WO2007119714A1 - Active ray curable hyperbranched polymer - Google Patents

Active ray curable hyperbranched polymer Download PDF

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Publication number
WO2007119714A1
WO2007119714A1 PCT/JP2007/057880 JP2007057880W WO2007119714A1 WO 2007119714 A1 WO2007119714 A1 WO 2007119714A1 JP 2007057880 W JP2007057880 W JP 2007057880W WO 2007119714 A1 WO2007119714 A1 WO 2007119714A1
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Prior art keywords
parts
hyperbranched polymer
acid
reaction
group
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PCT/JP2007/057880
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French (fr)
Japanese (ja)
Inventor
Tetsuo Kawakusu
Hirotoshi Kizumoto
Ryo Hamasaki
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Toyo Boseki Kabushiki Kaisha
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Priority to JP2007529294A priority Critical patent/JPWO2007119714A1/en
Publication of WO2007119714A1 publication Critical patent/WO2007119714A1/en

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    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • 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
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer

Definitions

  • the present invention relates to a resin that exhibits excellent properties as a resist for use in electronic materials and the like, and has a particularly excellent pigment dispersion performance, and has a highly sensitive UV curing function and a good base. It is intended to provide a resin having a developing property for aqueous solution.
  • a resin composition for a UV curable resist generally, a high molecular weight resin component having a structural unit in the molecule that causes a crosslinking reaction by UV in the presence of a photoinitiator such as an unsaturated bond and the resin composition thereof. It is used by blending a low molecular weight compound having a functional group such as an acrylate or metatalylate group having reactivity with a fat component, a photoinitiator, a sensitizer and the like.
  • photoinitiators and sensitizers can absorb light of various wavelengths of the irradiated UV light more efficiently, or the lifetime of the generated active species Molecular designs that can be kept longer are being studied.
  • reactive low molecular weight compounds used in blends have been proposed that have more acrylate and metatalylate groups in one molecule.
  • rosin components also have a structure that absorbs UV light with a relatively long wavelength, such as a fluorene skeleton or biphenyl skeleton, or a structure with a high concentration of unsaturated bonding groups per molecule. ing. Examples of these can be found in Patent Document 1 and Patent Document 2, respectively.
  • Patent Document 3 shows an example in which an effective crosslinking reactivity by irradiation with actinic rays such as ultraviolet rays is obtained by introducing an acrylate group or a methacrylate group at the terminal of a hyperbranched polymer.
  • Patent Document 4 describes that. An example can be seen.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2003-292576 (Example 1)
  • Patent Document 2 Japanese Patent Laid-Open No. 7-103213 (Claims)
  • Patent Document 3 Japanese Unexamined Patent Publication No. 2006-16534 (Claims)
  • Patent Document 4 Japanese Patent Application Laid-Open No. 2002-322348 (Technical Field to which Invention belongs and Prior Art) Disclosure of Invention
  • the object of the present invention is to solve the above-mentioned problems in the prior art, that is, to highly disperse and stabilize the fine particle pigment, and at the same time, to obtain excellent curing characteristics by actinic ray irradiation and good development characteristics by a basic aqueous solution.
  • the object is to provide an actinic ray curable resin that makes it possible. Means for solving the problem
  • the inventors of the present invention have arrived at the present invention as a result of intensive investigations, particularly focusing on the fact that hyperbranched polymers having a certain structure are excellent in the dispersibility of fine particle pigments. That is, the present invention is a polymer having the following hyperbranched structure.
  • R Divalent aliphatic hydrocarbon group having less than 20 carbon atoms
  • R ′ an (n + 1) -valent aliphatic hydrocarbon group having less than 20 carbon atoms, or a group represented by R ′′ N (R ”: a divalent aliphatic hydrocarbon group having less than 20 carbon atoms)
  • n An integer greater than or equal to 2
  • the hyperbranched polymer of the present invention is excellent in pigment dispersibility by having an aromatic ring at a specific concentration, and pigment particles once dispersed by having a hyperbranch structure having a specific aliphatic polyester skeleton force. Aggregation is suppressed, and the dispersed state is maintained stably. In addition, the curing reaction proceeds efficiently when actinic rays are irradiated due to the large amount of unsaturated bonds bound to the molecular ends.
  • hyperbranched polymer was named by Kim and Webster for a hyperbranched polymer with regularity of repeating units (see Polym. Prepr., 29 (198 8) 310), and one molecule It is defined as a possibly high-molecular-weight polymer synthesized by self-condensation of compounds with a total of 3 or more of two kinds of substituents that can react with each other.
  • the hyperbranched polymer described in the present invention applies to the terms proposed by Kim and Webster.
  • multi-branched polymers have been polyester-based, polyamide-based, A variety of types such as retane, polyetherolene, polyetherolonephone and polycarbonate are synthesized.
  • hyperbranched polymers have a structure in which a large amount of functional groups are densely present at the molecular ends extending in a cage shape, and various functional functionalities are utilized using these reactive functional groups. It is possible to introduce groups in large quantities and densely.
  • the resin of the present invention by introducing a large amount of attalylate groups and metatalylate groups at the molecular ends, cross-linking reactions between molecules occur with high efficiency by irradiation with actinic rays.
  • the hyper-branched polymer has a lower solution viscosity in the solution state because there is less entanglement between molecules. As a result, high solids can be easily prepared in preparing the resist coating.
  • the resin used as the core of the hyperbranched polymer of the present invention is a polyester having an aliphatic monomer as a repeating unit and having a no- and hyper-branched structure, heat resistance, other resin components and additives.
  • a general formula representing the structure of such a compound that is particularly preferred from the viewpoint of compatibility with the components and solubility in a general-purpose solvent is represented by Formula 1 for example.
  • R Divalent aliphatic hydrocarbon group having less than 20 carbon atoms
  • R ′ an (n + 1) -valent aliphatic hydrocarbon group having less than 20 carbon atoms, or a group represented by R ′′ N (R ”: a divalent aliphatic hydrocarbon group having less than 20 carbon atoms)
  • n An integer greater than or equal to 2
  • the compound represented by the above chemical formula 1 includes 2,2 dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 5-hydroxycyclohexane-1,3-dicarboxylic acid, 1,3-dihydroxy-5 carboxycyclohexanone.
  • 2-dimethylol pro Pionic acid and 2,2-dimethylolbutanoic acid are preferred.
  • the hyperbranched polymer of the present invention is, for example, the above-mentioned KR, [(R) L] type
  • glycidyl groups or hydroxyl-free groups are added to these molecular terminal functional groups. It can be obtained by adding a monocyclic aromatic compound having an unsaturated bond and a compound containing an unsaturated bond having a darisidyl group or a hydroxyl group-free.
  • the reaction may be carried out in the presence, or a polyvalent hydroxy compound, a polyvalent carboxylic acid compound, or a compound having both of them may be used as the branching point of the hyperperpendicular polymer molecule.
  • a polyvalent hydroxy compound examples include various general-purpose glycol compounds as a polyester resin raw material, and tri- or higher functional hydroxyl group-containing compounds such as trimethylolpropane, pentaerythritol, and dipentaerythritol.
  • examples of the polyvalent carboxylic acid compound include trivalent or higher functional carboxylic acid compounds such as various dibasic acids, trimellitic acid, pyromellitic acid, and benzophenone tetracarboxylic acid, which are general raw materials for polyester resin.
  • examples of the compound having both a hydroxyl group and a carboxylic acid group include glycolic acid, hydroxypivalic acid, 3-hydroxy-2-methylpropionic acid, lactic acid, glyceric acid, malic acid, and citrate.
  • the compound that serves as a branching point of the hyperbranched polymer molecule of the present invention is a linear polyester oligomer obtained by a condensation reaction of a dibasic acid component and a glycol component, or a trivalent or higher polyvalent polyvalent compound. It is also possible to use a branched polyester oligomer copolymerized with a carboxylic acid or a polyhydric hydroxy compound!
  • Dibasic acid compounds include aliphatic dibasic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,2-naphthalenecarboxylic acid Aromatic-basic acids such as 1,6-naphthalene dicarboxylic acid or 1,2-cyclohexanedicarboxylic acid 1,4-cyclohexanedicarboxylic acid, 4-methyl-1,2 cyclohexanedicarboxylic acid, and the like.
  • aliphatic dibasic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,2-naphthalenecarboxylic acid
  • Aromatic-basic acids such as 1,6-naphthalene dicarboxylic acid or 1,2-cyclohe
  • terephthalic acid isophthalic acid, orthophthalic acid, 1 1, 2 Naphthalene carboxylic acid, 1, 6 naphthalene dicarboxylic acid, particularly preferably terephthalic acid, 1, 2 naphthalene carboxylic acid, 1, 6 naphthalene dicarboxylic acid.
  • the glycol components include ethylene glycol, 1,2 propylene glycol, 1, 3 -propylene glycol, 1,2 butylene glycol, 1,3 butylene glycol, 2,3 butylene glycol, 1,4-butylene glycol, 2-methyl- 1,3 propylene glycol, neopentyl glycol, 3-methyl-1,5 pentanediol, 2,2,4 trimethyl-1,3 pentanediol, 2,4 jetyl 1,5 pentanediol, 2 ethyl-1,3 hexanediol 2, 2 Dimethyl-3 hydroxypropyl 2 ', 2, —Dimethyl-3 hydroxypropanoate, 2-nbutyl-2 ethyl-1, 3-propanepropanediol, 3 ethyl-1,5 pentanediol, 3 propyl 1,5 pentane Diol, 2, 2 Jetyl 1,3 Propanediol, 3-Octyl-1,5
  • Aliphatic diols 1,3 bis (hydroxymethyl) cyclohexane, 1,4 bis (hydroxymethyl) cyclohexane, 1,4 bis (hydroxyethyl) cyclohexane, 1,4 bis (hydroxypropyl) ) Cyclohexane, 1,4 bis (hydroxymethoxy) cyclohexane, 1,4 bis (hydroxyethoxy) cyclohexane, 2,2 bis (4 hydroxymethoxycyclohexyl) propane, 2,2 bis (4 hydroxy) Ethoxycyclohexyl) propane, bis (4-hydroxycyclohexyl) methane, 2, 2 bis (4-hydroxycyclohexyl) propane, 3 (4), 8 (9) —Tricyclo [5. 2. 1.
  • alicyclic glycols such as Dekanjimetano Lumpur, or aromatic glycols such as ethylene oxide Ya profile propylene oxide adduct of bisphenol a Among them, 2, 2-dimethyl 3 hydroxypropyl 2, 2, 1, 1 dimethyl 3 hydroxypropanate, 2, 2 bis (4 hydroxycyclohexyl) propane, 3 (4), 8 ( 9) —Tricyclo [5. 2. 1. 0 2 ' 6 ] decane dimethanol and polyester resin that can be used for the addition of bisphenol A ethylene oxide propylene oxide adduct. preferable.
  • the trifunctional or higher polyhydric carboxylic acid and polyhydric alcohol compound include trimellitic acid pyromellitic acid, benzophenone tetracarboxylic acid, glycerin, trimethylolpropan, pentaerythritol and the like. Can be mentioned.
  • the condensed water produced by the condensation reaction is azeotropically dehydrated with toluene-xylene, or the inert gas is blown into the reaction system and the water produced by the condensation reaction together with the inert gas.
  • the monoalcohol is blown out of the reaction system or distilled off under reduced pressure.
  • the catalyst used for the reaction is the same as a normal polyester resin polymerization catalyst, as well as various metal compounds such as titanium, tin, antimony, zinc and germanium, and strong acid compounds such as p-toluenesulfonic acid and sulfuric acid. Can be used.
  • an unsaturated bond-containing compound having a glycidyl group or a hydroxyl-free group are added.
  • compounds used in the case of a hyperbranched polymer having a hydroxyl group at the end include monocyclic aromatics such as trimellitic anhydride, phthalic anhydride, biphenyltetracarboxylic dianhydride, and benzophenone tetracarboxylic acid.
  • trimellitic anhydride which has one hydroxyl group and one carboxyl group in one molecule, generates a total of two carboxyl groups at the polymer end when the anhydride group reacts with the hydroxyl group. You can increase it further. In this sense, trimellitic anhydride is most preferable.
  • phenyl glycidyl ether In addition to the carboxyl group formed by the reaction of these hydroxyl groups with the anhydride compound, phenyl glycidyl ether, 4-fluoro-phenyl glycidyl ether, 4-methoxy thiol Unsaturated bonds and glycidyl groups such as monocyclic aromatic compounds containing a glycidyl group such as enyldaricidyl ether, glycidyl (meth) atalylate, allyl glycidyl ether, 4-hydroxybutyl atelate glycidyl ether, etc. It is also possible to react the contained compounds. Of these compounds, versatile surface powers such as phenol glycidyl ether, glycidyl atylate, glycidyl metatalylate and 4-hydroxybutyl atylate glycidyl ether are preferred.
  • the above anhydride compound may be further reacted with a hydroxyl group produced by the reaction of the above carboxyl group and glycidyl group.
  • the unsaturated bond-containing compound used in this reaction step is preferably maleic anhydride or 1,2,5,6-tetrahydroxyphthalic anhydride from the viewpoint of reactivity and versatility.
  • the terminal is a carboxyxyl group
  • the compound containing the glycidyl group can be reacted.
  • the acid anhydride compound may be reacted with the hydroxyl group produced here.
  • the actinic ray curable hyperbranched polymer of the present invention absorbs ultraviolet rays for the purpose of further improving the sensitivity to ultraviolet rays in a range without impairing the excellent pigment dispersibility and dispersion stability of the polymer.
