Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/02—Polycondensates containing more than one epoxy group per molecule
  • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
  • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

Definitions

• 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. 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.
• 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.
• a film-forming material having physical properties.
• Patent Documents 1 and 2 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,
• application to solder resist is generally known (Patent Documents 1 and 2).
• An acid-modified epoxy acrylate having a phenol aralkyl type epoxy resin (for example, NC-3000 manufactured by Nippon Kayaku Co., Ltd.) as a basic skeleton is generally known as a material exhibiting high toughness after curing, and as a solder resist using the same. The use is also being studied (Patent Document 3).
• Patent Document 4 For resin compositions containing an N-phenylphenolphthalein type epoxy resin together with a curing agent, for example, the possibility of various applications to adhesives, paints, coating agents, molding materials, etc. is shown. (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 developing photosensitive fluorene polyester compound is used as a color filter ink material as a binder resin.
• this binder resin is used, the film thickness is reduced due to the low heat resistance.
• 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 Laid-Open Patent Publication No. 11-14144 International Publication No. 2013/183735 Pamphlet Japanese Patent No. 2575572
• the curable resin composition using the N-phenylphenolphthalein type epoxy resin can obtain a relatively tough cured product, the present cured material properties are not sufficient.
• 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.
• the present invention relates to the following (1) to (18).
• 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 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.
• 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.
• 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.
• An 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.
• the reactive polyester compound (A) or (A ′) is 10 to 90% by weight, the reactive compound (B) is 3 to 80% by weight, and the balance with respect to the total solid content of the resin composition.
• the active energy ray-curable resin composition according to (7) including other components.
• (11) The active energy ray-curable resin composition according to any one of (6) to (10), further including a color pigment.
• 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.
• solder resists for printed wiring boards are 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.
• the reactive polyester compound (A) of the present invention comprises 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.
• the characteristics of the present invention are exhibited by simultaneously introducing an ethylenically unsaturated group and a hydroxyl group into a molecular chain by epoxy carboxylation.
• the epoxy resin (a) represented by the general formula (1) has a specific structure having an N-phenylphenolphthalein skeleton.
• 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 methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group and the like. An ethoxy group is preferred.
• 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 the monocarboxylic acid compound containing one carboxyl group in one molecule include (meth) acrylic acids, crotonic acid, ⁇ -cyanocinnamic acid, cinnamic acid, or saturated or unsaturated dibasic acid and unsaturated group-containing monoglycidyl.
• acrylic acids include, for example, (meth) acrylic acid, ⁇ -styrylacrylic acid, ⁇ -furfurylacrylic acid, (meth) acrylic acid dimer, saturated or unsaturated dibasic acid anhydride in one 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.
• 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.
• 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.
• those having no hydroxyl group in the compound are preferable.
• (meth) acrylic acid, a reaction product of (meth) acrylic acid and ⁇ -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.
• 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 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 carboxylation reaction hereinafter referred to as a first reaction
• 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).
• 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.
• the amount of the solvent preferably used should be adjusted as appropriate depending on the viscosity and use of the resin to be obtained.
• the solid content is preferably 90 to 30% by weight, more preferably 80%, based on the total amount of the charged solution. A solvent is used so that it becomes ⁇ 50% by weight.
• solvent examples 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.
• aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene
• aliphatic hydrocarbon solvents such as hexane, octane and decane
• examples thereof include petroleum ether, white gasoline, and solvent naphtha.
• ester solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, cyclic esters such as ⁇ -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 acidskind, and the like.
• alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate
• cyclic esters such as ⁇ -but
• 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.
• 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.
• the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.
• reaction can be performed alone or in a mixed organic solvent such as the reactive compound (B) other than (A) or (A ′).
• a mixed organic solvent such as the reactive compound (B) other than (A) or (A ′).
• the reaction 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.
• 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.
• 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.
• hydroquinone monomethyl ether 2-methylhydroquinone, hydroquinone, diphenylpicrylhydrazine, diphenylamine, 3,5-di-tert-butyl-4hydroxytoluene or the like as a thermal polymerization inhibitor.
• This reaction ends with 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 and reacted after the first reaction is completed.
• 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 charged amount of the polybasic acid anhydride (c) 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 such that the ratio of (number of moles of carboxylation 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. .
• the molecular weight of the reactive polyester compound (A) becomes low, which may cause a problem of tackiness or a low sensitivity.
• 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.
• 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.
• 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).
• 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.
• An oligomer etc. are mentioned.
• radical reaction type (meth) acrylate monomer examples 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.
• 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 ⁇ -capro of bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, and neopent glycol hydroxybivalate Di (meth) acrylate of kuton adduct, poly (meth) acrylate of reaction product of dip
• vinyl compounds examples include vinyl ethers, styrenes, and other vinyl compounds.
• vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether.
• styrenes include styrene, methyl styrene, and ethyl styrene.
