JP6556735B2 - Reactive polyester compound and active energy ray-curable resin composition using the same - Google Patents

Description

  The present invention relates to an N-phenylphenolphthalein type epoxy resin (a) having an excellent balance of hydroxyl group, epoxy group and softening point, and one or more polymerizable ethylenic groups in a molecule represented by acrylic acid or the like. It is obtained by polymerizing a compound (b) having both a saturated group and one or more carboxyl groups and a saturated or unsaturated polybasic acid anhydride (c) having at least two acid anhydride structures in one molecule. It relates to the reactive polyester compound (A). Furthermore, the present invention relates to a reactive polyester compound (A ′) obtained by reacting a reactive polyester compound (A) with a saturated or unsaturated dibasic acid anhydride (d).

  These reactive polyesters have good dispersibility in pigments, and from resin compositions containing these, film forming materials, solder resists, plating resists, color resists, color filter resists, black matrices, etc. A tough cured product suitable for various resists and optical waveguides can be obtained.

  With the aim of reducing the size and weight of portable devices and improving communication speed, printed wiring boards are required to have high precision and high density, and as a result, the demand for solder resist that covers the circuit itself has become increasingly sophisticated. . For this reason, solder resists are required to have the ability to withstand substrate adhesion, high insulation, and electroless gold plating while maintaining heat resistance and thermal stability. There has been a demand for a film-forming material having physical properties.

  For these materials, a reactive polycarboxylic acid compound in which a carboxyl group is introduced with an acid anhydride for the purpose of patterning with an alkaline developer after carboxylating an epoxy resin with acrylic acid or the like is used for resist, In particular, application to solder resists is generally known (Patent Documents 1 and 2).

  Acid-modified epoxy acrylates having a phenol aralkyl type epoxy resin (for example, NC-3000 manufactured by Nippon Kayaku Co., Ltd.) as a basic skeleton are generally known as materials exhibiting high toughness after curing, and as a solder resist using the same. The use is also being studied (Patent Document 3).

  Among these, in film formation applications, particularly solder resist applications, physical properties in a state where the solvent is only volatilized after the film formation is also an important factor. Specifically, if it is more flexible than necessary at this stage, peeling or patterning film contamination occurs. In particular, in applications such as so-called dry film, this characteristic is more important because a transfer process is included.

  In order to improve toughness before and after curing, it is a general technique to use a material having a high molecular weight, but in this case, there is a problem that developability is greatly impaired.

  In addition to this, the resin composition containing the N-phenylphenolphthalein type epoxy resin together with the curing agent has been shown for various applications to adhesives, paints, coating agents, molding materials, etc. (Patent Document 4). However, no mention is made regarding photocurability, and no description is made regarding application as a resist for a color filter or a black matrix.

  Patent Document 5 discloses that an alkali-developable photosensitive fluorene polyester compound is used as a color filter ink material as a binder resin. However, even when this binder resin is used, the film thickness is reduced due to the low heat resistance. In addition, since the balance between solubility and sensitivity is poor, the penetration of the developer into the exposed area occurs simultaneously with the dissolution of the unexposed area, resulting in protrusions and irregularities on the edge of the pixel, and the adhesion of the pixel to the substrate is reduced. It may cause problems that are bad, and it is not yet satisfactory as a compound.

Japanese Patent Publication No. 56-40329 Japanese Patent Publication No.57-45795 Japanese Patent Laid-Open No. 11-140144 International Publication No. 2013/183735 Pamphlet Japanese Patent No. 2575572

  Although the curable resin composition using the N-phenylphenolphthalein type epoxy resin can obtain a relatively tough cured material, the present cured material properties are not sufficient.

  Furthermore, there is a need for acid-modified epoxy acrylates that have higher dispersion in colored pigments, especially carbon black, and that have good development characteristics even at high pigment concentrations. At that time, a material having a relatively high molecular weight and appropriate developability is required.

  Accordingly, there is a demand for a material that has tough cured properties and good development characteristics, and also has good development characteristics even at high pigment concentrations.

In order to solve the above-mentioned problems, the inventors of the present invention have an active energy ray curable type containing a reactive polyester compound derived from an epoxy resin having a specific structure, that is, an epoxy resin having a structure represented by the general formula (1). It has been found that the resin composition can obtain a tough cured product, and has excellent resin physical properties even when the solvent is only dried.
Furthermore, it has been found that it has a particularly good color pigment dispersibility, and that it can be a resist material having good developability even at a high pigment concentration.

That is, the present invention relates to the following (1) to (18).
(1) An epoxy resin (a) represented by the general formula (1), a compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule, and 1 A reactive polyester compound (A) obtained by polymerizing a saturated or unsaturated polybasic acid anhydride (c) having at least two acid anhydride structures in the molecule.

(In General Formula (1), R ₁ is the same or different and represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, a represents the number of substituents R ₁ ; 1 or 2)

(2) The reactive polyester compound according to (1) above, wherein the polybasic acid anhydride (c) is a saturated or unsaturated tetrabasic acid anhydride having two acid anhydride structures in one molecule. A).
(3) The polybasic acid anhydride (c) is a monocyclic aromatic tetrabasic acid dianhydride, a bicyclic aromatic tetrabasic acid dianhydride, a polycyclic aromatic tetrabasic acid dianhydride, and The reactive polyester compound (A) according to the above (1), which is one or more selected from the group consisting of alicyclic acid anhydrides by nuclear hydrogenation reaction of these aromatic anhydrides.
(4) Polybasic acid anhydride (c) is pyromellitic acid anhydride, biphenyltetracarboxylic acid anhydride, naphthyltetracarboxylic acid anhydride, benzophenonetetracarboxylic acid dianhydride, diphenyl ether tetracarboxylic acid anhydride, diphenylsulfone Tetracarboxylic anhydride, ethylene glycol bistrimellitic anhydride, diol bistrimellitic anhydride, bisphthalic fluorene anhydride, biphenol bistrimellitic anhydride, butanetetracarboxylic anhydride, and the nucleus of these aromatic anhydrides The reactive polyester compound (A) according to the above (1), which is any one or two or more selected from the group consisting of alicyclic acid anhydrides by hydrogenation reaction.
(5) A reactive polyester compound obtained by further reacting the reactive polyester compound (A) according to any one of (1) to (4) with a saturated or unsaturated dibasic acid anhydride (d). (A ').
(6) The active energy ray-curable resin composition comprising the reactive polyester compound (A) according to any one of (1) to (4) or the reactive polyester compound (A ′) according to (5). object.
(7) The active energy ray-curable resin composition according to (6), further including a reactive compound (B) other than (A) or (A ′).
(8) 10 to 90% by weight of reactive polyester compound (A) or (A ′), 3 to 80% by weight of reactive compound (B), and the balance, based on the total solid content of the resin composition, The active energy ray-curable resin composition according to (7), including other components.
(9) Active energy as described in (7) or (8) which contains 3-80 weight% of (meth) acrylate monomers with respect to the total amount of solid content of a resin composition as a reactive compound (B). A linear curable resin composition.
(10) The active energy ray-curable resin composition according to (8) or (9), which further contains a photopolymerization initiator as another component.
(11) The active energy ray-curable resin composition according to any one of (6) to (10), further including a color pigment.
(12) The active energy ray-curable resin composition according to (11), which is a color filter resist.
(13) The active energy ray-curable resin composition according to (11) or (12), which is a black matrix resist.
(14) The active energy ray-curable resin composition according to any one of (6) to (11), which is a molding material.
(15) The active energy ray-curable resin composition according to any one of (6) to (11), which is a film forming material.
(16) The active energy ray-curable resin composition according to any one of (6) to (11), which is a resist material composition.
(17) A cured product of the active energy ray-curable resin composition according to any one of (6) to (11) above.
(18) An article overcoated with the active energy ray-curable resin composition according to any one of (6) to (11) above.