  • An acid anhydride compound having a functional skeleton or a glycidyl complex may be reacted and added.
  • Specific compounds used for this purpose include, for example, benzophenone tetracarboxylic dianhydride, anthracene-9-glycidyl ether, benzophenone such as 9,9-bis (4-phenylglycidyl ether) fluorene.
  • compounds having a skeleton such as anthracene and fluorene.
  • Benzophenone tetracarboxylic dianhydride is preferred.
  • any of the above reaction methods of hydroxyl group-free hydroxyl reaction and carboxyl group-glycidyl group reaction may be used in any order. . These reactions proceed in higher yields under milder conditions than those of hydroxyl groups and carboxyl groups or ester derivatives thereof. This is suitable for denaturation of highly reactive hyperbranched compounds, and it is difficult for side reactions to occur due to the formation of reaction by-products and an increase in molecular weight distribution due to cross-linking reactions, or gelling.
  • the concentration of the introduced aromatic ring is not less than 3000eqZton and less than 5000eqZton. If it is less than 3000 eqZton, excellent pigment dispersion performance cannot be obtained. In addition, if it is introduced in excess of 5000 eqZton from the number of reaction points present at the terminal, the amount of unsaturated bonds that contribute to actinic radiation curing performance is limited, and sufficient actinic radiation curing performance cannot be obtained.
  • the aromatic rings constituting these polycyclic aromatic compounds are not added to the “concentration of aromatic rings” in the present invention.
  • the concentration of aromatic rings referred to here represents the number of moles of monocyclic aromatic rings contained in one lton of hyperbranched polymer.
  • the number average molecular weight of the polyester (no, hyperbranched core portion) having a hyperbranched structure as an aliphatic monomer repeating unit is 2000 or more and less than 4000. If the number average molecular weight is less than 2000, initial pigment dispersibility can be obtained, but sufficient dispersion stability cannot be obtained, and pigment particles may aggregate during storage.
  • the hyper-branched compound of the aliphatic polyester skeleton used in the resin of the present invention has a high melt viscosity when the number average molecular weight exceeds 4,000, and it becomes difficult to control uniform reaction, and stable quality is obtained. It may disappear.
  • the unsaturated bond concentration of the actinic ray curable hyperbranched polymer of the present invention is not particularly limited because it has an appropriate concentration depending on the intended use and formulation, but at least 500 eqZton is preferred. If it is less than 500eqZton, sufficient actinic ray curability may not be obtained. If it exceeds 5000 eqZton, the adhesion to the substrate may decrease due to shrinkage of the curing reaction.
  • concentration said here is represented by the number-of-moles of the double bond contained in the resin It.
  • the acid value of the actinic radiation curable hyperbranched polymer of the present invention should also be adjusted to an appropriate concentration corresponding to each application and use conditions.
  • Is preferably 500 eq / ton or more, more preferably 800 eq / ton or more. If it exceeds 3000 eq Zton, the hydrophilicity of the resin is too high, and the water resistance of the cured reaction product may decrease.
  • the actinic ray curable hyperbranched polymer synthesis reaction conditions of the present invention are not particularly limited. However, preferably, the temperature is set in the range of 60 ° C to 150 ° C, and the reaction time is appropriately set so that the reaction is completed within this temperature range. At this time, it is also effective to add a reaction catalyst to accelerate the reaction, or to add a polymerization inhibitor or molecular oxygen so as not to cause gelation due to polymerization reaction or progress of polymerization. is there.
  • Reaction catalysts include amines such as triethylamine and benzyldimethylamine; quaternary ammonium salts such as tetramethylammonium chloride and triethylbenzylammonium chloride; imidazoles such as 2-ethyl 4-imidazole and the like. Amides; pyridines; phosphines such as tri-phenol phosphine; fofoform salts such as tetraphenol-phosphophospho-mubromide; sulfo-um salts; sulfonic acids; organometallic salts such as zinc octylate It is
  • polymerization inhibitor examples include known and conventional polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, and phenothiazine.
  • An organic solvent can be used in the synthesis of the actinic ray curable hyperbranched polymer of the present invention, or in the curable resin composition using the polymer.
  • the organic solvent is used in an amount sufficient to uniformly dissolve or disperse each component.
  • the solid content concentration in the synthesis of the actinic ray curable hyperbranched polymer is usually 10 to 90% by weight, preferably 20 to 70% by weight.
  • the solid content in the curable resin composition is 5 to 50% by weight, preferably 10 to 40% by weight.
  • organic solvent examples include aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve and butylcetosolve; carbitols such as carbitol and butylcarbitol; cellosolve acetate, carbitol acetate, ( Di) propylene glycol monomethyl ether acetate, butylcetosolve acetate, carbitol acetate, esters such as ethyl acetate, butyl acetate, ketones such as cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone; (di) ethylene glycol Examples include ethers such as dimethyl ether, diethylene glycol monoethyl ether, and dipropylene glycol jetyl ether.
  • ester-based or ether-based solvent in terms of toxicity and coating characteristics. These solvents are used alone or in combination of two or more. It is advisable to use an appropriate amount so as to obtain an optimum viscosity that is easy to handle.
  • the actinic rays used in the present invention may be visible rays, ultraviolet rays, electron beams, X-rays, ex-lines, ⁇ -lines, ⁇ -lines, etc. in order of wavelength.
  • ultraviolet rays are the most preferable actinic rays in practical use from the viewpoints of economy and efficiency.
  • the light source used for the ultraviolet irradiation used in the present invention sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a carbon arc lamp, a kinocene lamp, a metal nitride lamp, or the like is used.
  • the actinic rays having a wavelength shorter than that of ultraviolet rays are theoretically highly chemically reactive and are superior to ultraviolet rays. From the viewpoint of economic efficiency, ultraviolet rays are practical.
  • Photoinitiators include, for example, chloroacetophenone, 4-phenoxydichloroacetophenone, 4t-butyltrichloroacetophenone, cetoxyacetophenone, 2-hydroxy 2-methyl 1 phenylpropane 1 ion 1- (4-Isopropyl phenol) 2 Hydroxy 2-methylpropane 1-one, 2-Hydroxy mono 2-Methyl-1-phenol (4 dodecyl) propane 1-one, 4-— (2-Hydroxyethoxy Enyl) 2-hydroxy-1-2-methylpropane-1-one, 1-hydroxycyclohexyl roof ketone, 2-methyl-11- (4- (methylthio) phenol) 2-morpholinopropane-1-one, 2- Benzyl 1-dimethylamino 1- (4 morpholinophenyl) 1-butanone 1-1, phenyl 1-dimethylamino 1- (4 morpholinophenyl) 1-butanone 1-1, phenyl 1-dimethylamino 1- (4
  • photoinitiator among the above-mentioned photoinitiators, 2-hydroxy-2-methyl-1-phenylpropane 1-one, 1-hydroxycyclohexyl roofing ketone, 2-methyl-14- (methylthio) phenol ] 2 Morpholinopropane 1-on, 2-benzil-2 Dimethylamino 1- (4-morpholinophenol) 1-butanone 1
  • Acetophenones such as 1, benzyldimethyl ketal (2,2-dimethoxy-1,2,2-diphenylethane 1-on), anthraquinones such as 2-ethyl anthraquinone, and thixanthones such as 2,4-jetylthioxanthone are preferred in terms of curability and adhesion.
  • a photoinitiator may be used in combination with a photopolymerization initiator.
  • the photoinitiator include triethanolamine, methyl jetanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl dimethylaminobenzoate, 4 dimethylaminobenzoic acid 2 Ethyl hexyl, 2 dimethylaminoethyl benzoate, N, N dimethylbalatoluidine, 9,10 dimethoxyanthracene, 2 ethyl-9,10 dimethoxyanthracene, 9 10 diethoxyanthracene, 2 ethyl 9,10 jetoxyanthracene .
  • These photoinitiators can be used alone or in combination of two or more.
  • the amount of the photoinitiator to be added is 100% by weight with respect to a total of 100 parts by weight of the actinic ray curable hyperbranched polymer and the actinic ray polymerizable compound (described later) used as necessary. 3 parts by weight or more is preferred, more preferably 0.5 parts by weight or more. The upper limit is preferably 10 parts by weight or less, more preferably 5 parts by weight or less. If the amount is less than 3 parts by weight, the UV curability is insufficient and the adhesion tends to be poor, or the hardness tends to be low.
  • the total amount of the photoinitiator and the photoinitiator is preferably within the above range.
  • actinic ray curable hyperbranched polymer of the present invention can be blended with an appropriate amount of another actinic ray photopolymerizable compound having an actinic ray polymerizable double bond in the molecule, if necessary.
  • active light polymerizable compounds having one active light photopolymerizable double bond in the molecule include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n— and i-propyl (meth) acrylate, i-, n-butyl (meth) acrylate, isodecyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, lauryl (meth) acrylate Alkyl (meth) acrylates such as 2-ethoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, 2- Hydroxyalkyl (meth) acrylates such as hydroxybutyl meta acrylate, or polyoxyalkylene glycol mono (meth) acrylate such as polyethylene glycol mono (meth)
  • ta) acrylate, isoball (meth) acrylate, dicyclopentyl (meth) acrylate, (dicyclopentyl) oxy (meth) acrylate, and diisocyanate compound 1 In the molecule obtained by reacting a terminal isocyanate group-containing compound obtained by reacting at least one alcoholic hydroxyl group-containing compound in advance with an alcoholic hydroxyl group-containing (meth) acrylate, ) Urethane-modified mono (meth) atalylates having an allyloyloxy group, acrylic acid or methacrylic acid as a carboxylic acid component and polyhydric power rubonic acid and a polyhydric alcohol having two or more valences as an alcohol component. The resulting oligoester mono (meth) acrylates.
  • active photopolymerizable compounds having two photopolymerizable double bonds in the molecule include, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1, 3 butanediol di (Meth) Atarylate, 1, 4 Butanediol Di (Meth) Atarylate, Neopentyl Glycol Di (Meth) Atarylate, 1, 6 Hexanediol Di (Meth) Atarylate, 1,9-Nonanediol Dimetatalylate , Alkylene glycol di (meth) acrylates such as glycerin dimetatalylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, polypropylene glycol di ( Data) polyoxyalkylene glycol di (meth) Atari rate such as Atari
  • Other active photopolymerizable compounds having three or more photopolymerizable double bonds in the molecule include trimethylolpropane tri (meth) acrylate and tetramethylolmethanetri (meth). Atalylate, tetramethylol ethane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, ethylene oxide modified trimethylol propane (meth) acrylate, dipentaerythritol hex (meth) acrylate .
  • the actinic ray polymerizable compound is blended in an amount of 50% by weight or less based on the actinic ray curable hyperbranched polymer, if necessary.
  • the compounding amount varies depending on the application conditions, but if it exceeds 50% by weight, the UV curing reactivity becomes saturated and further curing does not improve the curability, but rather the reaction rate of unsaturated bonds decreases. To do.
  • the low molecular weight component becomes excessive, and the durability of the cured coating film deteriorates.
  • a crude resin composition using the actinic ray curable hyperbranched polymer of the present invention is easily produced by stirring and mixing at room temperature or, if necessary, heating.
  • known hydroquinone, hydroquinone monomethyl ether, 1-butyl-catechol, p-benzoquinone, 2,5-tert-butyl-hydroquinone, phenothiazine, etc. It is desirable to add a thermal polymerization inhibitor.
  • the addition amount is preferably 0.001 part by weight or more, more preferably 0.005 part by weight or more, with respect to 100 parts by weight of the actinic ray-polymerizable oligomer (A) containing the polyester of the present invention as a copolymerization component,
  • the upper limit is preferably 0.1 parts by weight or less, more preferably 0.05 parts by weight or less. If it is less than 0.001 part by weight, the effect may not be obtained, and if it exceeds 0.1 part by weight, the effect is saturated and it is not economical.
  • the photoinitiator, sensitizer, and actinic ray polymerizable compound in addition to the photoinitiator, sensitizer, and actinic ray polymerizable compound, other resin components such as epoxy resin and phenol resin can be blended. These resin components may be blended at an arbitrary ratio within the range without impairing the properties of the hyperbranched polymer of the present invention.
  • the coarse resin composition using the actinic ray curable hyperbranched polymer of the present invention is non-reactive such as epoxy resin, liquid polybutadiene, polyurethane polymer, silicon oligomer, etc., depending on the application.
  • fillers such as silicon oxide, talc, silica, calcium carbonate, bentonite, kaolin, glass fiber, mica, etc., antifoaming agent, flame retardant, cutting agent, tackifier, leveling agent Plasticizers, antioxidants, ultraviolet absorbers, flame retardants, dyes, and the like can be used as appropriate.
  • reaction accelerator in the curable resin composition using the actinic ray curable hyperbranched polymer of the present invention, addition of a reaction accelerator is more effective when the reaction needs to be accelerated.
  • the reaction accelerator include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-methylimidazole, benzyldimethylamine, and triethanolamine.
  • Tertiary amines such as amine, triethylamine, n-butylamine, di-n-butylamine, N, N-dimethylaminoethanol, N, N-dimethylaminoethanol, N, N-dipropylaminoethanol , Tertiary amine salts such as triacetate and tribenzoate of tridimethylaminomethylphenol, ureas such as allylthiourea and o-tolylthiourea, s-benzyl-isothiuol-mu p-toluenesulfinate N-butylphosphine, sodium jetyl dithiophosphate Phosphorus compounds such as these are used alone or in combination of two or more.
