to the acid value of the solid. [Table 1]

Examples 1, 2, 3 and Comparative Examples 1, 2, 3, 4: Preparation of epoxy carboxylic acid ester compound (A) Synthesis Example Epoxy resin AA amount (g) (Mohr ratio) DMPA amount (g) ( Mohr ratio) AV (mgKOH/g) Example 1-1 NC-3000H 14 (0.2) 107 (0.8) 2.4 Example 1_2 NC-3000H 36 (0.5) 67 (0.5) 2.1 Example 1-3 NC-3000H 58 (0.8) 27 (0.2) 2.8 Example 1-4 NC-3000H 22 (0.3) 27 (0.2) 0.9 Example 2-1 NC-2000 14(0.2) 107(0.8) 2.8 Example 2-2 NC- 2000 36(0.5) 67 (0.5) 2.3 Example 2-3 NC-2000 58 (0.8) 27 (0.2) 1.9 Example 2-4 NC-2000 22 (0.3) 27 (0.2) 0.5 Example 3-1 XD -1000 14 (0.2) 107 (0.8) 2.4 Example 3-2 XD-1000 36 (0.5) 67 (0.5) 2.1 Example 3-3 XD-1000 58 (0.8) 27 (0.2) 2.8 Example 3-4 XD-1000 22 (0.3) 27 (0.2) 0.9 Comparative Example 1 NC-3000H 72(1.0) 0 (0.0) 2.5 Comparative Example 2 NC-2000 72(1.0) 0 (0.0) 2.5 Comparative Example 3 XD-1000 72( 1.0) 0 (0.0) 2.5 Comparative Example 4-1 EOCN-103S 36 (0.5) 67 (0.5) 2.5 Comparative Example 4-2 jER-1002 18 (0.5) 34 (0.5) 1.4 133740.doc -39- 200920760 Test Example 1 : Storage stability of epoxy carboxylate compound (A) The epoxy carboxylate compound solution obtained in Example 1 and Comparative Example 1 was stored in a freezer at minus 5 ° C, and the time until crystals were produced was compared and shown in Table 2. [Table 2] Test Example 1: Storage stability of epoxy carboxylate compound Compound (A) Epoxy resin (b) / (c) Time Example 1-1 NC-3000H 0.2/0, 8 6 months or more Example 1-2 NC-3000H 0.5/0.5 6 months or more Example 1-3 NC-3000H 0.8/0.2 3 months Comparative Example 1 NC-3000H 1.0/0.0 3 weeks According to the above results, it is clear that with the molecule In the introduction of the compound (c) having one or more hydroxyl groups and one or more carboxyl groups, the storage stability of the resin solution is improved. Example 4: Preparation of Reactive Polycarboxylic Compound (B) of Epoxy Resin represented by General Formula (2) The carboxylic acid esters obtained as Examples 1-1, 1-2, and 1-3, respectively To 299 g of the compound (A) solution, tetrahydrophthalic anhydride (abbreviated as THPA) as the polybasic acid anhydride (d) described in Table 3 was added, and propylene glycol monomethyl ether monoacetate as a solvent was added thereto. The solid content was changed to 65% by mass, and heated to 100 ° C to carry out an acid addition reaction to obtain a reactive polycarboxylic acid compound (B) solution of the present invention (Examples 4-1, 4-2, 4-3, 4) -4). The solid acid value (mgKOH/g) is shown in Table 3. Example 5: Preparation of Reactive Polycarboxylic Acid Compound (B) of Epoxy Resin represented by General Formula (3) 133740.doc -40- 200920760 as Example 2-1, 2-2, 2-3 In 299 g of the carboxylic acid ester compound (A) solution obtained in each of 2-4, the tetrahydrophthalic anhydride as the polybasic acid anhydride (d) was added in an amount described in Table 3, and propylene glycol as a solvent was added. The oxime ether monoacetate is obtained by reacting the solid matter to 65 mass% of the reaction liquid, heating to 100 ° C, and performing an acid addition reaction for 3 hours to obtain a reactive polycarboxylic acid compound (B) solution of the present invention (Example 5_1) , 5-2, 5_3, 5_4, 5_5). The solid acid value (mgKOH/g) is shown in Table 3. Example 6: an epoxy carboxylic acid ester obtained by the polycarboxylic acid compound (b) of the epoxy resin represented by the general formula (4), which was obtained as an example 3-1, 3-2, and 3-3, respectively. To 299 g of the compound (A) solution, tetrahydrophthalic anhydride as the polybasic acid anhydride (d) described in Table 3 was added, and propylene glycol monomethyl ether monoacetate as a solvent was added to make the solid matter 65 % by mass, heated to 1 Torr to carry out an acid addition reaction to obtain a polycarboxylic acid compound (B) solution (Examples, ^ 2, 6-3, 6-4). The