  The active energy ray-curable resin composition of the present invention has excellent resin properties not only in obtaining a tough cured product but also in a state where the solvent is only dried. The cured product obtained from the active energy ray-curable resin composition of the present invention can be suitably used as a film-forming material that requires thermal and mechanical toughness.

  Furthermore, it is preferably used for applications requiring particularly high characteristics such as solder resists for printed wiring boards, interlayer insulating materials for multilayer printed wiring boards, solder resists for flexible printed wiring boards, plating resists, and photosensitive optical waveguides. I can do it.

  Furthermore, since it has a high dispersibility of colored pigments such as carbon black, it can exhibit good developability even at high pigment concentrations, so that resist materials for color resists and color filters, particularly black It can be suitably used for a matrix material or the like.

  The reactive polyester compound (A) of the present invention has one or more polymers in the molecule for imparting reactivity to the epoxy resin (a) represented by the following formula (1) having an N-phenylphenolphthalein skeleton. Polymerization of a compound (b) having both an ethylenically unsaturated group capable and one or more carboxyl groups and a saturated or unsaturated polybasic acid anhydride (c) having at least two acid anhydride structures in one molecule Obtained by reaction.

  That is, the feature of the present invention is exhibited by simultaneously introducing an ethylenically unsaturated group and a hydroxyl group into a molecular chain by epoxy carboxylation.

In the present invention, it is essential that the epoxy resin (a) represented by the general formula (1) has a specific structure having an N-phenylphenolphthalein skeleton. In the formula, R ₁ is the same or different and represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and a represents the number of substituents R ₁ and is 1 or 2. .

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ₁ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, a pentyl group, and a hexyl group. And a methyl group and an ethyl group are preferable.
Examples of the alkoxy group having 1 to 6 carbon atoms represented by R ₁ include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a t-butoxy group, and the like. An ethoxy group is preferred.
Of the epoxy resins (a) represented by the general formula (1), those in which R ₁ is all hydrogen atoms are preferred.
Furthermore, the method for producing the epoxy resin (a) represented by the general formula (1) is known and described in detail in Patent Document 4. Generally, a raw material phenol resin in which R ₁ is all hydrogen atoms is commercially available as PPPBP manufactured by SABIC.

  The compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule used in the present invention reacts to impart reactivity to active energy rays. It is what you want to do. These include monocarboxylic acid compounds and polycarboxylic acid compounds.

  Examples of monocarboxylic acid compounds containing one carboxyl group in one molecule include (meth) acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or saturated or unsaturated dibasic acid and unsaturated group-containing monoglycidyl. A reaction product with a compound is mentioned. In the above, examples of the acrylic acid include (meth) acrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic acid anhydride and 1 molecule. Half-esters that are (meth) acrylate derivatives having one hydroxyl group and equimolar reactants, half-esters that are equimolar reactants of saturated or unsaturated dibasic acids and monoglycidyl (meth) acrylate derivatives, etc. Is mentioned.

  Furthermore, as a polycarboxylic acid compound having a plurality of carboxyl groups in one molecule, a (meth) acrylate derivative having a plurality of hydroxyl groups in one molecule and a half ester, a saturated or unsaturated dibasic acid as an equimolar reaction product, and Examples thereof include half esters which are equimolar reaction products with glycidyl (meth) acrylate derivatives having a plurality of epoxy groups.

  As the compound (b) having at least one polymerizable ethylenically unsaturated group and at least one carboxyl group in one molecule, those having no hydroxyl group in the compound are preferable. Of these, most preferable are (meth) acrylic acid, a reaction product of (meth) acrylic acid and ε-caprolactone, or cinnamic acid in terms of sensitivity when an active energy ray-curable resin composition is used.

Any polybasic acid anhydride (c) used for producing the reactive polyester compound (A) of the present invention can be used as long as it has at least two acid anhydride structures in the molecule. That is, a saturated or unsaturated tetrabasic acid anhydride or a polybasic acid anhydride having at least two acid anhydride structures in one molecule can be used.
In the present invention, it is preferable to use a saturated or unsaturated tetrabasic acid anhydride having two acid anhydride structures.
Specifically, monocyclic aromatic tetrabasic acid dianhydrides such as pyromellitic acid anhydride, biphenyltetracarboxylic acid anhydride, naphthyltetracarboxylic acid anhydride, benzophenonetetracarboxylic acid dianhydride, diphenyl ether tetracarboxylic acid Bicyclic aromatic tetrabasic acid dianhydrides such as anhydrides, diphenylsulfone tetracarboxylic acid anhydrides, ethylene glycol bistrimellitic acid anhydrides, diol bistrimellitic acid anhydrides (eg hexanediol bistrimellitic acid anhydride) And polycyclic aromatic tetrabasic acid dianhydrides such as fluorene anhydride of bisphthalic acid and biphenol bistrimellitic acid anhydride, butanetetracarboxylic acid anhydride, and the like. Furthermore, alicyclic acid anhydrides obtained by the nuclear hydrogenation reaction of these aromatic anhydrides can also be suitably used. One or more polybasic acid anhydrides selected from these groups are particularly preferred.

  The reactive polyester compound (A) of the present invention comprises a carboxylation reaction (hereinafter referred to as a first reaction) between the aforementioned epoxy compound (a) and a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule. A diol compound in which an alcoholic hydroxyl group is formed, and then the resulting compound is subjected to a polyesterification reaction (hereinafter referred to as a second reaction) with a polybasic acid anhydride (c). Can be obtained as

The first reaction can be carried out without solvent or diluted with a solvent. The solvent that can be used here is not particularly limited as long as it is an inert solvent for the carboxylation reaction.
A preferable amount of the solvent to be used should be appropriately adjusted depending on the viscosity and use of the resin to be obtained. Preferably, the solid content is 90 to 30% by weight, more preferably 80%, based on the total amount of the charged solution. A solvent is used so that it may become -50weight%.

Specific examples of what can be used as the above solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane and decane, and Examples thereof include petroleum ether, white gasoline, and solvent naphtha.
Examples of ester solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, Mono- or polyalkylene glycol monoalkyl ether monoacetates such as triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, adipine Polyesters of polycarboxylic acids such as dialkyl acids Kind, and the like.
Examples of ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether. Glycol ethers, and cyclic ethers such as tetrahydrofuran.
Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

  In addition, the reaction can be carried out in a single or mixed organic solvent such as the reactive compound (B) other than (A) or (A ′). In this case, when it is used as a component of the active energy ray-curable resin composition, it can be used directly as a composition, which is preferable.