  • the addition amount of these reaction accelerators is compared with the case where the total amount of the actinic radiation curable hyperbranched polymer of the present invention and the actinic radiation polymerizable compound used as necessary is 100 parts by weight.
  • the amount is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more.
  • the upper limit is preferably 5 parts by weight or less, more preferably 3.5 parts by weight or less. If it is less than 0.05 parts by weight, the effect of promoting the reaction may not be obtained, and if it exceeds 3.5 parts by weight, the storage stability may be deteriorated.
  • the actinic ray curable hyperbranched polymer of the present invention is used as a resin grease for electronic materials or the like, various pigments are dispersed and blended depending on the application.
  • the conductive particles include gold, platinum, silver, palladium, rhodium, zinc, copper, nickel, iron, and alloys of these metals, graphite, carbon nanotubes, conductive carbon black, and the like.
  • the insulating particles include silica and alumina oxides, inorganic particles such as zeolite, and organic polymer particles.
  • organic pigments such as phthalocyanine, inorganic pigments such as titanium white and iron oxide, and various organic dyes such as azo dyes are dispersed and blended as colorants.
  • the 1 H-NMR analysis was performed and determined from the integration ratio.
  • the ⁇ 0. 2 g was dissolved in black port Holm 20 cm 3, and titrated with potassium hydroxide ethanol solvent solution of 0. 1N, was determined equivalents per ⁇ 10 6 g (eq / 10 6 g).
  • As the indicator phenolphthalein was used.
  • Pentaerythritol DMBA dimethylol butanoic acid
  • TMA trimellitic anhydride
  • PA phthalic anhydride
  • GMA Glycidylmetatalylate
  • TBPGE p-tert-butylphenol glycidyl ether
  • PETA Condensate of pentaerythritol and acrylic acid
  • TPP triphenylphosphine
  • the obtained actinic ray curable hyperbranched polymer (1) had a number average molecular weight of 4700, an acid value of 1800 eqZton, a glass transition temperature of 3 ° C, an unsaturated bond group concentration of 1900 eqZton, and an aromatic ring concentration of 3200 eqZton. These results are shown in Tables 2 and 3.
  • the resulting actinic radiation curable hyperbranched polymer (3) has a number average molecular weight of 5500, an acid value of 1510 eqZton, a glass transition temperature of 15 ° C, an unsaturated bond group concentration of l lOOeq / ton, and an aromatic ring concentration of 4000 eqZton. Met.
  • the actinic ray curable hyperbranched polymer (4) obtained had a number average molecular weight of 4800, an acid value of 2680 eqZton, a glass transition temperature of 18 ° C, an unsaturated bond group concentration of 750 eqZton, and an aromatic ring concentration of 3200 eqZton. It was.
  • the actinic ray curable hyperbranched polymer (5) obtained had a number average molecular weight of 7300, an acid value of 4 20 eqZton, a glass transition temperature of 35 ° C, an unsaturated bond group concentration of 300 eqZton, and an aromatic ring concentration of 4500 eqZton. .
  • a reaction kettle equipped with a partial condenser, thermometer, and stirring rod was charged with 136 parts of pentaerythritol, 8000 parts of dimethylolbutanoic acid, and 40 parts of paratoluenesulfonic acid (hereinafter abbreviated as PTS), and stirred at 100 ° C and homogeneous. A liquid mixed melt was obtained. Next, 100 parts of toluene was injected, the temperature was raised to 140 ° C, and water generated while refluxing toluene was distilled out of the system by azeotropic distillation. After continuing the reaction for 5 hours under the same conditions, toluene was distilled off from the system to obtain hyperbranched polymer A2. The resulting polycondensate had an acid value of 214 eqZton and a number average molecular weight of 3800.
  • the actinic ray curable hyperbranched polymer (6) obtained had a number average molecular weight of 7800, an acid value of 780 eqZton, a glass transition temperature of 28 ° C, an unsaturated bond group concentration of 650 eqZton, and an aromatic ring concentration of 350 OeqZton. It was. These results are shown in Tables 2 and 3.
  • Trimethylol properties in a reaction kettle equipped with a partial condenser, thermometer, and stir bar 134 parts, dimethylolbutanoic acid 7000 parts, and paratoluenesulfonic acid (hereinafter abbreviated as PTS) 40 parts were charged and stirred at 100 ° C. to obtain a uniform liquid mixed melt. Subsequently, 100 parts of toluene was injected, the temperature was raised to 140 ° C., and water generated while refluxing toluene was distilled out of the system by azeotropic distillation. After continuing the reaction for 5 hours under the same conditions, toluene was distilled off from the system to obtain a hyperbranched polymer A3. The resulting polycondensate had an acid value of 304 eqZton and a number average molecular weight of 3,500.
  • TEA triethylamine
  • TPP triphenylphosphine
  • the obtained active photocurable hyperbranched polymer (7) has a number average molecular weight of 5400, an acid value of 1500 eq / ton, a glass transition temperature of 32 ° C, an unsaturated bond group concentration of 850 eqZton, and an aromatic ring concentration of It was 3600eqZton.
  • a reaction kettle equipped with a partial condenser, thermometer, and stirring rod was charged with 134 parts of trimethylolpropan, 3500 parts of dimethylolpropionic acid, and 20 parts of paratoluenesulfonic acid (hereinafter abbreviated as PTS), and stirred at 100 ° C. A uniform liquid mixed melt was obtained.
  • PTS paratoluenesulfonic acid
  • 100 parts of toluene was injected, the temperature was raised to 140 ° C, and water generated while refluxing toluene was distilled out of the system by azeotropic distillation. After continuing the reaction for 3 hours under the same conditions, toluene was distilled off from the system to obtain a hyperbranched polymer A4.
  • the resulting polycondensate had an acid value of 232 eq / ton and a number average molecular weight of 2300.
  • the actinic ray-curable hyperbranched polymer (8) obtained had a number average molecular weight of 3800, an acid value of 1400 eqZton, a glass transition temperature of 27 ° C, an unsaturated bond group concentration of 900 eqZton, and an aromatic ring concentration of 4100 eqZton. .
  • the actinic ray curable hyperbranched polymer (9) obtained had a number average molecular weight of 4100, an acid value of 1700 eqZton, a glass transition temperature of 12 ° C, an unsaturated bond group concentration of 900 eqZton, and an aromatic ring concentration of 1900 eqZton. It was. These results are shown in Tables 2 and 3.
  • a reaction vessel equipped with a partial condenser, a thermometer, and a stirring rod was charged with 136 parts of pentaerythritol, 1776 parts of dimethylolbutanoic acid and 21 parts of PTS, and stirred at 100 ° C to obtain a uniform liquid mixed melt.
  • 100 parts of toluene was injected, the temperature was raised to 140 ° C., and water generated while refluxing toluene was distilled out of the system by azeotropic distillation. After the reaction was continued for 2 hours under the same conditions, toluene was distilled out of the system to obtain hyperbranched polymer A5.
  • the polycondensate obtained had an acid value of 250 eqZton and a number average molecular weight of 1500.
  • the resulting photocured hyperbranched polymer (11) has a number average molecular weight of 3200, an acid value of 124 Oeq / ton, a glass transition temperature of 24 ° C, an unsaturated bond group concentration of 900 eqZton, and an aromatic ring concentration of 4100 eq Zton.
  • the number average molecular weight of the obtained hyperbranched polymer (12) was 4700, the acid value was 1020 eqZton, the glass transition temperature was 35 ° C, the unsaturated bond group concentration was OeqZton, and the aromatic ring concentration was 3800 eqZton.
  • the hyperbranched polymer (A5) obtained in Comparative Example 11 (1000 parts), PGMEA (1000 parts), and toluene (1000 parts) were charged. After dissolution, the mixture was heated to 145 ° C. to distill off water in the system, and toluene was completely distilled off. . Add 794 parts of maleic anhydride and 5.5 parts of TEA as a catalyst, react at 80 ° C for 3 hours under nitrogen atmosphere, add 1350 parts of 4-hydroxybutyl acrylate diglycidyl ether and 27 parts of TPP as a catalyst. The reaction was further continued at 115 ° C for 4 hours.
  • a hyperperbranched polymer 13
  • the average molecular weight of the obtained hyperbranched polymer (13) was 4700
  • the acid value was 600 eqZton
  • the glass transition temperature was 5 ° C
  • the unsaturated bond group concentration was 4500 eqZton
  • the aromatic ring concentration was 200 eqZton.
  • the hyperbranched polymer (A5) obtained in Comparative Example 11 1000 parts
  • PGMEA 1000 parts
  • toluene 1000 parts
  • the number average molecular weight of the actinic ray curable hyperbranched polymer (14) was 4100, the acid value was 1600 eqZton, the glass transition temperature was 28 ° C, the unsaturated bond group concentration was 650 eqZton, and the aromatic ring concentration was 800 eqZton.
  • the obtained no-perbranched polymer (15) has a number average molecular weight of 3500, an acid value of 1500 eqZton, and a glass transition temperature of 45. C, aromatic ring concentration was 1900eqZton.
  • the hyper-branched polymer (16) obtained had a number average molecular weight of 5200, an acid value of 750 eqZton, a glass transition temperature of 32 ° C, an unsaturated bond group concentration of 1500 eqZton, and an aromatic ring concentration of 2800 eqZton.
  • a flask equipped with a Liebig condenser, thermometer and stir bar is charged with 194 parts of dimethyl terephthalate, 194 parts of dimethyl isophthalate, 146 parts of neopentyl glycol, 160 parts of ethylene glycol, and 0.2 part of tetrabutoxy titanate as a polymerization catalyst.
  • the polymerization reaction was carried out at 250 ° C under reduced pressure for 30 minutes, the temperature was lowered to 220 ° C, and the pressure was returned to normal pressure under N atmosphere. Then trimellitic anhydride
  • the number average molecular weight of the steal resin (A6) was 5000, and the acid value was 250 eqZton.
  • a flask equipped with a Liebig condenser, thermometer and stir bar is charged with 194 parts of dimethyl terephthalate, 194 parts of dimethyl isophthalate, 146 parts of neopentyl glycol, 160 parts of ethylene glycol, and 0.2 part of tetrabutoxy titanate as a polymerization catalyst.
  • a polymerization reaction was carried out at 250 ° C under reduced pressure for 20 minutes, and the product was taken out.
  • the number average molecular weight of the obtained polyester resin (A7) was 2000, and the acid value was 18 eq / ton.
  • the number average molecular weight was 11,000, the glass transition temperature was 54 ° C, the acid value was 20 eqZton, the unsaturated bond group concentration was 1000 eqZton, and the aromatic ring concentration was 3900 eq Zton.
  • the comparative examples (9), (10), (16) are examples of a force molecule having a hyperbranch structure, the aromatic ring is deficient in the molecule, the comparative example (11) is a hyperbranch structure, Examples that have sufficient aromatic hydrocarbon residues in the molecule but lack the number-average molecular weight of the base aliphatic hyperbranched core structure, and Comparative Example (12) are hyperbranched structures and In addition, examples of comparative synthesis examples (13) and (14) having a sufficient aromatic hydrocarbon residue in the molecule but not having an unsaturated bond group have a hyperbranched structure.
  • composition and physical properties of the above-obtained hyperbranched polymer (core) and the like are shown in Table 1, and the composition and physical properties of the hyperbranched polymer of the present invention synthesized therewith are shown together with the composition and physical properties of the comparative examples. Shown in 2 3.
  • a 30 wt% PG MEA solution of the actinic ray curable hyperbranched polymer obtained in Example (1) above was prepared, and a photosensitive composition was prepared by the following formulation.
  • Initiator (Irgacure 907) 10 parts by weight
  • Sensitizer (Michler's ketone) 2. 2 parts by weight
  • composition was kneaded and then dispersed with a paint shaker to prepare a carbon black dispersion paint.
  • the obtained carbon black-dispersed paint was applied to a 25 micron thick biaxially stretched PET film so that the coating thickness was 1 micron after drying, and the coating was dried with hot air at 120 ° C for 10 minutes.
  • UV irradiation treatment was performed at 50 mj / cm 2 to obtain a cured carbon black dispersed coating film.
  • the dispersion performance of the actinic ray curable hyperbranched polymer was evaluated by measuring the surface gloss of the prepared coating film. The gloss of the carbon black-dispersed coating film was measured at 45 degrees. The results are shown in Table 4.
  • the storage stability of the paint was evaluated by conducting a heating acceleration test to observe the paint state after storing the carbon black-dispersed paint before preparation of the coating film at 40 degrees X for 2 weeks.
  • the degree of paint state is shown in the following four stages. The results are shown in Table 4.
  • Hyperbranched polymer (1) (solid content 30%) 80 parts by weight (solid content)
  • Sensitizer (Michler's ketone) 1 part by weight
  • the hyperbranched polymer of the present invention clearly exhibits excellent pigment dispersibility and high curing reactivity when irradiated with low energy UV.
  • the present invention finds an actinic ray curable hyperbranched polymer capable of forming a cured coating film with extremely low energy by irradiation with actinic rays such as ultraviolet rays, and is excellent as a resist material used for electronic materials. It is an object of the present invention to provide an actinic ray curable resin composition that exhibits excellent characteristics.