solid acid value (mgK〇H/g) is shown in Table 3. Comparative Example 5: Comparative Preparation of Reactive Polycarboxylic Acid Compound The carboxylic acid ester compound solution obtained in Comparative Example 1 was added to 299 g of the tetracarboxylic acid as the polybasic acid anhydride (d) in the amount of 5 liters in Table 3. Phthalic anhydride, and propylene glycol monomethyl ether monoacetate as a solvent was added to make the solid content 65% by mass, and heated to 1 Torr. (: An acid addition reaction was carried out to obtain a reactive polycarboxylic acid compound solution (Comparative Example 5_丨, 5_2). The solid acid value (mgKOH/g) is shown in Table 3. Comparative Example 6: Comparative reactivity The polycarboxylic acid compound was prepared in 299 g of the carboxylic acid ester compound solution obtained in Comparative Example 2, and 133740.doc •41 was added.

200920760 The amount of tetrahydro(tetra)dicarboxylic acid as the polybasic (4) in the amount shown in Table 3, and the addition of propylene glycol monomethylidene monoacetate as a solvent to make the solid matter 65% by mass of the reaction liquid, and heating (four) generation A 3-hour acid addition reaction was carried out to obtain a reactive polycarboxylic acid compound solution (Comparative Example 6_丨, 幻幻. The solid acid value (mgKOH/g) is shown in Table 3. Comparative Example 7··Comparatively used for reactivity The carboxylic acid compound was prepared in 299 g of the epoxy carboxylic acid ester compound solution obtained in Comparative Example 3, and the amount of tetrahydrophthalic anhydride as the polybasic acid anhydride (d) described in Table 3 was added and added as The propylene glycol monomethyl ether monoacetate of the solvent was subjected to an acid addition reaction by heating the solid content to 65 mass% to obtain a polycarboxylic acid compound solution (Comparative Example 7_丨, 7_2). MgKOH/g) is shown in Table 3. Comparative Example 8: Comparative Preparation of Reactive Polycarboxylic Acid Compounds The preparation of the epoxy carboxylic acid ester compound solution 299 g obtained in Comparative Examples 4-1 and 4-2 was added. The amount of tetrahydrophthalic anhydride as a polybasic anhydride as described in Table 3 Further, propylene glycol monoterpene ether monoacetate as a solvent was added to make the solid matter 65% by mass, and heated to 〇〇. The hydrazine was subjected to an acid addition reaction to obtain a polyoxoic acid compound solution (Comparative Examples 8-1, 8- 2, 8-3). The solid acid value (mgKOH/g) is shown in Table 3. 133740.doc • 42- 200920760 [Table 3] Examples 4, 5, 6 and Comparative Examples 5, 6, and 7. 8 : Preparation of Reactive Polycarboxylic Acid Compound (B) Synthesis Example Compound (A) Epoxy Resin (b) / (〇) THPAt (g) Solid Acid Value Example 4-1 Example 1-1 NC-3000H 0.2/0.8 88 102 mgKOH/g Example 4-2 Example 1-2 NC-3000H 0.5/0.5 88 101 mgKOH/g Example 4-3 Example 1-3 NC-3000H 0.8/0.2 88 103 mgKOH/g Example 4-4 Example 1-2 NC-3000H 0.5/0.5 37 51 mgKOH/g Example 5-1 Example 2-1 NC-2000 0.2/0.8 88 100 mgKOH/g Example 5-2 Example 2 -2 NC-2000 0.5/0.5 88 103 mgKOH/g Example 5-3 Example 2-3 NC-2000 0.8/0.2 88 103 mgKOH/g Example 5-4 Example 2-2 NC-2000 0.5/0.5 37 50 mgKOH/g Example 5-5 Example 2-4 NC-2000 0.3/0.2 88 101 mgKOH/g Example 6-1 Example 3-1 XD-1000 0 .2/0.8 66 81 mgKOH/g Example 6-2 Example 3-2 XD-1000 0.5/0.5 66 82 mgKOH/g Example 6-3 Example 3-3 XD-1000 0.8/0.2 66 80 mgKOH/ g Example 6_4 Example 3-2 XD-1000 0.5/0.5 29 41 mgKOH/g Comparative Example 5-1 Comparative Example 1 NC-3000H 1.0/0.0 88 101 mgKOH/g Comparative Example 5-2 Comparative Example 1 NC-3000H 1.0/0.0 37 52 mgKOH/g Comparative Example 6-1 Comparative Example 2 NC-2000 1.0/0.0 88 101 mgKOH/g Comparative Example 6-2 Comparative Example 2 NC-2000 1.0/0.0 37 52 mgKOH/g Comparative Example 7- 1 Comparative Example 3 XD-1000 1.0/0.0 66 81 mgKOH/g Comparative Example 7-2 Comparative Example 3 XD-1000 1.0/0.0 29 40 mgKOH/g Comparative Example 8-1 Comparative Example 4-1 EOCN-103S 0.5/0.5 88 102 mgKOH/g Comparative Example 8-2 Comparative Example 4-2 jER-1002 0.5/0.5 88 100 mgKOH/g Comparative Example 8-3 Comparative Example 4-1 EOCN-103S 0.5/0.5 66 80 mgKOH/g