  During the reaction, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst used is that of the reactants, that is, the epoxy resin (a), the carboxylic acid compound (b), and optionally a solvent or the like. 0.1 to 10% by weight based on the total amount of reactants. The reaction temperature at that time is 60 to 150 ° C., and the reaction time is preferably 5 to 60 hours. Specific examples of the catalyst that can be used include, for example, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium octoate, Examples include known general basic catalysts such as zirconium octoate.

  Moreover, it is preferable to use hydroquinone monomethyl ether, 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4hydroxytoluene and the like as a thermal polymerization inhibitor.

  The end point of this reaction is the time when the acid value of the sample is 5 mgKOH / g or less, preferably 3 mgKOH / g or less, while sampling appropriately.

  The second reaction is an esterification reaction in which the polybasic acid anhydride (c) is gradually added to the reaction solution after the completion of the first reaction. Although the reaction can be carried out without a catalyst, a basic catalyst can be used to promote the reaction, and the amount of the catalyst used is 10% by weight or less based on the reaction product. The reaction temperature at this time is 40 to 120 ° C., and the reaction time is preferably 5 to 60 hours.

  The amount of polybasic acid anhydride (c) charged in the second reaction is a calculated value such that the solid content acid value of the reactive polyester compound (A) of the present invention is 50 to 150 mg · KOH / g. It is preferable to add and charge so that the ratio of (number of moles of carboxylated reaction product) / (number of moles of polybasic acid anhydride c) is in the range of 1 to 5. When this value is less than 1, an acid anhydride group remains at the terminal of the reactive polyester compound (A) of the present invention, which is not preferable because it has low thermal stability and may gel during storage. . On the other hand, when this value exceeds 5, the molecular weight of the reactive polyester compound (A) becomes low, which may cause a problem of tackiness or a low sensitivity. Further, when the solid content acid value is less than 50 mg · KOH / g, the solubility in an alkaline aqueous solution is insufficient, and when patterning is performed, there is a fear that it remains as a residue or in the worst case, patterning cannot be performed. On the other hand, if the solid content acid value exceeds 150 mg · KOH / g, the solubility in an alkaline aqueous solution becomes too high, and the photocured pattern may be peeled off.

In addition, it can carry out using the reactive compound (B) etc. which are mentioned later individually or as a mixed organic solvent. In this case, when it is used also as a component of the curable composition, it can be used directly as a composition, which is preferable.
Moreover, it is preferable to use the thing similar to the illustration in the said carboxylation reaction as a thermal-polymerization inhibitor.

In the present invention, the reactive polyester compound (A) can be obtained by further esterifying the reactive polyester compound (A) with a saturated or unsaturated dibasic acid anhydride (d).
Examples of the saturated or unsaturated dibasic anhydride (d) include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. , Itaconic anhydride, methylendomethylenetetrahydrophthalic anhydride, trimellitic anhydride and the like.
The reaction between the reactive polyester compound (A) and the saturated or unsaturated dibasic acid anhydride (d) is carried out by adding a saturated or unsaturated dibasic acid anhydride (d) per equivalent of hydroxyl group in the reactive polyester compound (A). It is preferable to react 0.1 to 1.0 equivalent. The reaction temperature is preferably 60 to 150 ° C., and the reaction time is preferably 1 to 10 hours. The solid content acid value of the reactive polyester compound (A ′) thus obtained is preferably about 50 to 150 mg · KOH / g.
The molecular weight of the reactive polyester compound (A) or (A ′) obtained by the present invention is about 1,000 to 10,000 as an average molecular weight.

  Specific examples of the reactive compound (B) that can be used in the present invention include a radical reactive (meth) acrylate monomer, a cationic reactive monomer, a vinyl compound, a reactivity sensitive to both radicals and cations. An oligomer etc. are mentioned.

  Examples of the radical reaction type (meth) acrylate monomer that can be used include monofunctional (meth) acrylate and polyfunctional (meth) acrylate.

  Monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether, Examples include phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.

  As polyfunctional (meth) acrylates, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, glycol di (meth) acrylate, Diethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (meth) acrylate, adipic acid epoxy di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, hydrogen Ε-Caprola of bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, and neopent glycol hydroxybivalate Tone adduct di (meth) acrylate, poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, reaction product of dipentaerythritol and ε-caprolactone, trimethylolpropane tri (meth) acrylate, triethylolpropane tri ( (Meth) acrylate and its ethylene oxide adduct, pentaerythritol tri (meth) acrylate and its ethylene oxide adduct, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and its ethylene oxide adduct, etc. Is mentioned.

  Examples of vinyl compounds that can be used include vinyl ethers, styrenes, and other vinyl compounds. Examples of vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of styrenes include styrene, methyl styrene, and ethyl styrene. Other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

  Furthermore, as so-called reactive oligomers, urethane acrylate having a functional group capable of acting on active energy rays and a urethane bond in the same molecule, and similarly a functional group capable of acting on active energy rays and an ester bond in the same molecule. Examples thereof include polyester acrylate, epoxy acrylate derived from an epoxy resin, and epoxy acrylate having a functional group capable of acting on active energy rays in the same molecule, and a reactive oligomer in which these bonds are used in combination.

  The cation reactive monomer is not particularly limited as long as it is generally a compound having an epoxy group. For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycyl ether, 3,4-epoxycyclohexylmethyl-3,4, -epoxycyclohexanecarboxylate (manufactured by Union Carbide Corporation) SyraCure UVR-6110 "), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (such as" ELR-4206 "manufactured by Union Carbide), limonene dioxide (Daicel Chemical Industries) “Celoxide 3000”, etc.), allyl cyclohexylene dioxide, 3,4, -epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxy) Chlohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate (such as “Syracure UVR-6128” manufactured by Union Carbide), bis (3,4 -Epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane, (1,1,2,2 , -Tetrakis (4-hydroxyphenyl) ethane) glycidyl ether (trade name: GTR-1800, manufactured by Nippon Kayaku Co., Ltd.).

  Among these, as the reactive compound (B), a radical curable (meth) acrylate monomer is preferable. In the case of the cationic type, the carboxylic acid and the epoxy react with each other, so that it is necessary to use a two-component mixed type.

The active energy ray-curable type of the present invention by mixing the reactive polyester compound (A) or (A ′) of the present invention with a reactive compound (B) other than (A) or (A ′) as necessary. A resin composition can be obtained. Further, the reactive polyester compounds (A) and (A ′) may be used in combination in the resin composition.
At this time, you may add another component suitably according to a use.

  That is, for the purpose of adapting the active energy ray-curable resin composition of the present invention to various uses, other components can be added to the resin composition up to 70% by weight. Examples of other components include a photopolymerization initiator, a coloring material (color pigment, etc.), a volatile solvent added for viscosity adjustment for the purpose of imparting coating suitability, a heat-sensitive polymerization initiator, and the like. Examples of other components that can be used are shown below.