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Abstract

Disclosed is a resin which is excellent when used as a resist. This resin is excellent in pigment dispersibility and enables to obtain an object development pattern at high rate by being sufficiently cured in an exposed portion even when irradiated with a low energy active ray. Specifically disclosed is an active ray curable hyperbranched polymer which is obtained by reacting a polyester, which has a hyperbranched structure wherein an aliphatic monomer is contained as a repeating unit while having a number average molecular weight of not less than 2000 but less than 4000, with a monocyclic aromatic compound having a glycidyl group or an acid anhydride group and an unsaturated bond-containing compound having a glycidyl group or an acid anhydride group. The concentration of aromatic rings introduced by the monocyclic aromatic compound is not less than 3000 eq/ton but less than 5000 eq/ton in the whole hyperbranched polymer.

Description

活性光線硬化型ハイパーブランチポリマー  Actinic radiation curable hyperbranched polymer
技術分野  Technical field
[0001] 本発明は電子材料用途等に用いられるレジスト用として優れた特性を発揮する榭 脂に関するもので、特に極めて優れた顔料分散性能を有し、かつ高感度な UV硬化 機能と良好な塩基性水溶液現像特性を併せ持った榭脂を提供するものである。 背景技術  [0001] The present invention relates to a resin that exhibits excellent properties as a resist for use in electronic materials and the like, and has a particularly excellent pigment dispersion performance, and has a highly sensitive UV curing function and a good base. It is intended to provide a resin having a developing property for aqueous solution. Background art
[0002] 近年、電子材料用途に用いられる種々封止剤やプリント配線基板用導電性塗料用 ノインダ一として用いられるレジスト用榭脂は生産効率向上を目的とした生産ライン スピードの高速化、或いは封止部位や配線パターンの複雑'緻密化により、熱や光 や電子線によって、より高効率に反応硬化する特性が要求されている。特に UV硬化 型レジスト榭脂は UV照射装置の簡便性や硬化反応の迅速性から着目され、開発 · 改良が進められて来た。  [0002] In recent years, various sealants used for electronic materials and resist resin used as a no-binder for conductive coatings for printed wiring boards have been increased in production line speed or sealed for the purpose of improving production efficiency. Due to the complexity and densification of stop parts and wiring patterns, the property of reaction hardening with higher efficiency by heat, light and electron beams is required. In particular, UV-curable resist resins have been developed and improved with the focus on the simplicity of UV irradiation equipment and the speed of the curing reaction.
[0003] UV硬化型レジスト用榭脂組成物としては一般に、不飽和結合等の光開始剤の存 在下 UVにより架橋反応を起こす構造単位を分子中に有した高分子量の榭脂成分と それら榭脂成分と反応性を有するアタリレート基、メタタリレート基等の官能基を有す る低分子量化合物、及び光開始剤、増感剤等をブレンドして、使用される。より感度 の高 ヽ UV硬化機能を付与するため、光開始剤や増感剤は照射される UV光が有す る種々波長の光をより効率よく吸収できる様、或いは発生した活性種の寿命がより長 く保たれる様な分子設計が検討され続けている。また、ブレンド使用される反応性低 分子化合物では一分子中により多くのアタリレート基、メタタリレート基を有するものが 提案されてきた。  [0003] As a resin composition for a UV curable resist, generally, a high molecular weight resin component having a structural unit in the molecule that causes a crosslinking reaction by UV in the presence of a photoinitiator such as an unsaturated bond and the resin composition thereof. It is used by blending a low molecular weight compound having a functional group such as an acrylate or metatalylate group having reactivity with a fat component, a photoinitiator, a sensitizer and the like. In order to provide a more sensitive UV curing function, photoinitiators and sensitizers can absorb light of various wavelengths of the irradiated UV light more efficiently, or the lifetime of the generated active species Molecular designs that can be kept longer are being studied. In addition, reactive low molecular weight compounds used in blends have been proposed that have more acrylate and metatalylate groups in one molecule.
一方榭脂成分も分子中にフルオレン骨格ゃビフ ニル骨格の様な比較的長波長 の UV光を吸収する骨格が導入されたり、一分子当たりの不飽和結合基濃度の高い 構造が提案されたりしている。それぞれ特許文献 1、特許文献 2にはそれらの一例が 見られる。  On the other hand, rosin components also have a structure that absorbs UV light with a relatively long wavelength, such as a fluorene skeleton or biphenyl skeleton, or a structure with a high concentration of unsaturated bonding groups per molecule. ing. Examples of these can be found in Patent Document 1 and Patent Document 2, respectively.
[0004] 近年、デンドリマーやノヽィパーブランチポリマーと呼ばれる多分岐構造を有するポリ マーの種々用途への応用が盛んに検討されている。これら多分岐ポリマーはとりわけ 分子末端に多量の官能基を有する事から、多様な機能を発揮する有機基を化学結 合により導入する事が出来る。ノ、ィパーブランチポリマー末端にアタリレート基、メタク リレート基を導入する事で紫外線等の活性光線照射による効果的な架橋反応性を得 ようとする一例が特許文献 3に示されている。 [0004] In recent years, polymers having a multi-branched structure called a dendrimer or a no-peribranched polymer The application of mer to various uses is actively studied. Since these multibranched polymers have a large amount of functional groups at the molecular terminals, organic groups that exhibit various functions can be introduced by chemical bonds. Patent Document 3 shows an example in which an effective crosslinking reactivity by irradiation with actinic rays such as ultraviolet rays is obtained by introducing an acrylate group or a methacrylate group at the terminal of a hyperbranched polymer.
或いはこれら多分基ポリマー骨格及び末端に導電性、光増感性を有する構造単位 を導入する事で、これらの特性がより効果的に増幅される事が知られており、特許文 献 4にはその一例が見られる。  Alternatively, it is known that these characteristics are more effectively amplified by introducing structural units having conductivity and photosensitization into the polymer skeleton and terminals, and Patent Document 4 describes that. An example can be seen.
[0005] し力しながら最近、液晶カラフィルターに見られる様な機能性微粒子顔料を高度に 分散かつ安定化させ、多様化する複雑な現像パターンをより高速でかつ正確に形成 させようとする要求が高まっている。し力しこの様な微粒子顔料を高度に分散かつ安 定化させる事は困難であり、これら顔料が有する本来の性能を充分引き出せていな いのが現状である。また、高度な分散性を得るために多量の分散剤を必要とし、その 結果として硬化性能等のその他特性を低下させる要因となっている。  Recently, however, there has been a demand for highly dispersed and stabilized functional fine particle pigments such as those found in liquid crystal color filters so that diversified complex development patterns can be formed more quickly and accurately. Is growing. However, it is difficult to highly disperse and stabilize such fine particle pigments, and the actual performances of these pigments are not sufficiently brought out. In addition, a large amount of dispersant is required to obtain a high degree of dispersibility, and as a result, other characteristics such as curing performance are deteriorated.
[0006] 特許文献 1：特開 2003— 292576号公報（実施例 1)  Patent Document 1: Japanese Patent Application Laid-Open No. 2003-292576 (Example 1)
特許文献 2：特開平 7— 103213号公報 (特許請求の範囲）  Patent Document 2: Japanese Patent Laid-Open No. 7-103213 (Claims)
特許文献 3：特開 2006— 16534号公報 (特許請求の範囲）  Patent Document 3: Japanese Unexamined Patent Publication No. 2006-16534 (Claims)
特許文献 4:特開 2002— 322348号公報 (発明の属する技術分野及び従来技術） 発明の開示  Patent Document 4: Japanese Patent Application Laid-Open No. 2002-322348 (Technical Field to which Invention belongs and Prior Art) Disclosure of Invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0007] 本発明の目的は、上記従来技術での問題点、即ち微粒子顔料を高度に分散かつ 安定化させ、同時に活性光線照射により優れた硬化特性と塩基性水溶液による良好 な現像特性が得られる事を可能にする活性光線硬化型榭脂を提供することにある。 課題を解決するための手段 [0007] The object of the present invention is to solve the above-mentioned problems in the prior art, that is, to highly disperse and stabilize the fine particle pigment, and at the same time, to obtain excellent curing characteristics by actinic ray irradiation and good development characteristics by a basic aqueous solution. The object is to provide an actinic ray curable resin that makes it possible. Means for solving the problem
[0008] 本発明者等は特にある種の構造を有するハイパーブランチポリマーが微粒子顔料 の分散性優れている事に着目し、鋭意検討した結果、本発明に到達した。すなわち 本発明は以下のハイパーブランチ構造を有したポリマーである。  [0008] The inventors of the present invention have arrived at the present invention as a result of intensive investigations, particularly focusing on the fact that hyperbranched polymers having a certain structure are excellent in the dispersibility of fine particle pigments. That is, the present invention is a polymer having the following hyperbranched structure.
[0009] (1)脂肪族単量体を繰り返し単位とするハイパーブランチ構造を有し数平均分子量 が 2000以上 4000未満であるポリエステルに、グリシジル基或 、は無水酸基を有す る単環式芳香族化合物、およびグリシジル基或いは無水酸基を有する不飽和結合 含有ィ匕合物が反応して得られたハイパーブランチポリマーであり、ノ、ィパーブランチ ポリマー全体における前記単環式芳香族化合物により導入された芳香環の濃度が 3 OOOeqZton以上 5000eqZton未満である活性光線硬化型ハイパーブランチポリ マー。 [0009] (1) A hyperbranched structure having a repeating unit of an aliphatic monomer and a number average molecular weight It is obtained by reacting a polyester having a molecular weight of 2000 or more and less than 4000 with a monocyclic aromatic compound having a glycidyl group or a hydroxyl group and an unsaturated bond-containing compound having a glycidyl group or a hydroxyl group. An actinic ray curable hyperbranched polymer, wherein the concentration of the aromatic ring introduced by the monocyclic aromatic compound in the entire hyperbranched polymer is 3 OOOeqZton or more and less than 5000eqZton.
[0010] (2)脂肪族単量体が下記化学式 1)で表される（1)に記載の活性線硬化型ハイパー ブランチポリマー。  [0010] (2) The actinic radiation curable hyperbranched polymer according to (1), wherein the aliphatic monomer is represented by the following chemical formula 1).
化学式 1) KR' [ (R) L]  Chemical formula 1) KR '[(R) L]
m n  m n
R：炭素数 20未満の 2価の脂肪族炭化水素基  R: Divalent aliphatic hydrocarbon group having less than 20 carbon atoms
R'：炭素数 20未満の (n+ 1)価の脂肪族炭化水素基、或いは R"N (R" :炭素 数 20未満の 2価の脂肪族炭化水素基)で示される基  R ′: an (n + 1) -valent aliphatic hydrocarbon group having less than 20 carbon atoms, or a group represented by R ″ N (R ”: a divalent aliphatic hydrocarbon group having less than 20 carbon atoms)
K、 L:互いに異なるエステル結合形成性官能基  K, L: different ester bond-forming functional groups
m: 0又は 1  m: 0 or 1
n: 2以上の整数  n: An integer greater than or equal to 2
発明の効果  The invention's effect
[0011] 本発明のハイパーブランチポリマーは特定濃度の芳香環を有している事で顔料分 散性に優れ、また特定の脂肪族ポリエステル骨格力もなるハイパーブランチ構造を 有する事で一度分散した顔料粒子の凝集が抑制され、分散状態が安定に維持され る。加えて分子末端に結合した多量の不飽和結合により、活性光線が照射された際 に効率よく硬化反応が進行する。  [0011] The hyperbranched polymer of the present invention is excellent in pigment dispersibility by having an aromatic ring at a specific concentration, and pigment particles once dispersed by having a hyperbranch structure having a specific aliphatic polyester skeleton force. Aggregation is suppressed, and the dispersed state is maintained stably. In addition, the curing reaction proceeds efficiently when actinic rays are irradiated due to the large amount of unsaturated bonds bound to the molecular ends.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0012] 本来ハイパーブランチポリマーという用語は Kimと Websterが、繰り返し単位の規則 性を有する多分岐ポリマーに対して名付けた言葉であり（Polym. Prepr. , 29 (198 8) 310参照）、 1分子中に互いに反応出来る 2種類の置換基を合計 3個以上持つ化 合物の自己縮合により合成される多分基高分子と定義される。本発明において述べ るハイパーブランチポリマーは、上記 Kimと Websterが提唱した用語に当てはまるも のである。この様な多分岐ポリマーとしては従来、ポリエステル系、ポリアミド系、ポリウ レタン系、ポリエーテノレ系、ポリエーテノレスノレホン、ポリカーボネート系など、種々のタ イブが合成されている。 [0012] Originally, the term hyperbranched polymer was named by Kim and Webster for a hyperbranched polymer with regularity of repeating units (see Polym. Prepr., 29 (198 8) 310), and one molecule It is defined as a possibly high-molecular-weight polymer synthesized by self-condensation of compounds with a total of 3 or more of two kinds of substituents that can react with each other. The hyperbranched polymer described in the present invention applies to the terms proposed by Kim and Webster. Conventionally, such multi-branched polymers have been polyester-based, polyamide-based, A variety of types such as retane, polyetherolene, polyetherolonephone and polycarbonate are synthesized.
[0013] これらハイパーブランチポリマーの榭状に伸びた分子末端には多量の官能基が密 集して存在している構造を採っており、これら反応性官能基を利用して種々の機能 性官能基を多量にかつ密に導入する事が可能である。  [0013] These hyperbranched polymers have a structure in which a large amount of functional groups are densely present at the molecular ends extending in a cage shape, and various functional functionalities are utilized using these reactive functional groups. It is possible to introduce groups in large quantities and densely.