Examples 7, 8, and 9 and Comparative Examples 9, 10, 11, and 12: Preparation of a hard coating composition and a cured product thereof, and hardness evaluation test and impact evaluation test thereof, etc. Examples 1 and 2 3 and 20 g of the reactive carboxylate compound (A) prepared in Comparative Examples 1, 2, and 3 '4, and 4 g of dipentaerythritol hexaacrylate as a monomer of the radical hardening type (C), as an ultraviolet reaction The type of initiator Irgacure 1 84 1.5 g was dissolved by heating. (In Examples 7-4, 8-4, and 9-4, 1.0 g of UVI-6990 was additionally added as a cationic initiator.) Further, a manual applicator was used so that the film thickness at the time of drying was 20 μm. 133740.doc -43- 200920760 It was coated on a polycarbonate plate and dried in an electric oven at 80 ° C for 30 minutes. After drying, an ultraviolet ray vertical exposure apparatus (manufactured by ORC Co., Ltd.) equipped with a high-pressure mercury lamp was used, and ultraviolet rays having an irradiation dose of 1000 mJ were irradiated and hardened to obtain a multilayer material.

The hardness of the coating film of the multilayer material was measured in accordance with JIS K 5600-5-4: 1999 (Test Example 2), and the impact test (Test Example 3) was carried out in accordance with ISO 6272-l:2002, and according to JIS K 5600- 7-4: 1999 to carry out the thermal shock test (Test Example 4). Each of the prepared test samples (Examples 7 to 9 and Comparative Examples 9 to 12) and the respective evaluation test results (Test Examples 2 to 4) are shown in Table 4. [Table 4] Examples 7, 8, and 9 and Comparative Examples 9, 10, 11, and 12: Preparation and evaluation of materials for hard coating Test sample Compound (A) Epoxy resin (b) / (c) Pencil hardness and impact resistance Example 7-1 NC-3000H 0.2/0.8 Η Ο - Example 7-2 Example 1-2 NC-3000H 0.5/0.5 2H 〇 - Example 7-3 Example 1-3 NC-3000H 0.8/0.2 3H Δ - Example 7-4 Example 1-4 NC-3000H 0.3/0.2 3H 〇 - Example 8-1 Example 2-1 NC-2000 0.2/0.8 Η 〇- Example 8-2 Example 2-2 NC-2000 0.5/0.5 2Η 〇 - Example 8-3 Example 2-3 NC-2000 0.8/0.2 3Η Δ - Example 8-4 Example 2-4 NC- 2000 0.3/0.2 3Η 〇 - Example 9-1 Example 3-1 XD-1000 0.2/0.8 ΗΒ - 〇 Example 9-2 Example 3-2 XD-1000 0.5/0.5 2Η - 〇 Example 9- 3 Example 3-3 XD-1000 0.8/0.2 3Η - Δ Example 9-4 Example 3-4 XD-1000 0.3/0.2 3Η - 〇Comparative Example 9 Comparative Example 1 NC-3000H 1.0/0.0 3Η X - Comparison Example 10 Comparative Example 2 NC-2000 1.0/0.0 3Η X - Comparative Example 11 Comparative Example 3 XD-1000 1.0/0.0 3Η - X Comparative Example 12-1 Comparative Example 4-1 EOCN-103S 0.5/0 .5 Η XX Comparative Example 12-2 Comparative Example 4-2 jER-1002 0.5/0.5 3Β X - Evaluation of impact resistance and thermal shock resistance: 〇: no damage, peeling; △: slight damage; X: peeling 133740.doc -44 - 200920760 «The above results are clear with and without the use of a compound (C) having both a thiol group and a carboxyl group in the molecule, and a comparison of all of the epoxy groups with acrylates, Comparative Examples 9, 1 and 11, The impact resistance of the hard coating material prepared in Examples 7, 8, and 9 was improved. The reason why the impact resistance is improved is that the density of the double bond is moderately lowered with the introduction of the compound (c), and the loose crosslinked structure formed by the hydrogen bond has a favorable influence with the introduction of the hydroxyl group. Further, in Comparative Examples ^ and 12_2 derived from a conventional difunctional epoxy resin, the hardenability was greatly deteriorated, and the impact resistance