  Examples of the radical photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloro Acetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1 Acetophenones such as -one; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone; 2,4-diethylthioxanthone, 2- Thioxanthones such as sopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylaminobenzophenone, etc. Benzophenones of the above; known general radical photoinitiators such as phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide .

  As cationic photopolymerization initiators, Lewis acid diazonium salt, Lewis acid iodonium salt, Lewis acid sulfonium salt, Lewis acid phosphonium salt, other halides, triazine initiator, borate initiator, And other photoacid generators.

  Examples of the diazonium salt of Lewis acid include p-methoxyphenyldiazonium fluorophosphonate, N, N-diethylaminophenyldiazonium hexafluorophosphonate (Sun Shine SI-60L / SI-80L / SI-100L, etc., manufactured by Sanshin Chemical Industry Co., Ltd.) and the like. Examples of Lewis acid iodonium salts include diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate. Examples of Lewis acid sulfonium salts include triphenylsulfonium hexafluorophosphonate (Cyracure UVI-6990 manufactured by Union Carbide). Etc.), triphenylsulfonium hexafluoroantimonate (such as Cyracure UVI-6974 manufactured by Union Carbide), etc. Examples of the phosphonium salt of a Lewis acid, triphenyl phosphonium hexafluoroantimonate, and the like.

  Other halides include 2,2,2-trichloro- [1-4 ′-(dimethylethyl) phenyl] ethanone (Trigonal PI manufactured by AKZO, etc.), 2.2-dichloro-1--4- (phenoxyphenyl). ) Etanone (Sandray 1000 manufactured by Sandoz), α, α, α-tribromomethylphenylsulfone (BMPS manufactured by Iron Chemical Co., Ltd.) and the like. Examples of triazine-based initiators include 2,4,6-tris (trichloromethyl) -triazine, 2,4-trichloromethyl- (4′-methoxyphenyl) -6-triazine (such as Triazine A manufactured by Panchi), 2, 4-trichloromethyl- (4′-methoxystyryl) -6-triazine (such as Triazine PMS manufactured by Panchim), 2,4-trichloromethyl- (pipronyl) -6-triazine (such as Triazine PP manufactured by Panchim), 2, 4-trichloromethyl- (4′-methoxynaphthyl) -6-triazine (such as Triazine B manufactured by Panchim), 2 [2 ′ (5 ″ -methylfuryl) ethylidene] -4,6-bis (trichloromethyl)- s-triazine (manufactured by Sanwa Chemical Co., Ltd.), 2 2'-furyl-ethylidene) -4,6-bis (trichloromethyl) -s-triazine (manufactured by Sanwa Chemical Co., Ltd.).

  Examples of the borate initiator include NK-3876 and NK-3881 manufactured by Nippon Senshoku Dye Co., Ltd. Other photoacid generators include 9-phenylacridine, 2,2′-bis (o-chlorophenyl)- 4,4 ′, 5,5′-tetraphenyl-1,2-biimidazole (such as biimidazole manufactured by Kurokin Kasei), 2,2-azobis (2-amino-propane) dihydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) V50, etc.), 2,2-azobis [2- (imidazolin-2-yl) propane] dihydrochloride (VA044 manufactured by Wako Pure Chemical Industries, Ltd.), [Eta-5-2-4- (cyclopentadecyl) (1,2 , 3,4,5,6, eta)-(methylethyl) -benzene] iron (II) hexafluorophosphonate (Irgacure 261 manufactured by Ciba Geigy, etc.) Bis (Y5- cyclopentadienyl) bis [2,6-difluoro-3-(1H-pyr-1-yl) phenyl] titanium (such as Ciba Geigy Corp. CGI-784), and the like.

  In addition, an azo initiator such as azobisisobutyronitrile, a peroxide radical initiator sensitive to heat such as benzoyl peroxide, and the like may be used in combination. Further, both radical and cationic initiators may be used in combination. One type of initiator can be used alone, or two or more types can be used in combination.

  In addition, for example, thermosetting catalysts such as melamine, thixotropic agents such as Aerosil, silicone-based and fluorine-based leveling agents and antifoaming agents, polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether, stabilizers, antioxidants, etc. Can be used.

  In addition, as a pigment material other than the colored pigment, for example, a material not intended for coloring, a so-called extender pigment can be used. Examples include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay and the like.

  Other resins that are not reactive with active energy rays (so-called inert polymers), such as other epoxy resins, phenol resins, urethane resins, polyester resins, ketone formaldehyde resins, cresol resins, xylene resins, diallyl phthalate resins, styrene Resins, guanamine resins, natural and synthetic rubbers, acrylic resins, polyolefin resins, and modified products thereof can also be used. These are preferably used in the range of up to 40% by weight.

  In particular, when the reactive polyester compound (A) or (A ′) is to be used for a solder resist application, it is preferable to use a known general epoxy resin as a resin that does not show reactivity to active energy rays. This is because the carboxyl group derived from (A) or (A ') remains after being reacted and cured by active energy rays, and as a result, the cured product is inferior in water resistance and hydrolyzability. Therefore, by using an epoxy resin, the remaining carboxyl group is further carboxylated to form a stronger cross-linked structure.

  Further, depending on the purpose of use, a volatile solvent may be added to the resin composition in the range of 50% by weight, more preferably up to 35% by weight for the purpose of adjusting the viscosity.

  The active energy ray-curable resin composition of the present invention contains 10 to 90% by weight, preferably 20 to 87% by weight of the reactive polyester compound (A) or (A ′) in the composition, and the reactive compound (B) 3 -80% by weight, more preferably 5 to 70% by weight. If necessary, other components may be contained up to about 70% by weight.

  The active energy ray-curable resin composition of the present invention is easily cured by active energy rays. Specific examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X rays, gamma rays and laser rays, particle rays such as alpha rays, beta rays and electron rays. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in view of suitable applications of the present invention.

  The color pigment that can be used in the present invention is used to make the active energy ray resin composition of the present invention a coloring material. Since the balance between the skeleton of the reactive polyester compound (A) or (A ′) used in the present invention and the hydroxyl group is in a specific range, it is assumed that particularly excellent affinity to the pigment, that is, dispersibility is exhibited. Is done.

  Although this mechanism is not clear, since the dispersion proceeds well, the pigment concentration can be increased as a result, and in a composition that requires development, the dispersion is in a more favorable state. Good patterning characteristics are exhibited, and there are few development residues in the development and dissolution area, which is preferable.

Examples of the color pigment include organic pigments such as phthalocyanine, azo, and quinacridone, carbon black, and inorganic pigments such as titanium oxide. Of these, carbon black is most preferred because of its high dispersibility.
The content of the color pigment in the curable resin composition of the present invention is not particularly limited, but is usually 1 to 70 parts by weight, preferably 2 to 50 parts by weight with respect to 10 parts by weight of the reactive polyester compound of the present invention. Range.

  In the present invention, the molding material refers to a material in which an uncured composition is put into a mold or an object is molded by pressing the mold and then a curing reaction is caused by active energy rays, or a laser is applied to the uncured composition. It refers to a material that is used for applications in which it is irradiated with a focused light such as to cause a curing reaction to be molded.