[0014] 本発明の榭脂の場合、アタリレート基、メタタリレート基を分子末端に多量に導入さ せる事で、活性光線照射により、高効率で分子間の架橋反応が密に起こる。力 tlえて、 ノ、ィパーブランチポリマーは通常の線状構造を有するポリマーに比較し、溶液状態 では分子間の絡み合 、が少なくなるため溶液粘度が低くなる。結果としてレジスト塗 料を調製する上でハイソリッドィ匕が容易となる。  [0014] In the case of the resin of the present invention, by introducing a large amount of attalylate groups and metatalylate groups at the molecular ends, cross-linking reactions between molecules occur with high efficiency by irradiation with actinic rays. Compared with a polymer having a normal linear structure, the hyper-branched polymer has a lower solution viscosity in the solution state because there is less entanglement between molecules. As a result, high solids can be easily prepared in preparing the resist coating.
[0015] 本発明のハイパーブランチポリマーのコアとなる榭脂は脂肪族単量体を繰り返し単 位とし、ノ、ィパーブランチ構造を有するポリエステルであることが、耐熱性、他榭脂成 分や添加物成分との相溶性、及び汎用溶剤への溶解性の観点から特に好ましぐそ れら化合物の構造を表す一般式は例えばィヒ学式 1で表される。  [0015] The resin used as the core of the hyperbranched polymer of the present invention is a polyester having an aliphatic monomer as a repeating unit and having a no- and hyper-branched structure, heat resistance, other resin components and additives. A general formula representing the structure of such a compound that is particularly preferred from the viewpoint of compatibility with the components and solubility in a general-purpose solvent is represented by Formula 1 for example.
化学式 1) KR' [ (R) L]  Chemical formula 1) KR '[(R) L]
m n  m n
R：炭素数 20未満の 2価の脂肪族炭化水素基  R: Divalent aliphatic hydrocarbon group having less than 20 carbon atoms
R'：炭素数 20未満の (n+ 1)価の脂肪族炭化水素基、或いは R"N (R" :炭素 数 20未満の 2価の脂肪族炭化水素基)で示される基  R ′: an (n + 1) -valent aliphatic hydrocarbon group having less than 20 carbon atoms, or a group represented by R ″ N (R ”: a divalent aliphatic hydrocarbon group having less than 20 carbon atoms)
K、 L:互いに異なるエステル結合形成性官能基  K, L: different ester bond-forming functional groups
m: 0又は 1  m: 0 or 1
n: 2以上の整数  n: An integer greater than or equal to 2
[0016] 上記化学式 1で示される化合物としては 2, 2 ジメチロールプロピオン酸、 2, 2— ジメチロールブタン酸、 5 ヒドロキシシクロへキサン一 1, 3 ジカルボン酸、 1, 3— ジヒドロキシ 5 カルボキシシクロへキサン、 5—（2 ヒドロキシエトキシ）シクロへキ サン 1, 3 ジカルボン酸、 1, 3—（2 ヒドロキシエトキシ）ー5 カルボキシシクロ へキサン、 N, N—ビス（メチルプロピオネート）モノエタノールァミン、 N— (メチルプロ ピオネート)ジエタノールァミン等が挙げられる力 これら原料化合物としての汎用性 及び重合反応工程の簡便さ、及び溶剤溶解性の面からは、 2, 2—ジメチロールプロ ピオン酸、 2, 2—ジメチロールブタン酸が好ましい。 [0016] The compound represented by the above chemical formula 1 includes 2,2 dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 5-hydroxycyclohexane-1,3-dicarboxylic acid, 1,3-dihydroxy-5 carboxycyclohexanone. Xanthone, 5- (2 hydroxyethoxy) cyclohexane 1,3 dicarboxylic acid, 1,3- (2 hydroxyethoxy) -5 carboxycyclohexane, N, N-bis (methylpropionate) monoethanolamine N- (methylpropionate) diethanolamine, etc. From the viewpoint of versatility as these raw material compounds, simplicity of the polymerization reaction process, and solvent solubility, 2, 2-dimethylol pro Pionic acid and 2,2-dimethylolbutanoic acid are preferred.
[0017] 本発明のハイパーブランチポリマーは、例えば第 1段階で上記 KR，[ (R) L]型ィ匕 [0017] The hyperbranched polymer of the present invention is, for example, the above-mentioned KR, [(R) L] type
m n 合物を縮合させ、末端に多量の水酸基或いはカルボン酸基、或いはこれらの誘導体 官能基を有するハイパーブランチポリマーを形成した後、第 2段階でこれら分子末端 の官能基にグリシジル基または無水酸基を有する単環式芳香族化合物、およびダリ シジル基または無水酸基を有する不飽和結合含有化合物等を付加させて得ることが できる。  After condensing the mn compound to form a hyperbranched polymer having a large amount of hydroxyl or carboxylic acid groups or derivatives or functional groups thereof at the terminal, in the second step, glycidyl groups or hydroxyl-free groups are added to these molecular terminal functional groups. It can be obtained by adding a monocyclic aromatic compound having an unsaturated bond and a compound containing an unsaturated bond having a darisidyl group or a hydroxyl group-free.
[0018] 上記第 1段階の反応は上記 KR' [ (R) L]型化合物を単独で縮合反応触媒の存  [0018] In the first stage reaction, the above KR ′ [(R) L] type compound is used alone for the presence of a condensation reaction catalyst.
m n  m n
在下に反応させても良いし、多価ヒドロキシ化合物や多価カルボン酸化合物、或いは それらを合わせ持つ化合物をノ、ィパーブランチポリマー分子の分岐点として用いて も良 、。上記多価ヒドロキシィ匕合物としてはポリエステル榭脂原料として汎用の種々 グリコール化合物やトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリト ール等の 3官能以上の水酸基含有ィ匕合物が挙げられる。また、多価カルボン酸化合 物としては同様にポリエステル榭脂原料として汎用の種々二塩基酸、トリメリット酸、ピ ロメリット酸、ベンゾフエノンテトラカルボン酸等の 3官能以上のカルボン酸化合物が 挙げられる。更には水酸基とカルボン酸基を合わせ持った化合物例として、グリコー ル酸、ヒドロキシピバリン酸、 3—ヒドロキシー2—メチルプロピオン酸、乳酸、グリセリン 酸、リンゴ酸、クェン酸等が挙げられる。  The reaction may be carried out in the presence, or a polyvalent hydroxy compound, a polyvalent carboxylic acid compound, or a compound having both of them may be used as the branching point of the hyperperpendicular polymer molecule. Examples of the polyhydric hydroxy compound include various general-purpose glycol compounds as a polyester resin raw material, and tri- or higher functional hydroxyl group-containing compounds such as trimethylolpropane, pentaerythritol, and dipentaerythritol. In addition, examples of the polyvalent carboxylic acid compound include trivalent or higher functional carboxylic acid compounds such as various dibasic acids, trimellitic acid, pyromellitic acid, and benzophenone tetracarboxylic acid, which are general raw materials for polyester resin. . Furthermore, examples of the compound having both a hydroxyl group and a carboxylic acid group include glycolic acid, hydroxypivalic acid, 3-hydroxy-2-methylpropionic acid, lactic acid, glyceric acid, malic acid, and citrate.
[0019] 本発明のハイパーブランチポリマー分子の分岐点となる化合物としては上記以外 に、二塩基酸成分とグリコール成分の縮合反応で得られる線状のポリエステルオリゴ マーやこれらに 3官能以上の多価カルボン酸や多価ヒドロキシィ匕合物を共重合した 分岐型ポリエステルオリゴマーを用いても良!、。  [0019] In addition to the above, the compound that serves as a branching point of the hyperbranched polymer molecule of the present invention is a linear polyester oligomer obtained by a condensation reaction of a dibasic acid component and a glycol component, or a trivalent or higher polyvalent polyvalent compound. It is also possible to use a branched polyester oligomer copolymerized with a carboxylic acid or a polyhydric hydroxy compound!
[0020] 上記分岐点となりうる線状、或いは分岐型ポリエステルオリゴマーの構成原料として は汎用の種々二塩基酸ゃグリコールィヒ合物、或いは 3官能以上の多価カルボン酸 や多価アルコールィ匕合物を用いる事ができる。二塩基酸ィ匕合物としては、コハク酸、 アジピン酸、ァゼライン酸、セバシン酸、ドデカン酸等の脂肪族系二塩基酸、テレフタ ル酸、イソフタル酸、オルソフタル酸、 1, 2—ナフタレンカルボン酸、 1, 6—ナフタレ ンジカルボン酸等の芳香族系-塩基酸、或いは 1, 2—シクロへキサンジカルボン酸 、 1, 4ーシクロへキサンジカルボン酸、 4ーメチルー 1, 2 シクロへキサンジカルボン 酸等の脂環族二塩基酸が挙げられるが、耐熱特性から、好ましくはテレフタル酸、ィ ソフタル酸、オルソフタル酸、 1, 2 ナフタレンカルボン酸、 1, 6 ナフタレンジカル ボン酸、特に好ましくはテレフタル酸、 1, 2 ナフタレンカルボン酸、 1, 6 ナフタレ ンジカルボン酸である。 [0020] As a constituent material of the linear or branched polyester oligomer that can serve as the branching point, various general dibasic acid glycol glycol compounds, or trifunctional or higher polyvalent carboxylic acids and polyhydric alcohol compounds are used. Can be used. Dibasic acid compounds include aliphatic dibasic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,2-naphthalenecarboxylic acid Aromatic-basic acids such as 1,6-naphthalene dicarboxylic acid or 1,2-cyclohexanedicarboxylic acid 1,4-cyclohexanedicarboxylic acid, 4-methyl-1,2 cyclohexanedicarboxylic acid, and the like. Among them, terephthalic acid, isophthalic acid, orthophthalic acid, 1 1, 2 Naphthalene carboxylic acid, 1, 6 naphthalene dicarboxylic acid, particularly preferably terephthalic acid, 1, 2 naphthalene carboxylic acid, 1, 6 naphthalene dicarboxylic acid.
また、グリコール成分としてはエチレングリコール、 1, 2 プロピレングリコール、 1, 3 —プロピレングリコール、 1, 2 ブチレングリコール、 1, 3 ブチレングリコール、 2, 3 ブチレングリコール、 1, 4ーブチレングリコール、 2—メチルー 1, 3 プロピレング リコール、ネオペンチルグリコール、 3—メチルー 1, 5 ペンタンジオール、 2, 2, 4 トリメチルー 1, 3 ペンタンジオール、 2, 4 ジェチルー 1, 5 ペンタンジオール 、 2 ェチルー 1, 3 へキサンジオール、 2, 2 ジメチルー 3 ヒドロキシプロピル 2' , 2，—ジメチルー 3 ヒドロキシプロパネート、 2— nブチル—2 ェチル—1, 3— プロパンジオール、 3 ェチルー 1, 5 ペンタンジオール、 3 プロピル 1, 5 ぺ ンタンジオール、 2, 2 ジェチルー 1, 3 プロパンジオール、 3—ォクチルー 1, 5— ペンタンジオール等の脂肪族系ジオール類や 1, 3 ビス（ヒドロキシメチル）シクロへ キサン、 1, 4 ビス（ヒドロキシメチル）シクロへキサン、 1, 4 ビス（ヒドロキシェチル） シクロへキサン、 1, 4 ビス（ヒドロキシプロピル）シクロへキサン、 1, 4 ビス（ヒドロキ シメトキシ）シクロへキサン、 1, 4 ビス（ヒドロキシエトキシ）シクロへキサン、 2, 2ビス（ 4 ヒドロキシメトキシシクロへキシル）プロパン、 2, 2 ビス（4ヒドロキシエトキシシクロ へキシル）プロパン、ビス（4 -ヒドロキシシクロへキシル）メタン、 2, 2 ビス（4 -ヒドロ キシシクロへキシル）プロパン、 3 (4) , 8 (9)—トリシクロ [5. 2. 1. 02' 6]デカンジメタノ ール等の脂環族系グリコール類、或いはビスフエノール Aのエチレンオキサイドゃプ ロピレンオキサイド付加物等の芳香族系グリコール類が挙げられるがこれらのうち、 2 , 2 -ジメチル 3 ヒドロキシプロピル 2，， 2，一ジメチル 3 ヒドロキシプロパネ ート、 2, 2 ビス（4 ヒドロキシシクロへキシル）プロパン、 3 (4) , 8 (9)—トリシクロ [5 . 2. 1. 02' 6]デカンジメタノール、およびビスフエノール Aのエチレンオキサイドゃプ ロピレンオキサイド付加物が得られるポリエステル榭脂の耐熱特性と原料としての汎 用性力も好ましい。 [0022] 更に上記 3官能以上の多価カルボン酸や多価アルコールィ匕合物としては、トリメリッ ト酸ゃピロメリット酸、ベンゾフエノンテトラカルボン酸、グリセリン、トリメチロールプロパ ン、ペンタエリスリトール等が挙げられる。 The glycol components include ethylene glycol, 1,2 propylene glycol, 1, 3 -propylene glycol, 1,2 butylene glycol, 1,3 butylene glycol, 2,3 butylene glycol, 1,4-butylene glycol, 2-methyl- 1,3 propylene glycol, neopentyl glycol, 3-methyl-1,5 pentanediol, 2,2,4 trimethyl-1,3 pentanediol, 2,4 jetyl 1,5 pentanediol, 2 ethyl-1,3 hexanediol 2, 2 Dimethyl-3 hydroxypropyl 2 ', 2, —Dimethyl-3 hydroxypropanoate, 2-nbutyl-2 ethyl-1, 3-propanepropanediol, 3 ethyl-1,5 pentanediol, 3 propyl 1,5 pentane Diol, 2, 2 Jetyl 1,3 Propanediol, 3-Octyl-1,5-pentanediol, etc. Aliphatic diols, 1,3 bis (hydroxymethyl) cyclohexane, 1,4 bis (hydroxymethyl) cyclohexane, 1,4 bis (hydroxyethyl) cyclohexane, 1,4 bis (hydroxypropyl) ) Cyclohexane, 1,4 bis (hydroxymethoxy) cyclohexane, 1,4 bis (hydroxyethoxy) cyclohexane, 2,2 bis (4 hydroxymethoxycyclohexyl) propane, 2,2 bis (4 hydroxy) Ethoxycyclohexyl) propane, bis (4-hydroxycyclohexyl) methane, 2, 2 bis (4-hydroxycyclohexyl) propane, 3 (4), 8 (9) —Tricyclo [5. 2. 1. 0 2 '6] alicyclic glycols such as Dekanjimetano Lumpur, or aromatic glycols such as ethylene oxide Ya profile propylene oxide adduct of bisphenol a Among them, 2, 2-dimethyl 3 hydroxypropyl 2, 2, 1, 1 dimethyl 3 hydroxypropanate, 2, 2 bis (4 hydroxycyclohexyl) propane, 3 (4), 8 ( 9) —Tricyclo [5. 2. 1. 0 2 ' 6 ] decane dimethanol and polyester resin that can be used for the addition of bisphenol A ethylene oxide propylene oxide adduct. preferable. [0022] Further, the trifunctional or higher polyhydric carboxylic acid and polyhydric alcohol compound include trimellitic acid pyromellitic acid, benzophenone tetracarboxylic acid, glycerin, trimethylolpropan, pentaerythritol and the like. Can be mentioned.