was low. Examples 10, 11, 12 and Comparative Examples 13, 14, 15, and 16: Preparation of dry film type resist composition and cured product thereof were added in Examples 4, 5, and 6 and Comparative Examples 5, 6, 7, and 8. The obtained reaction I" oxime carboxylic acid compound (B) 54.44 g, as other reactive compound (c) HX-220 (trade name; dimethacrylate monomer manufactured by Sakamoto Chemical Co., Ltd.) 3.54 g, Irgacure_9〇7 (manufactured by Ciba Specialty Chemicals) 4.72 g as a photopolymerization initiator and 0.47 g of Kayacure DETX-S (manufactured by Sakamoto Chemical Co., Ltd.), gtr_ 18 as a hardening component (manufactured by Sakamoto Chemical Co., Ltd.) 14.83 g, melamine 1 〇 5 g as a thermosetting catalyst, and methyl ethyl ketone 2 〇 95 g as a concentration adjusting solvent, which were kneaded using a bead mill The dispersion was uniformly dispersed to obtain a photoresist resin composition. The obtained composition was uniformly applied onto a polyethylene terephthalate film as a support film by a wire bar coater #2 0 ', and passed through a hot air drying oven at a temperature of 7 (rc to a thickness of 20 μm). After the resin layer, a polyethylene film as an outer film was attached to the resin layer to obtain a dry film. The outer film of the obtained dry film was peeled off while using a heating roll of 80 ° C, and 133740. Doc -45- 200920760 The resin layer was attached to the entire substrate surface of a polyimide substrate (copper circuit thickness: 1 2 μηι; polyimine film thickness: 25 μm). Further, Example 10-5 The mixture of (Α) and (Β) used in 11-6, 12-5 means a ratio of 5〇:5〇 by weight of the solution, and Examples 1-1 and 2-, respectively. The acid-modified carboxylic acid ester compound (Α) prepared in 1, or 3-1 is polyascorbic acid equivalent to the epoxy resin prepared in Examples 4-1, 5-1, or 6-1. The compound (Β) is mixed with the resultant. Then, using an ultraviolet exposure device (〇RC Manufacturing Co., Ltd.; model: HMW-680GW), by drawing a circuit diagram The reticle and the staged exposure meter manufactured by Kodak for evaluating the sensitivity were irradiated with ultraviolet rays of 5 〇〇 mJ/cm 2 . Thereafter, the film on the dry film was peeled off to confirm the peeling state. The sodium carbonate aqueous solution was spray-developed, and the resin of the ultraviolet non-irradiated portion was removed. After washing with water, the printed circuit board was subjected to a heat-hardening reaction for 60 minutes in a hot air dryer of i 5 to obtain a cured film. The evaluation method was tested (Test Example 5 to 1 〇), and the properties of the dry film type photoresist cured films obtained in Examples 10, 11, and 12 and Comparative Examples 13, 14, 15, and 16 were evaluated. The evaluation result of the evaluation test of the film is shown in Table 5. Test Example 5: Evaluation of the refractive index of the polyimide printed circuit board on which the cured film of the photoresist was formed so that the side of the cured film was located on the top side (m〇 Untain f〇id), fully bend the bent portion with your fingers. Restore the bent portion and observe the photoresist film with a magnifying glass. Evaluation criteria: 〇: no crack; △: a few cracks were observed; X: peel test Example 6: Evaluation of thermal and thermal shock resistance 133740.doc • 4 6- 200920760 In the range of -65~120C, the thermal shock test was carried out on the polyimide substrate with hardened yttrium formed by photoresist. The test method was based on jjS C50I2-9.1: 1993. After the test, use ce] The iophane tape (registered trademark) was subjected to a peeling test. Evaluation criteria: 〇··No peeling: slight peeling was observed; x: peeling test was performed. Example 7: Evaluation of high-temperature moisture resistance 'Polycene formed with a cured film of photoresist The amine printed substrate was placed in an autoclave of 120 for 1 hour. The