• Other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.
• 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.
• the reactive compound (B) is preferably a radically curable (meth) acrylate monomer.
• 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.
• 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.
• other components may be added to the resin composition up to 70% by weight.
• 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.
• radical photopolymerization initiators 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 isopropyl
• Known general radical-type photoreaction initiators such as benzophenones; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.
• 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 the iodonium salt of Lewis acid include diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate.
• Examples of the sulfonium salt of Lewis acid include triphenylsulfonium hexafluorophosphonate (Cyracure UVI-6990 manufactured by Union Carbide). Etc.), triphenylsulfonium hexafluoroantimonate (made by Union Carbide, Cyracure UVI-6974) ). Examples of the phosphonium salt of a Lewis acid, triphenyl phosphonium hexafluoroantimonate, and the like.
• halides include 2,2,2-trichloro- [1-4 ′-(dimethylethyl) phenyl] ethanone (eg, Trigonal PI manufactured by AKZO), 2.2-dichloro-1--4- (phenoxyphenyl) ) Etanone (Sandoz 1000 manufactured by Sandoz, etc.), ⁇ , ⁇ , ⁇ -tribromomethylphenyl sulfone (manufactured by Steel Chemical Co., Ltd., BMPS, etc.) and the like.
• 2,2,2-trichloro- [1-4 ′-(dimethylethyl) phenyl] ethanone eg, Trigonal PI manufactured by AKZO
• 2.2-dichloro-1--4- (phenoxyphenyl) ) Etanone Sandoz 1000 manufactured by Sandoz, etc.
• ⁇ , ⁇ , ⁇ -tribromomethylphenyl sulfone manufactured by Steel Chemical Co.,
• triazine initiators examples 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 Panchi), 2 [2 ′ (5 ′′ -methylfuryl) ethylidene] -4,6-bis (trichloromethyl)- s-Triazine (manufactured by Sanwa Chemical Co., Ltd.) , 2 (2'-
• borate initiator examples 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 (biimidazole manufactured by Kurogane Kasei Co., Ltd.), 2,2-azobis (2-amino-propane) dihydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) V50), 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 (Ir
• azo initiators such as azobisisobutyronitrile, peroxide radical initiators that are sensitive to heat, such as benzoyl peroxide, and the like may be used in combination.
• 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.
• 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.
• 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.
• a pigment material other than the colored pigment for example, a so-called extender pigment not intended for coloring can be used.
• extender pigment examples include talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, silica, clay and the like.
• resins that are not reactive with active energy rays 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.
• the reactive polyester compound (A) or (A ′) when the reactive polyester compound (A) or (A ′) is to be used for solder resist applications, 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.
• a volatile solvent may be added to the resin composition in a range of 50% by weight, more preferably up to 35% by weight.
• the active energy ray-curable resin composition of the present invention comprises 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 Up to 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.
• 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.
• 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.
• 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.
• the color pigment examples 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.
• 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.
• the film-forming material is used for the purpose of coating the surface of the 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.
• adhesive materials such as adhesives and adhesives, resist materials such as solder resists, etching resists, and resists for micromachines.
• dry film also corresponds to the film forming material. .
• 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.
• the unreacted reactive polyester compound (A) or (A ′) is also preferable to use as an alkaline water developing resist material composition taking advantage of the feature that it is soluble in an alkaline aqueous solution.
• 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.
• active energy rays such as ultraviolet rays
• 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.
• 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.
• the reactive polyester compound of the present invention is excellent in spite of its relatively high molecular weight. Developability can be exhibited.
• 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.
• 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 2 Synthesis of Reactive Polyester Compound (A-2) 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 synthesized epoxy resin N-phenylphthalein type epoxy resin, epoxy equivalent: 266 g / equivalent
• propylene glycol monomethyl ether monoacetate as a solvent for reaction to a solid content of 70%
• the reaction is carried out at a temperature of 98 ° C.
• AA acrylic acid
• Mw 72
• 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.
• Example 4 Preparation of hard coat composition 20 g of reactive polyester compound (A-1, A-2, A′-3, H-1 or H-2) solution 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.
• reactive polyester compound A-1, A-2, A′-3, H-1 or H-2
• an ultraviolet-ray exposure apparatus manufactured by Oak Seisakusho
• 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.
• the photocurable resin composition in the present invention has impact resistance while having relatively high hardness.
• 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.
• 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 ⁇ m 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 ⁇ m, polyimide film thickness: 25 ⁇ m) 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.
• 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).
• 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, 50 g of H-1 or H-2) 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 at 90 ° C. for 150 seconds on a hot plate. The film thickness after drying was 1 ⁇ m. 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).
• Adhesion The minimum pattern size of a resist that can be resolved at an exposure amount that faithfully reproduces a 20 ⁇ m 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 ⁇ m or less, and the adhesion was ⁇ , and the one exceeding 10 ⁇ m was rated as x.
• Heat-resistant A heat resistance test (300 ° C., 1 hour) was performed on the 20 ⁇ m mask pattern, and the film thickness reduction rate (%) at that time was shown.
• 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 Preparation of photosensitive colored resin composition for color filter
• 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.
• IRGACURE907 2,4-diethylthioxanthone (Nippon Kayaku Co., Ltd.) 0.4
• 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 ⁇ m.
• 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.
• 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).
• ⁇ E ab color difference
• Table 4 it means that light resistance is so favorable that (DELTA) Eab value is small.
• 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.
• 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.

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