[0023] 上記第 1段階の反応は縮合反応で生成する縮合水をトルエンゃキシレンにより共 沸脱水させる事で、或いは反応系内に不活性ガスを吹き込み不活性ガスと共に縮合 反応で生成した水やモノアルコールを反応系外に吹き出す又は減圧下に溜去する 事で進められる。反応に用いられる触媒としては通常のポリエステル榭脂重合触媒 同様、チタン系、錫系、アンチモン系、亜鉛系、ゲルマニウム系等の種々金属化合物 や p―トルエンスルホン酸や硫酸等の強酸ィ匕合物を用いる事が出来る。  [0023] In the first stage reaction, the condensed water produced by the condensation reaction is azeotropically dehydrated with toluene-xylene, or the inert gas is blown into the reaction system and the water produced by the condensation reaction together with the inert gas. The monoalcohol is blown out of the reaction system or distilled off under reduced pressure. The catalyst used for the reaction is the same as a normal polyester resin polymerization catalyst, as well as various metal compounds such as titanium, tin, antimony, zinc and germanium, and strong acid compounds such as p-toluenesulfonic acid and sulfuric acid. Can be used.
[0024] 次いで第 2段階の反応では第 1段階で得られた水酸基末端又はカルボキシル基末 端を多量に有したノヽィパーブランチポリマーのコア骨格にグリシジル基または無水酸 基を有する単環式芳香族化合物およびグリシジル基または無水酸基を有する不飽 和結合含有化合物が付加される。具体的に用いられる化合物としては末端が水酸基 のハイパーブランチポリマーの場合、無水トリメリット酸、無水フタル酸、ビフエ-ルテト ラカルボン酸二無水物、ベンゾフヱノンテトラカルボン酸等の単環式芳香族化合物、 1, 2, 5, 6—テトラヒドロキシ無水フタル酸、 1, 2, 5, 6—テトラヒドロキシ 1 メチル 無水フタル酸、無水マレイン酸、無水ィタコン酸、ドデセ-ル無水コハク酸、オタテ- ル無水コハク酸等の不飽和結合含有無水酸化合物、或いは水酸基をカルボキシル 基に置き換えるため、コハク酸無水物、プロピオン酸無水物、へキサヒドロ無水フタル 酸、メチルへキサヒドロ無水フタル酸、を付加させてもよい。これら化合物のうち、ビフ ェ -ルテトラカルボン酸二無水物、ベンゾフヱノンテトラカルボン酸は無水酸基を分子 中に 2個有しており、多量に反応させた場合、ポリマーがゲルィ匕することがある。一方 、 1分子中に無水酸基とカルボキシル基を 1個ずつ有する無水トリメリット酸は無水酸 基が水酸基と反応すると、合計 2個のカルボキシル基がポリマー末端に生成する事 になり、末端結合基数を更に増やす事が出来る。この意味で無水トリメリット酸が最も 好ましい。  [0024] Next, in the second-stage reaction, a monocyclic aromatic compound having a glycidyl group or an anhydride group in the core skeleton of the no-perbranched polymer having a large amount of hydroxyl terminal or carboxyl group terminal obtained in the first stage. And an unsaturated bond-containing compound having a glycidyl group or a hydroxyl-free group are added. Specific examples of compounds used in the case of a hyperbranched polymer having a hydroxyl group at the end include monocyclic aromatics such as trimellitic anhydride, phthalic anhydride, biphenyltetracarboxylic dianhydride, and benzophenone tetracarboxylic acid. Compound, 1, 2, 5, 6-tetrahydroxyphthalic anhydride, 1, 2, 5, 6-tetrahydroxy 1 methyl phthalic anhydride, maleic anhydride, itaconic anhydride, dodecyl succinic anhydride, otate An unsaturated bond-containing anhydride compound such as succinic anhydride, or succinic anhydride, propionic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride may be added to replace the hydroxyl group with a carboxyl group. Good. Of these compounds, biphenyltetracarboxylic dianhydride and benzophenone tetracarboxylic acid have two hydroxyl-free groups in the molecule, and the polymer will gel when reacted in large quantities. There is. On the other hand, trimellitic anhydride, which has one hydroxyl group and one carboxyl group in one molecule, generates a total of two carboxyl groups at the polymer end when the anhydride group reacts with the hydroxyl group. You can increase it further. In this sense, trimellitic anhydride is most preferable.
[0025] これら水酸基と無水酸化合物との反応により生成するカルボキシル基に更にフエ二 ルグリシジルエーテル、 4 フルオローフエ-ルグリシジルエーテル、 4ーメトキシーフ ェニルダリシジルエーテルのようなグリシジル基を含有する単環式芳香族化合物、グ リシジル (メタ）アタリレート、ァリルグリシジルエーテル、 4—ヒドロキシブチルアタリレー トグリシジルエーテル等の不飽和結合とグリシジル基を含有する化合物を反応させる 事も出来る。これら化合物の内、汎用性の面力 フエ-ルグリシジルエーテル、グリシ ジルアタリレート、グリシジルメタタリレート、 4ーヒドロキシブチルアタリレートグリシジル エーテルが好ましい。 [0025] In addition to the carboxyl group formed by the reaction of these hydroxyl groups with the anhydride compound, phenyl glycidyl ether, 4-fluoro-phenyl glycidyl ether, 4-methoxy thiol Unsaturated bonds and glycidyl groups such as monocyclic aromatic compounds containing a glycidyl group such as enyldaricidyl ether, glycidyl (meth) atalylate, allyl glycidyl ether, 4-hydroxybutyl atelate glycidyl ether, etc. It is also possible to react the contained compounds. Of these compounds, versatile surface powers such as phenol glycidyl ether, glycidyl atylate, glycidyl metatalylate and 4-hydroxybutyl atylate glycidyl ether are preferred.
[0026] また、更に上記カルボキシル基とグリシジル基の反応により生成する水酸基に上記 無水酸化合物を反応させても良 ヽ。この反応段階で用いられる不飽和結合含有ィ匕 合物としては、反応性と汎用性の面から、無水マレイン酸、 1, 2, 5, 6-テトラヒドロキ シ無水フタル酸が好まし 、。  [0026] Further, the above anhydride compound may be further reacted with a hydroxyl group produced by the reaction of the above carboxyl group and glycidyl group. The unsaturated bond-containing compound used in this reaction step is preferably maleic anhydride or 1,2,5,6-tetrahydroxyphthalic anhydride from the viewpoint of reactivity and versatility.
[0027] 一方、末端がカルボンキシル基の場合には上記グリシジル基を含有する化合物を 反応させる事が出来る。また更にここで生成する水酸基に対し、上記無水酸化合物 を反応させても良い。  On the other hand, when the terminal is a carboxyxyl group, the compound containing the glycidyl group can be reacted. Furthermore, the acid anhydride compound may be reacted with the hydroxyl group produced here.
[0028] 本発明の活性光線硬化型ハイパーブランチポリマーには、このポリマーが有する優 れた顔料分散性、及び分散安定性を損ねな 、範囲で紫外線に対する感度をより向 上させる目的で、紫外線吸収能のある骨格を有する無水酸化合物、或いはグリシジ ルイ匕合物を反応付加させても良い。この目的のために用いられる具体的化合物とし ては例えば、ベンゾフエノンテトラカルボン酸二無水物、アントラセンー9ーグリシジル エーテル、 9, 9—ビス（4 -フエ-ルグリシジルエーテル）フルオレンの様なベンゾフ ェノン、アントラセン、フルオレン等の骨格を有する化合物が挙げられるがこれらのう ち、汎用性からは。ベンゾフエノンテトラカルボン酸二無水物が好ましい。  The actinic ray curable hyperbranched polymer of the present invention absorbs ultraviolet rays for the purpose of further improving the sensitivity to ultraviolet rays in a range without impairing the excellent pigment dispersibility and dispersion stability of the polymer. An acid anhydride compound having a functional skeleton or a glycidyl complex may be reacted and added. Specific compounds used for this purpose include, for example, benzophenone tetracarboxylic dianhydride, anthracene-9-glycidyl ether, benzophenone such as 9,9-bis (4-phenylglycidyl ether) fluorene. And compounds having a skeleton such as anthracene and fluorene. Among these, from the viewpoint of versatility. Benzophenone tetracarboxylic dianhydride is preferred.
[0029] 本発明の榭脂の合成に際しては上記、水酸基と無水酸基の反応、及びカルボキシ ル基とグリシジル基の反応、の何れの反応方法をどの様な順序'組み合わせで用い ても構わな 、。これらの反応は水酸基とカルボキシル基或いはそのエステル誘導体と の反応に比較し、よりマイルドな条件で反応が高収率に進行する。この事は反応性 に富むハイパーブランチ化合物の変性には適しており、反応副成物の生成や架橋 反応による分子量分布の増大、或いはゲルイ匕と!、つた副反応が起こりにく 、。  [0029] In synthesizing the resin of the present invention, any of the above reaction methods of hydroxyl group-free hydroxyl reaction and carboxyl group-glycidyl group reaction may be used in any order. . These reactions proceed in higher yields under milder conditions than those of hydroxyl groups and carboxyl groups or ester derivatives thereof. This is suitable for denaturation of highly reactive hyperbranched compounds, and it is difficult for side reactions to occur due to the formation of reaction by-products and an increase in molecular weight distribution due to cross-linking reactions, or gelling.
[0030] 上記反応の組み合わせにより得られる本発明の榭脂中、単環式芳香族化合物によ つて導入された芳香環濃度は 3000eqZton以上 5000eqZton未満である。 3000 eqZton未満では優れた顔料分散性能が得られない。また、末端に存在する反応点 数から、 5000eqZtonを越えて導入すると、活性光線硬化性能に寄与する不飽和 結合の導入量が制限され、充分な活性光線硬化性能が得られなくなる。また、ナフタ レン構造、アントラセン構造、フルオレン構造等を有する多環式芳香族化合物を多量 に導入すると、榭脂全体の溶剤溶解性が低下し、結果として顔料分散性能が低下し てしまう。これら多環式芳香族化合物を構成する芳香環は本発明にお 、て「芳香環 の濃度」には加算されない。なおここで言う芳香環の濃度はハイパーブランチポリマ 一 lton中に含まれる単環式芳香環のモル数を表す。 [0030] In the resin of the present invention obtained by a combination of the above reactions, a monocyclic aromatic compound is used. Therefore, the concentration of the introduced aromatic ring is not less than 3000eqZton and less than 5000eqZton. If it is less than 3000 eqZton, excellent pigment dispersion performance cannot be obtained. In addition, if it is introduced in excess of 5000 eqZton from the number of reaction points present at the terminal, the amount of unsaturated bonds that contribute to actinic radiation curing performance is limited, and sufficient actinic radiation curing performance cannot be obtained. In addition, when a large amount of polycyclic aromatic compounds having a naphthalene structure, an anthracene structure, a fluorene structure, etc. are introduced, the solvent solubility of the entire resin decreases, and as a result, the pigment dispersion performance decreases. The aromatic rings constituting these polycyclic aromatic compounds are not added to the “concentration of aromatic rings” in the present invention. The concentration of aromatic rings referred to here represents the number of moles of monocyclic aromatic rings contained in one lton of hyperbranched polymer.
[0031] 本発明のハイパーブランチポリマーにおいて、脂肪族単量体繰り返し単位とするハ ィパーブランチ構造を有するポリエステル (ノ、ィパーブランチコア部）の数平均分子 量は 2000以上 4000未満である。数平均分子量が 2000未満では初期の顔料分散 性は得られるものの、充分な分散安定性が得られず、保存中に顔料粒子の凝集が起 こることがある。一方、本発明の榭脂に用いられる脂肪族ポリエステル骨格のハイパ 一ブランチ化合物は数平均分子量が 4000を越えると溶融粘度が高くなり、均一な反 応コントロールが困難になり、安定した品質が得られなくなる場合がある。 [0031] In the hyperbranched polymer of the present invention, the number average molecular weight of the polyester (no, hyperbranched core portion) having a hyperbranched structure as an aliphatic monomer repeating unit is 2000 or more and less than 4000. If the number average molecular weight is less than 2000, initial pigment dispersibility can be obtained, but sufficient dispersion stability cannot be obtained, and pigment particles may aggregate during storage. On the other hand, the hyper-branched compound of the aliphatic polyester skeleton used in the resin of the present invention has a high melt viscosity when the number average molecular weight exceeds 4,000, and it becomes difficult to control uniform reaction, and stable quality is obtained. It may disappear.