substrate was taken out, air-dried at room temperature, and then subjected to a peeling test using O cellophane tape (registered trademark). Evaluation criteria: 〇: no peeling; Δ: slight peeling was observed; χ: peeling test was produced. Example 8: Sensitivity evaluation sensitivity was based on the concentration remaining in the exposed portion of the staged exposure meter at the time of development. Part to judge. When the number of stages (value) is large, it is determined that there is high sensitivity (unit: level) in the rich portion of the exposure table. Test Example 9: Evaluation of the developability The evaluation was performed based on the time until the pattern-shaped portion was completely developed when the exposed portion of the transmission pattern mask was developed, that is, the evaluation of the imaging time (unit: second). ^ Test Example 10: Evaluation of hardenability The sclerosing valence was 15 利用. . The lead level of the cured film after the end of heating is expressed. Evaluation 僧t,»· v None The steam system is based on JISK5600-5-4: 1999. 133740.doc -47- 200920760 [Table 5] Examples 10, 11, 12 and Comparative Examples 13, 14, 15, Sample Compounds (B) Epoxy Resin (b) / (c) Example 10-1 Example 4-1 NC-3000H 0.2/0.8 Example 10-2 Example 4-2 NC-3000H 0.5/0.5 Example 10-3 Example 4-3 NC-3000H 0.8/0.2 Example 10-4 Example 4- 4 NC-3000H 0.5/0.5 Example 10-5 (A) + (B) Example (1-1) + (4-1) NC-3000H 0.2/0.8 Example 11-1 Example 5-1 NC- 2000 0.2/0.8 Example 11-2 Example 5-2 NC-2000 0.5/0.5 Example 11-3 Example 5-3 NC-2000 0.8/0.2 Example 11-4 Example 5-4 NC-2000 0.5 /0.5 Example 11-5 Example 5-5 NC-2000 0.3/0.2 Example 11-6 (A) + (B) Example (2-1) + (5-1) NC-2000 0.2/0.8 Implementation Example 12-1 Example 6-1 XD-1000 0.2/0.8 Example 12-2 Example 6-2 XD-1000 0.5/0.5 Example 12-3 Example 6-3 XD-1000 0,8/0.2 Implementation Example 12-4 Example 6-4 XD-1000 0.5/0.5 Example] 2-5 (A) + (B) Example (3-1) + (6-1) XD-1000 0.2/0.8 Comparative Example 13 -1 Comparative Example 5-1 NC-3000H 1.0/0.0 Comparative Example 13-2 Comparative Example 5-2 NC-3000H 1.0/0.0 Comparative Example 14-1 Comparative Example 6-1 NC-2000 1.0/0.0 Comparative Example] 4-2 Comparative Example 6-2 NC-2000 1.0/0.0 6_性〇〇<1〇〇〇〇△〇〇〇..... XXX 〇--X 〇- price sensitive evaluation; £ 489107 resistance----light and film ff:..... dry cold shadow 〇〇△〇〇〇〇〇〇〇489007 48907 生29735 5 6 9 5 0 7 2 1 9 0 5 ΛΊ 1 1 4 3 3 2 3 4 5 3 3 2 3 4 5 3

Then 2H3H3H3H2H2H3H3H3HH2H2H3H3H3H2H Comparative Example 15-1 Comparative Example 7-1 XD-1000 1.0/0.0 Comparative Example 15-2 Comparative Example 7-2 XD-1000 1.0/0,0 Comparative Example 16-1 Comparative Example 8-1 EOCN-103S 0.5/0.5 Comparative Example 16-2 Comparative Example 8-2 jER-1002 0.5/0.5 Comparative Example 16-3 Comparative Example 8-3 EOCN-103S 0.5/0.5

- - 9 50 4H - - Cannot develop 3H - - 7 50 3H - - Cannot develop 3H Unirradiated part does not dissolve X Δ 7 50 3H X △ Cannot develop 3H - - 9 45 3H - - Cannot develop 4B Irradiation part loss XX 9 45 3H From the above results, it is clear that the photoresist composition of the present invention can obtain a cured product having a relatively high hardness, and has good developability and sensitivity as a photoresist. Further, in the case of Examples 10 and 11, it has high folding endurance. Further, in Example 12, it has high cold shock resistance and high temperature moisture resistance. The photoresist composition of the comparative example and the cured product thereof did not show good evaluation of the resistance, the developability and the sensitivity of the resistance to the folding and thermal changes, and could not satisfy the as a dry pancreas. The properties of photoresist materials. Example 13 and Comparative Examples 17, 18·· Flame Retardant Resin, and Preparation of Comparative Resin and Photoresist Prepared in 16_〗 Example 1 0-2 and Comparative Example 3-1 Composition 9·5 g, phosphoric acid vinegar-based flame retardant (sp_7〇3H manufactured by Shikoku Chemicals Co., Ltd.) 