  Specific applications include a sheet formed into a flat shape, a sealing material for protecting the element, a so-called nanoimprint material that performs fine molding by pressing a "mold" that has been micro-processed into an uncured composition, Furthermore, particularly suitable applications include peripheral sealing materials such as light-emitting diodes and photoelectric conversion elements, which have particularly severe thermal requirements.

  In the present invention, the film forming material is used for the purpose of coating the surface of a substrate. Specific applications include gravure inks, flexo inks, silk screen inks, offset inks and other ink materials, hard coats, top coats, overprint varnishes, clear coats and other coating materials, laminating, optical disk and other various adhesives. This corresponds to adhesive materials such as adhesives and adhesives, resist materials such as solder resists, etching resists, and resists for micromachines. Furthermore, after the film forming material is temporarily applied to the peelable substrate and formed into a film, it is bonded to the original target substrate to form a film, so-called dry film also corresponds to the film forming material. .

  Among these, the introduction of the carboxyl group of the reactive polyester compound (A) or (A ′) increases the adhesion to the base material, so that it is used as an application for coating a plastic base material or a metal base material. Is preferred.

  Furthermore, it is also preferable to use the unreacted reactive polyester compound (A) or (A ′) as an alkaline water developing resist material composition taking advantage of the feature that it is soluble in an alkaline aqueous solution.

  In the present invention, the resist material composition is formed by forming a film layer of the composition on a substrate, and then partially irradiating active energy rays such as ultraviolet rays, and the physical difference between irradiated and unirradiated parts. This refers to an active energy ray-sensitive composition that is intended to be drawn using. Specifically, the composition is used for the purpose of removing the irradiated part or the unirradiated part by dissolving the irradiated part or the non-irradiated part with, for example, a solvent or an alkaline solution.

  The active energy ray-curable resin composition for resists of the present invention can be applied to various materials that can be patterned, and is particularly useful for solder resist materials, interlayer insulating materials for build-up methods, and optical waveguides. It is also used for printed wiring boards, electrical / electronic / optical substrates such as optoelectronic substrates and optical substrates.

  As a particularly suitable application, printing inks, especially color filters, etc. are utilized by making use of the characteristics that permanent resist applications such as solder resists, pigment dispersibility are good by making use of the characteristics that can obtain a tough cured product. The use of color resists and black matrix resists is preferred.

  In addition, it is particularly suitably used as a dry film application that requires mechanical strength before the curing reaction with active energy rays. That is, since the balance of the hydroxyl group and epoxy group of the epoxy resin (a) used in the present invention is in a specific range, the reactive polyester compound of the present invention is excellent in spite of its relatively high molecular weight. Developability can be exhibited.

  There are no particular restrictions on the method for forming the film, but an intaglio printing method such as gravure, a relief printing method such as flexo, a stencil printing method such as silk screen, a lithographic printing method such as offset, a roll coater, a knife coater, a die coater, Various coating methods such as curtain coater and spin coater can be arbitrarily adopted.

  The cured product of the active energy ray-curable resin composition of the present invention refers to a product obtained by irradiating and curing the active energy ray-curable resin composition of the present invention with active energy rays.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. In the examples, “parts” represents parts by weight and “%” represents percent by weight unless otherwise specified.

The epoxy equivalent, softening point, acid value and molecular weight were measured under the following conditions.
1) Epoxy equivalent: Method according to JIS K 7236: 2001 2) Softening point: Method according to JIS K 7234: 1986 3) Acid value: Method according to JIS K 0070: 1992 4) Molecular weight: Under the following conditions GPC analysis model: TOSOH HLC-8220GPC
Column: TSKGEL Super HZM-N
Eluent: THF (tetrahydrofuran); 0.35 ml per minute. 40 ° C
Detector: Differential refractometer Molecular weight standard: Polystyrene

Synthesis Example 1 Synthesis of Epoxy Resin (a) (R ₁ = Compound of All Hydrogen Atoms in General Formula (1)) According to the description in Example 1 of Patent Document 4, the following synthesis was performed.
While applying a nitrogen gas purge to a flask equipped with a thermometer, cooler, and stirrer, 256 g of phenolic compound N-phenylphenolphthalein (PPB made by SABIC, purity 99% or more), 842 g of epichlorohydrin, and 180 g of methanol were added. In addition, the water bath was heated to 75 ° C. When the internal temperature exceeded 65 ° C., 21 g of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 70 ° C. for 1 hour. After completion of the reaction, washing was performed twice with 300 g of water to remove the generated salt and the like, followed by heating for 3 hours with stirring under reduced pressure (˜70 ° C., −0.08 MPa to −0.09 MPa). The epichlorohydrin and the like were distilled off. To the residue, 600 g of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 70 ° C. Under stirring, 26 g of a 30% by weight aqueous sodium hydroxide solution was added and reacted for 1 hour, followed by washing with water until the washing water became neutral. Methyl isobutyl ketone and the like were distilled off from the washed solution under reduced pressure using a rotary evaporator to obtain 305 g of the target epoxy resin (compound of general formula (1) where R ₁ = all hydrogen atoms). The epoxy equivalent of the obtained epoxy resin is 266 g / eq. The softening point was 89 ° C., the ICI melt viscosity was 0.42 Pa · s (150 ° C.), and it was solid at room temperature.

Example 1: Synthesis of Reactive Polyester Compound (A-1) In Synthesis Example 1 as an epoxy resin (a) having two or more epoxy groups in a molecule in a 2 L flask equipped with a stirrer and a reflux tube 266 g of synthesized epoxy resin (N-phenylphthalein type epoxy resin, epoxy equivalent: 266 g / equivalent) and propylene glycol monomethyl ether monoacetate as a solvent for reaction to a solid content of 70%, and ethylenic in the molecule 72.1 g of acrylic acid (abbreviation AA, Mw = 72) as monocarboxylic acid compound (b) having an unsaturated group, 1.01 g of triphenylphosphine as a catalyst, 0.17 g of 2-methylhydroquinone as a polymerization inhibitor The diol is reacted at a temperature of 98 ° C. until the acid value of the reaction solution is 1.0 mg · KOH / g or less. A compound (theoretical molecular weight: 649.69) was obtained.
Next, propylene glycol monomethyl ether monoacetate was added as a solvent to the diol compound solution thus obtained so that the solid content was 65% by weight, and polybasic acid anhydride (c) was added to 109.1 g of merit acid (abbreviation PMDA, Mw = 218.1) was added. After the addition, the temperature was raised to 95 ° C. and reacted for 6 hours to obtain a resin solution containing 65% by weight of the alkaline aqueous solution-soluble polyester compound (A) of the present invention (this solution is referred to as A-1). When the acid value was measured, it was 48.03 mg · KOH / g (solid content acid value: 73.89 mg · KOH / g). The average molecular weight of the compound (A-1): 2,000.