[0032] 本発明の活性光線硬化型ハイパーブランチポリマーの有する不飽和結合濃度は 使用される用途、配合処方により適当な濃度があるため特に限定されないが少なくと も 500eqZton以上が好ま 、。 500eqZton未満では充分な活性光線硬化性が得 られないことがある。また 5000eqZtonを越えると、硬化反応収縮により、基材との密 着性が低下してしまうことがある。なお、ここで言う不飽和結合基濃度は榭脂 It中に 含まれる二重結合のモル数で表す。  [0032] The unsaturated bond concentration of the actinic ray curable hyperbranched polymer of the present invention is not particularly limited because it has an appropriate concentration depending on the intended use and formulation, but at least 500 eqZton is preferred. If it is less than 500eqZton, sufficient actinic ray curability may not be obtained. If it exceeds 5000 eqZton, the adhesion to the substrate may decrease due to shrinkage of the curing reaction. In addition, the unsaturated bond group density | concentration said here is represented by the number-of-moles of the double bond contained in the resin It.
[0033] 本発明の活性光線硬化型ハイパーブランチポリマーの有する酸価もまた、各用途 や使用条件に対応し、適当な濃度に調製されるべきであるが、アルカリ水による現像 特性を得るためには 500eq/ton以上であることが好ましく、より好ましくは 800eq/ ton以上であり、 3000eqZtonを越えると、榭脂の親水性が高くなりすぎ、硬化反応 物の耐水性が低下する場合がある。  [0033] The acid value of the actinic radiation curable hyperbranched polymer of the present invention should also be adjusted to an appropriate concentration corresponding to each application and use conditions. In order to obtain development characteristics with alkaline water, Is preferably 500 eq / ton or more, more preferably 800 eq / ton or more. If it exceeds 3000 eq Zton, the hydrophilicity of the resin is too high, and the water resistance of the cured reaction product may decrease.
[0034] 本発明の活性光線硬化型ハイパーブランチポリマー合成反応条件は特に限定され ないが、好ましくは、温度を 60°Cから 150°Cの範囲とし、この温度範囲で反応が完了 するように反応時間を適宜設定して行うのがよい。この際、反応促進のために反応触 媒を添加したり、あるいは、重合反応や重合進行によるゲルィ匕等を起こすことのない よう、重合禁止剤や分子状酸素を添加したりすることも有効である。 [0034] The actinic ray curable hyperbranched polymer synthesis reaction conditions of the present invention are not particularly limited. However, preferably, the temperature is set in the range of 60 ° C to 150 ° C, and the reaction time is appropriately set so that the reaction is completed within this temperature range. At this time, it is also effective to add a reaction catalyst to accelerate the reaction, or to add a polymerization inhibitor or molecular oxygen so as not to cause gelation due to polymerization reaction or progress of polymerization. is there.
[0035] 反応触媒としては、トリェチルァミン、ベンジルジメチルァミン等のアミン類;テトラメチ ルアンモ -ゥムクロライド、トリェチルベンジルアンモ -ゥムクロライド等の四級アンモ -ゥム塩； 2—ェチル 4—イミダゾール等のイミダゾール類、アミド類；ピリジン類；トリフ ェ-ノレホスフィン等のホスフィン類；テトラフエ-ノレホスホ-ゥムブロマイド等のホソホ- ゥム塩；スルホ -ゥム塩；スルホン酸類；ォクチル酸亜鉛等の有機金属塩等が挙げら れる。 [0035] Reaction catalysts include amines such as triethylamine and benzyldimethylamine; quaternary ammonium salts such as tetramethylammonium chloride and triethylbenzylammonium chloride; imidazoles such as 2-ethyl 4-imidazole and the like. Amides; pyridines; phosphines such as tri-phenol phosphine; fofoform salts such as tetraphenol-phosphophospho-mubromide; sulfo-um salts; sulfonic acids; organometallic salts such as zinc octylate It is
[0036] 重合禁止剤としては、ハイドロキノン、ハイドロキノンモノメチルエーテル、ピロガロー ル、 tーブチルカテコール、フエノチアジン等の公知、慣用の重合禁止剤等が挙げら れる。  [0036] Examples of the polymerization inhibitor include known and conventional polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, and phenothiazine.
[0037] 本発明の活性光線硬化型ハイパーブランチポリマーの合成、あるいは、それを用い た硬化性榭脂組成物には有機溶剤を使用することができる。有機溶剤は、各成分を 均一に溶解、もしくは分散させるに足る量で用いられる。活性光線硬化型ハイパーブ ランチポリマーの合成における固形分濃度は通常、 10〜90重量％、好ましくは 20〜 70重量％である。また、硬化性榭脂組成物中の固形分濃度は、 5〜50重量％、好ま しくは 10〜40%重量％である。  [0037] An organic solvent can be used in the synthesis of the actinic ray curable hyperbranched polymer of the present invention, or in the curable resin composition using the polymer. The organic solvent is used in an amount sufficient to uniformly dissolve or disperse each component. The solid content concentration in the synthesis of the actinic ray curable hyperbranched polymer is usually 10 to 90% by weight, preferably 20 to 70% by weight. The solid content in the curable resin composition is 5 to 50% by weight, preferably 10 to 40% by weight.
[0038] 有機溶剤としては、トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類 ；セロソルブ、ブチルセ口ソルブ類；カルビトール、ブチルカルビトール等のカルビトー ル類；セロソルブアセテート、カルビトールアセテート、（ジ）プロピレングリコールモノメ チルエーテルアセテート、ブチルセ口ソルブアセテート、カルビトールアセテート、酢 酸ェチル、酢酸ブチル等のエステル類、シクロへキサノン、メチルイソブチルケトン、メ チルェチルケトン等のケトン類；（ジ）エチレングリコールジメチルエーテル、ジェチレ ングリコールモノェチルエーテル、ジプロピレングリコールジェチルエーテル類のェ 一テル類等が挙げられる。この中でも、毒性や、塗布特性の面カゝらエステル系、エー テル系の溶剤を使用することが望ましい。これらの溶媒は 1種または 2種以上を混合 して用いることができ、取り扱いが容易な最適粘度となるよう適当量使用するとよい。 [0038] Examples of the organic solvent include aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve and butylcetosolve; carbitols such as carbitol and butylcarbitol; cellosolve acetate, carbitol acetate, ( Di) propylene glycol monomethyl ether acetate, butylcetosolve acetate, carbitol acetate, esters such as ethyl acetate, butyl acetate, ketones such as cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone; (di) ethylene glycol Examples include ethers such as dimethyl ether, diethylene glycol monoethyl ether, and dipropylene glycol jetyl ether. Of these, it is desirable to use an ester-based or ether-based solvent in terms of toxicity and coating characteristics. These solvents are used alone or in combination of two or more. It is advisable to use an appropriate amount so as to obtain an optimum viscosity that is easy to handle.
[0039] 本発明に用いる活性光線は、波長の長 、ものから順に、可視光線、紫外線、電子線 、 X—線、 ex一線、 β一線、 γ—線等を使用することができる。これらの中で、経済性 及び、効率性の点から、実用的には紫外線が最も好ましい活性光線である。本発明 に用いる紫外線照射に用いる光源としては、太陽光線、ケミカルランプ、低圧水銀灯 、高圧水銀灯、カーボンアーク灯、キノセンランプ、メタルノヽライドランプなどが使用さ れる。紫外線よりも波長の短い前記活性光線は、化学反応性が高ぐ理論的には紫 外線より優れている力 経済性の観点から紫外線が実用的である。  The actinic rays used in the present invention may be visible rays, ultraviolet rays, electron beams, X-rays, ex-lines, β-lines, γ-lines, etc. in order of wavelength. Among these, ultraviolet rays are the most preferable actinic rays in practical use from the viewpoints of economy and efficiency. As the light source used for the ultraviolet irradiation used in the present invention, sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a carbon arc lamp, a kinocene lamp, a metal nitride lamp, or the like is used. The actinic rays having a wavelength shorter than that of ultraviolet rays are theoretically highly chemically reactive and are superior to ultraviolet rays. From the viewpoint of economic efficiency, ultraviolet rays are practical.
[0040] 本発明の活性光線硬化型ハイパーブランチポリマーを用いた硬化性榭脂組成物に おいては光開始剤を配合することができる。光開始剤としては、例えば、クロロアセト フエノン、 4ーフエノキシジクロロアセトフエノン、 4 t—ブチルトリクロロアセトフエノン、 ジェトキシァセトフエノン、 2—ヒドロキシ 2—メチル 1 フエニルプロパン 1ーォ ン、 1— (4—イソプロピルフエ-ル） 2 ヒドロキシ一 2—メチルプロパン一 1—オン、 2 ヒドロキシ一 2—メチルー 1 フエ-ル（4 ドデシル）プロパン一 1 オン、 4— (2 —ヒドロキシエトキシフエニル） 2—ヒドロキシ一 2—メチルプロパン一 1—オン、 1— ヒドロキシシクロへキシルーフエ-ルケトン、 2—メチルー 1一〔4 （メチルチオ）フエ- ル〕 2—モルフォリノプロパン一 1—オン、 2—ベンジル一 2—ジメチルァミノ一 1— ( 4 モルフォリノフエニル）一ブタノン一 1、フエニル 2 ヒドロキシ一 2 プロピルケトン 、ヒドロキシァセトフエノン、 OC—アミノアセトフエノンなどのァセトフエノン類、ベンジル ジメチルケタール（2, 2—ジメトキシ一 1 , 2—ジフエ-ルェタン一 1—オン）などのケタ 一ノレ類、ベンゾイン、ベンゾインメチルエーテル、ベンゾインェチルエーテル、ベンゾ インイソプロピルエーテル、ベンゾインイソブチルエーテル、ベンゾインアルキルエー テル、 α—メチルベンゾインなどのべンゾイン類、ベンゾフエノン、 ο ベンゾィル安息 香酸メチル、 4—フエ-ルペンゾフエノン、 ρ クロルべンゾフエノン、ヒドロキシベンゾ フエノン、 4—ベンゾィル 4 '—メチルージフエ-ルサルファイド、アクリル化べンゾフ ェノン、 3, 3，一ジメチルー 4—メトキシベンゾフエノン、 3, 3 ' , 4, 4 '—テトラ（t—ブチ ルパーォキシカルボ-ル）ベンゾフエノン、 4, 4 ' （ジメチルァミノ）ベンゾフエノン、 p ージメチルァミノべンゾフエノン、〔4 （メチルフエ-ルチオ）フエ-ル〕フエ-ルメタノ ンなどのベンゾフエノン類、 9, 10 アントラキノン、 1 クロルアントラキノン、 2 クロ ルアントラキノン、 2—ェチルアントラキノンなどのアントラキノン類、 2—ヒドロシ一 2— メチルプロピオフエノン、 1— (4—イソプロピルフエ-ル） 2 ヒドロキシ一 2—メチル プロピオフエノンなどのプロピオフエノン類、ジベンゾスベロンなどのスベロン類、ミヒラ ーケトン（4, 4 ビス（ジメチルァミノ）ベンゾフエノン）などのミヒラーケトン類、ベンジ ルなどのベンジル類、ジフヱ-ルジスルフイド、テトラメチルチウラムジスルフイド、 2- クロ口チォキサントン、 2—メチルチオキサントン、イソプロピルチォキサントン、 2, 4— ジクロロチォキサントン、 2, 4 ジメチルチオキサントン、 2, 4 ジェチルチオキサン トン、 2, 4 ジイソプロピノレチォキサントン、 1 クロロー 4 プロポキシチォキサントン などのチォキサントン類などの含ィォゥ化合物類、メチレンブルー、ェォシン、フルォ レセインなどの色素類などがあげられる。 [0040] In the curable resin composition using the actinic ray curable hyperbranched polymer of the present invention, a photoinitiator can be blended. Photoinitiators include, for example, chloroacetophenone, 4-phenoxydichloroacetophenone, 4t-butyltrichloroacetophenone, cetoxyacetophenone, 2-hydroxy 2-methyl 1 phenylpropane 1 ion 1- (4-Isopropyl phenol) 2 Hydroxy 2-methylpropane 1-one, 2-Hydroxy mono 2-Methyl-1-phenol (4 dodecyl) propane 1-one, 4-— (2-Hydroxyethoxy Enyl) 2-hydroxy-1-2-methylpropane-1-one, 1-hydroxycyclohexyl roof ketone, 2-methyl-11- (4- (methylthio) phenol) 2-morpholinopropane-1-one, 2- Benzyl 1-dimethylamino 1- (4 morpholinophenyl) 1-butanone 1-1, phenyl 2 hydroxy 1-2 propylene ketone, hydroxy Acetophenones such as tophenone, OC-aminoacetophenone, ketanols such as benzyl dimethyl ketal (2,2-dimethoxy-1,2-diphenyl-1-one), benzoin, benzoin methyl ether, benzoin Benzyl ethers such as til ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin alkyl ether, α-methylbenzoin, benzophenone, ο-benzoyl methyl benzoate, 4-phenol penzophenone, ρ chlorbenzophenone, hydroxybenzophenone 4-benzoyl 4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3,1-dimethyl-4-methoxybenzophenone, 3, 3 ', 4, 4'-tetra (t-butylperoxycarbo -Le) Benzophenone, 4, 4 ' (Dimethylamino) benzophenone, p-dimethylaminobenzobenzophenone, [4 (methylphenolthio) phenol] phenol methanol 9,10 anthraquinone, 1 chloroanthraquinone, 2 chloroanthraquinone, anthraquinones such as 2-ethyl anthraquinone, 2-hydroxy 2-methylpropiophenone, 1- (4-isopropylphenol ) Propiophenones such as 2-hydroxy-1-2-methylpropiophenone, suberones such as dibenzosuberone, Michler ketones such as Michler's ketone (4,4 bis (dimethylamino) benzophenone), benzyls such as benzyl, diphenyl -Ludisulfide, Tetramethylthiuramdisulfide, 2-Chlorothixanthone, 2-Methylthioxanthone, Isopropylthixanthone, 2,4-Dichlorothixanthone, 2,4 Dimethylthioxanthone, 2,4 Jetylthioxanthone, 2, 4 Diisopropino regio Sandton, 1-chloro-4 propoxy Chio xanthone containing Iou compounds such Chiokisanton such as, methylene blue, Eoshin, and dyes such as Furuo Resein like.