〇, 5 g of mixed (four) 'obtained hardened resin composition 1 wire bar coater #20, the composition was applied to a film thickness of 25 μm The polyimide film was passed through a temperature of 70. (: The hot air drying oven, forming a resin layer having a thickness of about 15 (four). Using an ultraviolet exposure device (〇Rc Manufacturing Co., Ltd.; model: HMW picking GW), after irradiating a material line of 5〇〇mJ/cm2, 15 (In the hot air dryer of TC, the printed substrate was subjected to a heat hardening reaction to obtain a cured film (Example 13, Comparative Example 17, 18, respectively). Test Example 11: Evaluation of flame retardancy Example 13 The cured film obtained in Comparative Examples 17 and 18 and the film of the polyimide intermediate substrate were cut into a strip having a length of 20 cm and a width of 2 cm. The cut film was vertically suspended 'with the igniter from the lower end Ignition and evaluation of flame retardancy. For comparison of flame retardancy and folding endurance, the flexural test data of Example 10-2, Comparative and 16 1 are collectively described in Table 6 below for reference. 133740.doc - 49- 200920760 [Table 6] Test Example 11: Evaluation of flame retardancy of Example 13 and Comparative Examples 17 and 18

Example Compound (B) Epoxy Resin (b) / (c) Fissile Flame Retardant Example 13 Example 10-2 NC-3000H 0.5/0.5 Ο 〇 Comparative Example 17 Comparative Example 13-1 NC-3000H 1.0 /0.0 X 〇Comparative Example 18 Comparative Example 16-1 EOCN-103S 0.5/0.5 XX Flame retardancy evaluation criteria: 〇: Ignition, but the fire was extinguished before all the burnout. X: All burned out. From the above results, it is clear that the carboxylic acid ester compound of the present invention is a material which can simultaneously have flame retardancy and flexibility. Example 1 4, 1 5, 16 and Comparative Examples 19, 20, 2 1 and 22: Preparation of Colored Pigment Dispersion Resin The reactions obtained in Examples 4, 5 and 6 and Comparative Examples 5, 6, 7, and 8 were carried out. Polycarboxylic acid compound (Β) 20 g, DPHA (trade name; acrylate monomer manufactured by Sakamoto Chemical Co., Ltd.) as another reactive compound (C), 5.0 g, propylene glycol monomethyl ether as an organic solvent Acetate 1 〇g, and 10 g of Mitsubishi carbon black MA-100 as a coloring pigment were mixed and stirred. 35 g of glass beads were placed therein and dispersed by a paint shaker for 1 hour. The dispersion after completion of the dispersion was applied onto a polyethylene terephthalate film by a bar coater #2, and dried in a warm air dryer at 80 ° C for 1 minute to obtain each carbon black dispersion resin. Test Example 12: Evaluation of Pigment Dispersibility Using a 60° reflection gloss meter (1G-331 gloss meter manufactured by Horiba, Ltd.), the results obtained in Examples 14, 15, and 6 and Comparative Examples 19, 20, 21, and 22 were obtained. The gloss of the surface of the coating film of the carbon black dispersion resin was measured, and the dispersibility of carbon black was evaluated. At this time, the higher gloss indicates that the pigment dispersibility is good. The results are shown in Table 7 in 133740.doc -50- 200920760. [Table 7] Examples 14, 15, 16 and Comparative Examples 19, 20, 2 and 22: Evaluation of Pigment Dispersibility Evaluation Sample Compound (B) Epoxy Resin (b) / (c) Gloss Example 14-1 Example 4-1 NC-3000H 0.2/0.8 44 Example 14-2 Example 4-2 NC-3000H 0.5/0.5 58 Example 14-3 Example 4-3 NC-3000H 0.8/0.2 40 Example 14-4 Example 4-4 NC-3000H 0.5/0.5 55 Example 15-1 Example 5-1 NC-2000 0.2/0.8 55 Example 15-2 Example 5-2 NC-2000 0.5/0.5 68 Example 15- 3 Example 5-3 NC-2000 0.8/0.2 46 Example 15-4 Example 5-4 NC-2000 0.5/0.5 63 Example 16-1 Example 6-1 XD-1000 0.2/0.8 45 Example 16 -2 Example 6-2 XD-1000 0.5/0.5 62 Example 16-3 