Example 2 Synthesis of Reactive Polyester Compound (A-2) In Synthesis Example 1 as an epoxy compound (a) having two or more epoxy groups in a molecule in a 2 L flask equipped with a stirrer and a reflux tube 266 g of synthesized epoxy resin (N-phenylphthalein type epoxy resin, epoxy equivalent: 266 g / equivalent) and propylene glycol monomethyl ether monoacetate as a solvent for reaction to a solid content of 70%, and ethylenic in the molecule 72.1 g of acrylic acid (abbreviation AA, Mw = 72) as monocarboxylic acid compound (b) having an unsaturated group, 1.01 g of triphenylphosphine as a catalyst, 0.17 g of 2-methylhydroquinone as a polymerization inhibitor The reaction is carried out at a temperature of 98 ° C. until the acid value of the reaction solution becomes 1.0 mg · KOH / g or less. This gave a molecular compound (theoretical molecular weight: 649.69).
Next, propylene glycol monomethyl ether monoacetate was added to the diol compound solution thus obtained so that the solid content was 65% by weight as a solvent, and polybasic acid anhydride (c) was added to this solution as 3,5% by weight. 147.1 g of 3 ′, 4,4′-biphenyltetracarboxylic dianhydride (abbreviation BPDA, Mw = 294.2) was added. After the addition, the temperature was raised to 95 ° C. and reacted for 6 hours to obtain a resin solution containing 65% by weight of the alkaline aqueous solution-soluble polyester compound (A) of the present invention (this solution is referred to as A-2). The acid value was measured and found to be 45.77 mg · KOH / g (solid content acid value: 70.41 mg · KOH / g). The average molecular weight of the compound (A-2): 3,000.

Example 3 Synthesis of Reactive Polyester Compound (A′-3) Synthesis Example 1 was carried out as an epoxy compound (a) having two or more epoxy groups in a molecule in a 2 L flask equipped with a stirrer and a reflux tube. 266 g of the epoxy resin synthesized in step (N-phenylphthalein type epoxy resin, epoxy equivalent: 266 g / equivalent) and propylene glycol monomethyl ether monoacetate as a solvent for reaction to a solid content of 70%, and ethylene in the molecule 72.1 g of acrylic acid (abbreviation AA, Mw = 72) as a monocarboxylic acid compound (b) having a polymerizable unsaturated group, 1.01 g of triphenylphosphine as a catalyst, 0.17 g of 2-methylhydroquinone as a polymerization inhibitor The reaction is carried out at a temperature of 98 ° C. until the acid value of the reaction solution becomes 1.0 mg · KOH / g or less. Le compounds (theoretical molecular weight: 649.69) was obtained.
Next, propylene glycol monomethyl ether monoacetate was added as a solvent to the diol compound solution thus obtained so that the solid content was 65% by weight, and polybasic acid anhydride (c) was added to 109.1 g of merit acid (abbreviation PMDA, Mw = 218.1) was added. After the addition, the temperature was raised to 95 ° C. and reacted for 6 hours, and then 57.8 g of tetrahydrophthalic anhydride (abbreviated as THPA, Mw = 152.2) as a dibasic acid anhydride and a solid content as a solvent. Propylene glycol monomethyl ether monoacetate was added so that it might become 65 weight%, and it was made to react at 100 degreeC for 6 hours, and the resin solution containing 65 weight% of aqueous alkali-soluble polyester compound (A ') of this invention was obtained ( This solution is designated as A′-3). When the acid value was measured, it was 61.63 mg · KOH / g (solid acid value: 94.82 mg · KOH / g). The average molecular weight of the compound (A′-3): 2,600.

Comparative Example 1: Synthesis of Reactive Polycarboxylate Compound (H-1) 288 g of NC-3000H (manufactured by Nippon Kayaku, softening point 70 ° C., epoxy equivalent 288 g / eq), one or more polymerizable ethylenes in the molecule 72 g of acrylic acid (abbreviation AA, Mw = 72) as a compound (b) having both an unsaturated group and one or more carboxyl groups, 1.1 g of triphenylphosphine as a catalyst, and propylene glycol monomethyl ether monoacetate as a solvent It was added so that it might become 80%, and it was made to react at 100 degreeC for 24 hours, and the carboxylate compound solution was obtained. Next, to 360 g of the carboxylate compound solution thus obtained, 70.4 g of tetrahydrophthalic anhydride (abbreviation THPA, Mw = 152.2) and propylene glycol monomethyl ether so that the solid content is 65% by weight as a solvent. Monoacetate was added, and the mixture was heated to 100 ° C. for acid addition reaction to obtain a reactive polycarboxylate solution (this solution is referred to as H-1). When the acid value was measured, it was 60.2 mg · KOH / g (solid content acid value: 39.13 mg · KOH / g). Average molecular weight of compound (H-1): 3,500

Comparative Example 2: Synthesis of reactive polyester compound (H-2)
(Compound of Synthesis Example 1 of Patent Document 5)
In a 500 ml four-necked flask, 231 g of bisphenolfluorene type epoxy resin (epoxy equivalent 231 g / eq), 0.45 g of triethylbenzylammonium chloride, 0.1 g of 2,6-di-isobutylphenol, 72.0 g of acrylic acid, Were mixed, and dissolved by heating at 90 to 100 ° C. while blowing air at a rate of 25 ml per minute. Although this solution was cloudy, the temperature was gradually raised as it was, and the solution was heated to 120 ° C. to be completely dissolved. Although the solution gradually became transparent and viscous, the stirring was continued as it was, and during this time, the acid value was measured, and this heating and stirring was continued until the acid value became less than 2.0 mgKOH / g. It took 8 hours for the acid value to reach the target (acid value 0.8). Then, it cooled to room temperature and obtained the colorless and transparent solid. Next, 303 g of the bisphenolfluorene type epoxy acrylate resin thus obtained was dissolved in 223.2 g of propylene glycol monomethyl ether monoacetate to obtain a solution, and then 38 g of 1,2,3,6-tetrahydrophthalic anhydride. Then, 73.5 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were added, the temperature was gradually raised and reacted at 110 to 115 ° C. for 2 hours, and 65% by weight of the reactive polyester compound to be compared was added. A resin solution containing was obtained (this solution is referred to as H-2). When the acid value was measured, it was 37.31 mg · KOH / g (solid content acid value: 57.4 mg · KOH / g). Molecular weight of compound (H-2): 20,000

Example 4, Comparative Example 4: Preparation of hard coat composition
Reactive polyester compound (A-1, A-2, A′-3, H-1 or H-2) solution 20 g synthesized in Examples 1 to 3 and Comparative Examples 1 and 2, radical curable monomer (B) 4 g of dipentaerythritol hexaacrylate and 1.5 g of Irgacure 184 as an ultraviolet reactive initiator were dissolved by heating.
Further, this was coated on a polycarbonate plate by a hand applicator so as to have a film thickness of 20 microns at the time of drying, and solvent drying was carried out in an electric oven at 80 ° C. for 30 minutes. After drying, an ultraviolet-ray exposure apparatus (manufactured by Oak Seisakusho) equipped with a high-pressure mercury lamp was irradiated with an ultraviolet ray with an irradiation dose of 1000 mJ and cured to obtain an article overcoated with the resin composition.
The hardness of the coating film of the article overcoated with this resin composition was measured according to JIS K5600-5-4: 1999, and an impact test was conducted according to ISO6272-1: 2002.

  As is clear from the above results, the photocurable resin composition in the present invention has impact resistance while having relatively high hardness.

Example 5, Comparative Example 5: Preparation of dry film type resist composition
54.44 g of the reactive polyester compound (A-1, A-2, A′-3, H-1 or H-2) solution obtained in Examples 1 to 3 and Comparative Examples 1 and 2, and other reactivity Compound (B) HX-220 (Nippon Kayaku Co., Ltd. diacrylate monomer) 3.54g, Photopolymerization initiator Irgacure 907 (Ciba Specialty Chemicals) 4.72g and Kayacure DETX-S 0.47 g (manufactured by Nippon Kayaku Co., Ltd.) and (1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane) glycidyl ether (GTR-1800 (manufactured by Nippon Kayaku)) as a curing component 14.83 g, 1.05 g of melamine as a thermosetting catalyst, and 20.95 g of methyl ethyl ketone as a concentration adjusting solvent are kneaded in a bead mill and uniformly dispersed to obtain a resist resin composition. Obtained.
The obtained composition was uniformly applied to a polyethylene terephthalate film as a support film by a roll coating method, passed through a hot air drying furnace at a temperature of 70 ° C., and a resin layer having a thickness of 30 μm was formed. A polyethylene film to be a protective film was attached to obtain a dry film. The obtained dry film was applied to a polyimide printed circuit board (copper circuit thickness: 12 μm, polyimide film thickness: 25 μm) using a heating roll at a temperature of 80 ° C., and a resin layer was attached to the entire surface of the substrate while peeling off the protective film.

  Next, in order to estimate the mask on which the circuit pattern was drawn and sensitivity using an ultraviolet exposure apparatus (Oak Manufacturing Co., Ltd., model HMW-680GW), Kodak Step Tablet No. 2 was irradiated with ultraviolet rays. Then, the film on a dry film was peeled and the peeling state was confirmed. Thereafter, spray development was performed with a 1% aqueous sodium carbonate solution to remove the resin on the non-irradiated part of the ultraviolet rays. After washing with water and drying, the printed circuit board was subjected to a heat curing reaction in a hot air drier at 150 ° C. for 60 minutes to obtain a cured film.

(Peelability evaluation)
The peelability was determined by the ease of the film that peels after the exposure.
○: Peels cleanly at the interface △: Peelable if peeled carefully
X: There exists a part which aggregates and peels partially (or the whole surface).

(Sensitivity evaluation)
Sensitivity was determined by how many density portions remained in the exposed portion that passed through the step tablet during development. The higher the number of steps (value), the higher sensitivity is determined in the dark part of the tablet (unit: step).

(Developability evaluation)
The developability was evaluated based on the time until the pattern shape portion was completely developed, that is, the so-called break time when developing the exposed portion that passed through the pattern mask (unit: second). ×: Development not possible

(Curability evaluation)
The evaluation of curability was shown by the pencil hardness of the cured film after heating at 150 ° C.
The evaluation method was based on JIS K5600-5-4: 1999.

  As is clear from the above results, the resist composition of the present invention has a balance between sensitivity and developability in addition to good peelability.

Example 6, Comparative Example 6: Preparation of photosensitive colored resin composition for black matrix Reactive polyester compounds (A-1, A-2, A'-) obtained in Examples 1 to 3 and Comparative Examples 1 and 2 3, H-1 or H-2) 50 g of solution (solid content conversion: 32.5 g), 5 g of dipentaerythritol hexaacrylate, 4 g of CGI-124 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator, 224 g (solid content conversion: 56 g, of which carbon black 43 g, polymer dispersant 13 g) was dispersed in propylene glycol monomethyl ether using Dispcrbyk (urethane polymer dispersant, manufactured by Big Chemie). A photosensitive black resin composition was obtained by mixing with 218 g of acetate.

  The photosensitive black resin composition thus obtained was spin-coated on a 10 cm square glass substrate and dried on a hot plate at 90 ° C. for 150 seconds. The film thickness after drying was 1 μm. Next, this sample was image-exposed with a high-pressure mercury lamp through a mask, and then subjected to spray development using a KOH aqueous solution having a temperature of 23 ° C. and a concentration of 0.04% by weight to form a black pixel (black matrix).

  Pixels formed using each of the photosensitive black resin compositions prepared above were evaluated according to the following items, and the results are shown in Table 3.

(Adhesion)
The minimum pattern size of a resist that can be resolved at an exposure amount that faithfully reproduces a 20 μm mask pattern was observed with a microscope at a magnification of 200 times. The smaller the minimum pattern size, the better the adhesion. The minimum pattern dimension was 10 μm or less, and the adhesion was ◯, and the one exceeding 10 μm was rated as x.

(Pixel sharpness)
The shape of the fine black pixel at an exposure amount that faithfully reproduces a 20 μm mask pattern was observed with a microscope at a magnification of 1000 times. Those having good linearity are indicated by sharpness ◯, and resist patterns having protrusions and irregularities are indicated by ×.

(Pigment dispersibility)
The gloss of the coating film surface with a 20 μm mask pattern was measured using a 60 ° reflection gloss meter to evaluate the dispersibility of the carbon black. At this time, a higher gloss indicates better pigment dispersibility.

(Heat-resistant)
A heat resistance test (300 ° C., 1 hour) was performed on the 20 μm mask pattern, and the film thickness reduction rate (%) at that time was shown.

  As is clear from the above results, the photocurable resin composition in the present invention has adhesiveness, linearity, dispersibility, and heat resistance, and can be particularly suitably used for a black matrix or the like.

Example 7, Comparative Example 7: Preparation of photosensitive colored resin composition for color filter Reactive polyester compounds (A-1, A-2, A'-) obtained in Examples 1 to 3 and Comparative Examples 1 and 2 3, 15.4 g of H-1 or H-2) solution (solid content conversion: 10.0 g), 7.5 g of dipentaerythritol hexaacrylate, and 2-methyl-1 [4 (methylthio) as a photopolymerization initiator. ) Phenyl] 2-morpholinopropane-11-one (BASF, trade name IRGACURE907) 0.8 g, 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd.) 0.4 g, Kotanon 1-1 [9-ethyl] 6 1 (2 methyl benzoyl) 1 9H 1 rubrazol-3 1 yl] 1 1 1 (O 1 acetyloxime)] (BASF, trade name IRGACUREOXEO 2) 0.2 g 0.3 g of Megafac F-554 (manufactured by DIC Corporation) as a basic surfactant, 40.2 g as a colorant dispersion as a colorant, and propylene glycol monomethyl ether acetate as a solvent are mixed to obtain a solid content of 20 A colored composition having a mass% was obtained.
The colorant dispersion is a C.I. I. Pigment Blue 15: 6 / xanthene acid dye C.I. I. Acid Red 52 = 78/22 (mass ratio) 15 g of mixture, BYK-LPN21116 (manufactured by BYK Corporation) as a dispersing agent 11 g (solid content concentration = 40 mass%), reactive polyester compound (A) or (A ') Using a solution of 12.5 g and propylene glycol monomethyl ether acetate as a solvent to a solid content concentration of 20% by mass, the mixture was mixed and dispersed by a bead mill to prepare a colorant dispersion.