Example 6-3 XD-1000 0.8/0.2 48 Example 16-4 Example 6-4 XD-1000 0.5/0.5 59 Comparison Example 19-1 Comparative Example 5-1 NC-3000H 1.0/0.0 35 Comparative Example 19-2 Comparative Example 5-2 NC-3000H 1.0/0.0 31 Comparative Example 20-1 Comparative Example 6-1 NC-2000 1.0/0.0 20 Comparative Example 21-1 Comparative Example 7-1 XD-1000 1.0/0.0 30 Comparative Example 21-2 Comparative Example 7-2 XD-1000 1.0/0.0 25 Comparative Example 22-1 Comparative Example 8-1 EOCN-103S 0.5/0.5 23 ratio Comparative Example 22-2 Comparative Example 8-2 jER-1002 0.5/0.5 15 Comparative Example 22-3 Comparative Example 8-3 EOCN-103S 0.5/0.5 17 From the above results, it is clear that the reactive polycarboxylic acid compound of the present invention ( B) The dispersion of the pigment is improved. The pigment dispersion effect is considered to be due to the difference in the effect of the addition of the epoxy resin of the specific structure to the epoxy resin and the compound (c) of the specific structure in the molecule. Example 1 7 and Comparative Examples 23 and 24: Preparation of Colored Pigment Dispersion Resin 20 g of the reactive polycarboxylic acid compound (B) obtained in Example 4-2 and Comparative Examples 5-1 and 8-1 was used. Other reactive compound (C) DPHA (trade name; acrylate monomer manufactured by Nippon Kayaku Co., Ltd.) 5·0 g, as organic 133740.doc -51 - 200920760 solvent propylene glycol monomethyl ether acetate 丨〇g, mixed with Mitsubishi carbon black MA-100 1〇g as a coloring pigment. 35 g of glass beads were placed therein and dispersed by shaking the paint for 1 hour. The obtained carbon black dispersion resin liquid was collected in a sample bottle to obtain a colored pigment dispersion. Test Example 13: Evaluation of storage stability of the coloring pigment dispersion liquid The coloring pigment dispersion prepared in Example 17 and Comparative Examples 23 and 24 was allowed to stand at 40 ° C for 2 weeks, and the state of the dispersion liquid was visually evaluated. The results are shown in Table 8. [Table 8] Example 17 and Comparative Example 23, s parity sample compound (B) Example 17 Example 4-2 Comparative Example 23 Comparative Example 5-1 Comparative Example 24 Comparative Example 8-1 The pigment dispersion liquid was stable and stable. Evaluation of Epoxy Resin NC-3000H 0.5/0.5 NC-3000H 1.〇/〇.〇EOCN-103S 0.5/0.5 Stability Evaluation County··〇: homogeneous solution; △: dispersion gradient; χ: pigmentation

Stability △ Δ X From the above results, it was confirmed that the color pigment dispersion of the example did not cause separation of the dispersion even after 2 weeks at 4 ° C to maintain a uniform state. On the other hand, in Comparative Example 23, a transparent layer (varnish floating matter) appeared in the upper layer, and the dispersed state was unstable. In Comparative Example 24, the colored pigment was precipitated, and it became a bear which did not become uniform even if it was stirred. According to the above results, it is clear that in the reactive polycarboxylic acid compound (B) of the present invention, in the epoxy resin (4) having a specific structure as a basic skeleton, one or more polymerizable ethylenic unsaturations in the introduced molecule are combined. a compound (b) having one or more carboxyl groups, and a compound (4) having more than one hydroxyl group and more than one molecule in the molecule, can improve the dispersibility of the pigment, and can provide 133740.doc -52 - 200920760 liter of the pigment dispersion thereof. Save stability. [Industrial Applicability] The active energy ray-cured body fat of the present invention is exemplified as a hard coating material and can be used as a material for compatibility, flexibility, toughness, and flame retardancy. The active light ray hardening 5L tree of the present invention can be used as, for example, an active energy ray-curable printing ink, a color resist, for the purpose of developing a photo resist material which is necessary for flexibility and exhibiting good pigment dispersibility. In particular, it is particularly suitably used as a color resist for LCD (liquid_efyStal display), in particular, a black matrix or the like, as a material having a resistivity such as pigment dispersibility and developability. 133740.doc -53-

Claims (1)

200920760 X. Patent Application Range: 1. A reactive epoxy carboxylate compound which is an epoxy resin (a) represented by the formula (1), which has more than one polymerizable ethylene in one molecule. A compound (b) having one or more carboxyl groups and one or more compounds (c) having one or more hydroxyl groups and one or more carboxyl groups in one molecule are obtained by reacting: [Chemical 9] (1) (wherein 1 is the same or different from each other, and represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms; & represents a divalent polycyclic hydrocarbon group having a carbon number of 7 to 16 or an anisotropic number of 7 to 18 An aralkyl group; m represents an integer of 丨~4, and n is an average value, indicating a positive number of 1 to 1〇). 2. The reactive epoxy carboxylate compound of claim 1, (a) is the formula (2): wherein the epoxy resin I33740.doc 200920760 (In the case of gold, R3 is the same or different, and represents a hydrogen atom, a helium atom or a tanshin of the charcoal ~4 '0' represents an integer from 1 to 4, and p is an average value, indicating a positive number from 1 to 10) . 3 · For example, the reactive ring capsule of the item 1 is a ruthenium carboxylic acid S 曰 compound, wherein the epoxy resin (a) is of the formula (3): [Chem. 11] (wherein R4 is the same or different from each other' represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 4 carbon atoms; q represents an integer of 1 to 4, and !* is an average value indicating a positive number of 1 to 1 Å). 4. The reactive epoxy carboxylate compound of claim 1, wherein the epoxy resin U) is of the formula (4): [Chemical 12] (wherein R5 is the same or different from each other, and represents a wind atom, a halogen atom or a hydrocarbon group having a carbon number of 1 to 4; s represents an integer of 1 to 4, and t is an average value, and represents a positive number of 133740.doc 200920760 1 to 10; ). A reactive polycarboxylic acid compound which is a combination of a reactive carboxylic acid ester compound of any one of claims 1 to 4 and a polybasic acid anhydride (reacted by a sentence of 0) And a reactive polyacid carboxylic acid compound (4) according to any one of the claims, and/or a reactive polycarboxylic acid compound (Β) according to claim 5, 7 The active energy ray-curable resin composition of Item 6 further contains a reactive compound (c) other than (A) or (A). 8. The active energy ray-curable resin composition according to claim 6 or 7, wherein Further, it contains a coloring pigment. The active energy ray-curable resin composition of the above-mentioned item 6 to 8 further contains a photopolymerization initiator. The active energy ray hardening of any of the items 6 to 9 of the month. The resin composition is a material for molding. The active energy ray-curable resin composition according to any of the items 6 to 9 of the present invention is a material for forming a film. 12 · As shown in the items 6 to 9 You are a ji eve, winter μ· Ah 1 & The resin composition is a photoresist material composition. The active energy ray of the active energy ray of the item is a cured product of the hardened resin composition of any one of claims 6 to 9. An article which is covered by any of the hardening type resin compositions of any one of claims 6 to 9. 133740.doc 200920760 VII. Designation of representative drawings: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of this representative figure is simple: 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: 133740.doc