  The photosensitive colored resin composition thus obtained was spin-coated on a 10 cm square glass substrate and dried on a hot plate at 90 ° C. for 120 seconds. The film thickness after drying was 2.5 μm. Next, the sample was image-exposed with a high-pressure mercury lamp through a mask, and spray-developed using a KOH aqueous solution having a temperature of 23 ° C. and a concentration of 0.04% by weight. Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-beta was performed in a clean oven at 200 ° C. for 30 minutes to form a dot pattern of colored pixels on the substrate.

  Pixels formed using each of the photosensitive colored resin compositions prepared above were evaluated according to the following items, and the results are shown in Table 4.

(Coloring heat resistance)
About the obtained dot pattern, using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), a C light source, a chromaticity coordinate value (x, y) and a stimulus value (Y) in the CIE color system with a 2-degree field of view. Was measured. Next, the chromaticity coordinate value (x, y) and stimulation value (Y) after additional beta for 90 minutes at 200 ° C. were measured, and the color change before and after the additional beta, ie, ΔE _ab was evaluated. As a result, the case where the value of ΔE _ab was less than 3.0 was evaluated as ◯, the case of 3.0 or more and less than 5.0 was evaluated as Δ, and the case of 5.0 or more was evaluated as ×. The evaluation results are shown in Table 4. In addition, it means that heat resistance is so favorable that ( _DELTA ) _Eab value is small.

(Light resistance)
The obtained substrate was irradiated with white LEDs for 1000 hours. The substrate before and after the irradiation, the spectral characteristics were measured using a color analyzer (Otsuka Electronics Co., Ltd. MCPD2000), was determined color difference (△ _{E ab).}
As a result, the case where the value of ΔE _ab was less than 3.0 was evaluated as ◯, the case of 3.0 or more and less than 5.0 was evaluated as Δ, and the case of 5.0 or more was evaluated as ×. The evaluation results are shown in Table 4. In addition, it means that light resistance is so favorable that (DELTA) _Eab value is small.

(Voltage holding ratio evaluation)
The substrate on which this pixel is formed and the substrate on which ITO electrodes are simply deposited in a predetermined shape are bonded together with a sealant mixed with 0.018 mm glass beads, and then liquid crystal MLC6608 (trade name) manufactured by Merck is injected. Thus, a liquid crystal cell was produced.
Next, the liquid crystal cell was placed in a constant temperature layer of 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system VHR-1A type (trade name) manufactured by Toyo Techni Riki Co., Ltd. The applied voltage at this time is a square wave of 5.0 V, and the measurement frequency is 60 Hz. Here, the voltage holding ratio is a value of (liquid crystal cell potential difference after 16.7 milliseconds / voltage immediately after application). The evaluation results are shown in Table 4.

  As is clear from the above results, the photocurable resin composition in the present invention has coloring heat resistance, light resistance and high voltage holding ratio (reliability), and is particularly preferably used for a color filter or the like. I can do it.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

In addition, this application is based on the Japan patent application (2014-171375) for which it applied on August 26, 2014, The whole is used by reference. Also, all references cited herein are incorporated as a whole.

As the active energy ray-curable resin of the present invention, as a material having both curability and toughness, a hard coat material, a resist material that can be developed with an alkali, and an application that exhibits good pigment dispersibility have been shown. A curable printing ink, a color resist, particularly a material having both resist suitability such as pigment dispersibility and developability, can be particularly preferably used for a black matrix for LCD.

Claims (18)

An epoxy compound (a) represented by the general formula (1), a compound (b) having one or more polymerizable ethylenically unsaturated groups and one or more carboxyl groups in one molecule, and one molecule A reactive polyester compound (A) obtained by polymerizing a saturated or unsaturated polybasic acid anhydride (c) having at least two acid anhydride structures.

(In General Formula (1), R ₁ is the same or different and represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, a represents the number of substituents R ₁ ; 1 or 2)   The reactive polyester compound (A) according to claim 1, wherein the polybasic acid anhydride (c) is a saturated or unsaturated tetrabasic acid anhydride having two anhydride structures in one molecule.   The polybasic acid anhydride (c) is a monocyclic aromatic tetrabasic dianhydride, bicyclic aromatic tetrabasic dianhydride, polycyclic aromatic tetrabasic dianhydride, and aromatics thereof. The reactive polyester compound (A) according to claim 1, wherein the reactive polyester compound (A) is one or more selected from the group consisting of alicyclic acid anhydrides obtained by a nuclear hydrogenation reaction of anhydrides.   Polybasic acid anhydride (c) is pyromellitic acid anhydride, biphenyltetracarboxylic acid anhydride, naphthyltetracarboxylic acid anhydride, benzophenonetetracarboxylic acid dianhydride, diphenylethertetracarboxylic acid anhydride, diphenylsulfonetetracarboxylic acid By nuclear hydrogenation reaction of anhydrides, ethylene glycol bistrimellitic anhydride, diol bistrimellitic anhydride, fluorene bisphthalate anhydride, biphenol bistrimellitic anhydride, butanetetracarboxylic anhydride, and these aromatic anhydrides The reactive polyester compound (A) according to claim 1, wherein the reactive polyester compound (A) is at least one selected from the group consisting of alicyclic acid anhydrides.   A reactive polyester compound (A ') obtained by further reacting the reactive polyester compound (A) according to any one of claims 1 to 4 with a saturated or unsaturated dibasic acid anhydride (d).   An active energy ray-curable resin composition comprising the reactive polyester compound (A) according to any one of claims 1 to 4 or the reactive polyester compound (A ') according to claim 5. See contains further (A) or (A ') other than the reactive compound (B),
The active energy ray-curable resin composition according to claim 6, wherein the reactive compound (B) is a (meth) acrylate monomer, a vinyl compound, a urethane acrylate, a polyester acrylate, an epoxy acrylate, or a compound having an epoxy group . 10 to 90% by weight of the reactive polyester compound (A) or (A ′), 3 to 80% by weight of the reactive compound (B), and the other components, with respect to the total solid content of the resin composition The active energy ray-curable resin composition according to claim 7, comprising:   The active energy ray-curable resin composition according to claim 7 or 8, wherein the reactive compound (B) contains a (meth) acrylate monomer in an amount of 3 to 80% by weight based on the total solid content of the resin composition. object.   Furthermore, the active energy ray hardening-type resin composition of Claim 8 or 9 containing a photoinitiator as another component.   Furthermore, the active energy ray hardening-type resin composition as described in any one of Claims 6-10 containing a coloring pigment.   The active energy ray-curable resin composition according to claim 11, which is a color filter resist.   The active energy ray-curable resin composition according to claim 11, which is a black matrix resist.   The active energy ray-curable resin composition according to any one of claims 6 to 11, which is a molding material.   The active energy ray-curable resin composition according to any one of claims 6 to 11, which is a film forming material.   The active energy ray-curable resin composition according to any one of claims 6 to 11, which is a resist material composition.   Hardened | cured material of the active energy ray hardening-type resin composition as described in any one of Claims 6-11.   An article overcoated with the active energy ray-curable resin composition according to any one of claims 6 to 11.