その他に 1 , 1—ジクロロアセトフエノン、 1—ヒドロキシ一シクロへキシル一フエ-ルー ケトン、ァゾビスイソブチル二トリル、ベンゾィルパーオキサイド、ジ—tert—ブチルバ 一オキサイド、 2, 4, 6 トリメチロールべンゾフエノン、 4 メチルベンゾフエノン、 2— ヒドロシ一 2—メチル 1—〔4— (1—メチルビ-ル）フエ-ル〕プロパノン、ビス（2, 6 ージメトキシベンゾィル）ー 2, 4, 4 トリメチルーペンチルフォスフィンオキサイド、 2, 2—ジクロロ一 p フエノキシァセトフエノン、 1—フエ二ノレ一 1, 2—プロパンジオン一 2 (o エトキシカルボニル）ォキシム、 2, 4, 6 トリメチルベンゾィルジフエニルホスフィ ンオキサイド、メチルフエ-ルグリオキシエステル、 9, 10 フエナンスレンキノン、カン ファーキノン、ジベンゾスベロン、 1—〔4— (2 ヒドロキシエトキシ）一フエ-ル〕 2— ヒドロキシ一 2—メチル 1—プロパン一 1—オン、 2 -ベンジル - 2-ジメチルァミノ —1— (4 モルフォリノフエ-ル）一ブタノン一 1、フエナンスレンキノン、 1, 4 ジべ ンゾィルベンゼン、 10—ブチル一2—クロロアタリドン、 2, 2，一ビス（o クロ口フエ二 ル） 4, 5, 4，， 5，ーテトラキス（3, 4, 5 トリメトキシフエ-ル） 1, 2，ービイミダゾ ール、 2, 2，一ビス（o クロ口フエ-ル）一 4, 5, 4，， 5，一テトラフエ-ル一 1, 2，一ビ イミダゾール、 2 ベンゾィルナフタレン、 4 ベンゾィルビフエ-ル、 4 ベンゾィル ジフエ-ルエーテル、アクリル化べンゾフエノンなどもある。これらは、単独にまたは 2 種以上併用して使用される。 [0042] 光開始剤としては、前述の光開始剤の中で、 2 ヒドロキシー2—メチルー 1 フエ二 ルプロパン 1 オン、 1ーヒドロキシシクロへキシルーフエ二ルケトン、 2—メチルー 1 4 （メチルチオ）フエ-ル〕 2 モルフォリノプロパン 1 オン、 2 べンジル —2 ジメチルァミノ一 1— (4 モルフォリノフエ-ル）一ブタノン一 1などのァセトフエ ノン類、ベンジルジメチルケタール（2, 2—ジメトキシ一 1, 2—ジフエニルェタン一 1 オン）などのケタール類、 2 ェチルアントラキノンなどのアントラキノン類、 2, 4— ジェチルチオキサントンなどのチォキサントン類が硬化性や密着性の点で好ましい。 In addition, 1, 1-dichloroacetophenone, 1-hydroxy monocyclohexyl monophenol, azobisisobutyl nitrile, benzoyl peroxide, di-tert-butyl dioxide, 2, 4, 6 tri Methylolbenzophenone, 4-methylbenzophenone, 2-hydroxy 2-methyl 1- [4- (1-methylvinyl) phenol] propanone, bis (2,6-dimethoxybenzoyl) -2, 4 , 4 Trimethyl-pentylphosphine oxide, 2,2-dichloro-l p-phenoxyacetophenone, 1-phenolinole 1,2-propanedione-2- (o ethoxycarbonyl) oxime, 2, 4, 6 trimethylbenzo Yildiphenylphosphine oxide, methylphenylglyoxyester, 9, 10 phenanthrenequinone, camphorquinone, dibenzosuberone, 1- [4- (2 (Droxyethoxy) monophenyl] 2-hydroxy-1-2-methyl 1-propane-1-one, 2-benzyl-2-dimethylamino —1— (4 morpholinophenol) monobutanone 1, phenanthrene Quinone, 1, 4 Dibenzol benzene, 10-Butyl-2-chloro attaridone, 2, 2, 1 bis (o-phenyl) 4, 5, 4, 5, 5-tetrakis (3, 4, 5 Tri (Methoxyphenyl) 1, 2, -biimidazole, 2, 2, monobis (o-clogging fumes) 1, 4, 5, 4, 5, monotetraphenyl 1, 2, 1, monoimidazole, There are also 2 benzoylnaphthalene, 4 benzoyl biphenyl, 4 benzoyl diphenyl ether, and acrylated benzophenone. These may be used alone or in combination of two or more. [0042] As the photoinitiator, among the above-mentioned photoinitiators, 2-hydroxy-2-methyl-1-phenylpropane 1-one, 1-hydroxycyclohexyl roofing ketone, 2-methyl-14- (methylthio) phenol ] 2 Morpholinopropane 1-on, 2-benzil-2 Dimethylamino 1- (4-morpholinophenol) 1-butanone 1 Acetophenones such as 1, benzyldimethyl ketal (2,2-dimethoxy-1,2,2-diphenylethane 1-on), anthraquinones such as 2-ethyl anthraquinone, and thixanthones such as 2,4-jetylthioxanthone are preferred in terms of curability and adhesion.
[0043] また、光重合開始剤に光開始助剤を組み合わせて用いることもできる。光開始助剤 の具体例としては、トリエタノールァミン、メチルジェタノールァミン、トリイソプロパノー ルァミン、 4ージメチルァミノ安息香酸メチル、 4ージメチルァミノ安息香酸ェチル、 4 ジメチルァミノ安息香酸イソァミル、 4 ジメチルァミノ安息香酸 2 ェチルへキシ ル、安息香酸 2 ジメチルアミノエチル、 N, N ジメチルバラトルイジン、 9, 10 ジ メトキシアントラセン、 2 ェチルー 9, 10 ジメトキシアントラセン、 9 10 ジエトキシ アントラセン、 2 ェチル 9, 10 ジェトキシアントラセンが挙げられる。これら光開 始助剤は、それぞれ単独で、又は 2種以上組み合わせて用いることができる。  [0043] Further, a photoinitiator may be used in combination with a photopolymerization initiator. Specific examples of the photoinitiator include triethanolamine, methyl jetanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl dimethylaminobenzoate, 4 dimethylaminobenzoic acid 2 Ethyl hexyl, 2 dimethylaminoethyl benzoate, N, N dimethylbalatoluidine, 9,10 dimethoxyanthracene, 2 ethyl-9,10 dimethoxyanthracene, 9 10 diethoxyanthracene, 2 ethyl 9,10 jetoxyanthracene . These photoinitiators can be used alone or in combination of two or more.
[0044] この光開始剤の配合量は、活性光線硬化型ハイパーブランチポリマーと必要に応じ て使用される活性光線重合性ィ匕合物（後述する）の合計 100重量部に対して、 0. 3 重量部以上が好ましぐより好ましくは 0. 5重量部以上である。上限は好ましくは 10 重量部以下、より好ましくは 5重量部以下である。 0. 3重量部未満であると UV硬化 性が不足して密着性が悪くなつたり、硬度が低くなる傾向にある。一方 10重量部を越 えると、硬化性が飽和し経済的でなぐさらには硬化性榭脂組成物としての保存安定 性が悪くなつたり硬度が低くなる傾向にある。また、厚膜硬化の場合には密着性が悪 くなる場合がある。また、光重合開始剤に加えて、光開始助剤を用いる場合には、光 重合開始剤と光開始助剤の合計量が上記の範囲となるようにするのが好ましい。  [0044] The amount of the photoinitiator to be added is 100% by weight with respect to a total of 100 parts by weight of the actinic ray curable hyperbranched polymer and the actinic ray polymerizable compound (described later) used as necessary. 3 parts by weight or more is preferred, more preferably 0.5 parts by weight or more. The upper limit is preferably 10 parts by weight or less, more preferably 5 parts by weight or less. If the amount is less than 3 parts by weight, the UV curability is insufficient and the adhesion tends to be poor, or the hardness tends to be low. On the other hand, if it exceeds 10 parts by weight, the curability is saturated and economical, and the storage stability of the curable resin composition tends to be poor, and the hardness tends to be low. In addition, in the case of thick film curing, adhesion may be deteriorated. Further, when a photoinitiator is used in addition to the photoinitiator, the total amount of the photoinitiator and the photoinitiator is preferably within the above range.
[0045] 本発明の活性光線硬化型ハイパーブランチポリマーは必要に応じて分子内に活性 光線重合性二重結合を有するその他活性光線光重合性化合物を適量配合する事 ができる。分子内に 1個の活性光線光重合性二重結合を有するその他の活性光線 重合性ィ匕合物としては、例えば、メチル (メタ)アタリレート、ェチル (メタ)アタリレート、 n—および i—プロピル (メタ）アタリレート、 i一， n—ブチル (メタ）アタリレート、イソデシ ル (メタ）アタリレート、 2—ェチルへキシル (メタ）アタリレート、ラウリル (メタ）アタリレー ト、 2—エトキシェチル (メタ）アタリレート、エトキシジエチレングリコール (メタ）アタリレ ートなどのアルキル (メタ）アタリレート類、 2—ヒドロキシェチル (メタ）アタリレートや 2 —ヒドロキシプロピル (メタ）アタリレート、 2—ヒドロキシブチルメタアタリレートなどのヒド ロキシアルキル (メタ）アタリレート類、ある 、はポリエチレングリコールモノ (メタ）アタリ レート、ポリプロピレングリコールモノ（メタ）アタリレートなどのポリオキシアルキレングリ コールモノ（メタ）アタリレート類、ジメチルアミノエチル (メタ）アタリレート、ジェチルアミ ノエチル (メタ）アタリレートなどのアミノアルキル (メタ）アタリレート類がある。その他、 タ）アタリレート、イソボ-ル (メタ）アタリレート、ジシクロペンチ-ル (メタ）アタリレート、 (ジシクロペンテ-ル)ォキシ (メタ）アタリレート、さらには、ジイソシァネートイ匕合物と 1 個以上のアルコール性水酸基含有化合物を予め反応させて得られる末端イソシァネ ート基含有化合物に、さらにアルコール性水酸基含有 (メタ)アタリレート類を反応さ せて得られる分子内に 1個の (メタ）アタリロイルォキシ基を有するウレタン変性モノ (メ タ）アタリレート類、カルボン酸成分としてアクリル酸またはメタクリル酸および多価力 ルボン酸とアルコール成分として 2価以上の多価アルコールとを反応させて得られる オリゴエステルモノ (メタ）アタリレート類などがある。 [0045] The actinic ray curable hyperbranched polymer of the present invention can be blended with an appropriate amount of another actinic ray photopolymerizable compound having an actinic ray polymerizable double bond in the molecule, if necessary. Other active light polymerizable compounds having one active light photopolymerizable double bond in the molecule include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n— and i-propyl (meth) acrylate, i-, n-butyl (meth) acrylate, isodecyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, lauryl (meth) acrylate Alkyl (meth) acrylates such as 2-ethoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, 2- Hydroxyalkyl (meth) acrylates such as hydroxybutyl meta acrylate, or polyoxyalkylene glycol mono (meth) acrylate such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate , Dimethylaminoethyl (meth) Tarireto, there is aminoalkyl (meth) Atari rate such as Jechiruami aminoethyl (meth) Atari rate. In addition, ta) acrylate, isoball (meth) acrylate, dicyclopentyl (meth) acrylate, (dicyclopentyl) oxy (meth) acrylate, and diisocyanate compound 1 In the molecule obtained by reacting a terminal isocyanate group-containing compound obtained by reacting at least one alcoholic hydroxyl group-containing compound in advance with an alcoholic hydroxyl group-containing (meth) acrylate, ) Urethane-modified mono (meth) atalylates having an allyloyloxy group, acrylic acid or methacrylic acid as a carboxylic acid component and polyhydric power rubonic acid and a polyhydric alcohol having two or more valences as an alcohol component. The resulting oligoester mono (meth) acrylates.
分子内に 2個の光重合性二重結合を有するその他の活性光線重合性化合物として は、例えば、エチレングリコールジ (メタ）アタリレート、プロピレングリコールジ (メタ）ァ タリレート、 1, 3 ブタンジオールジ (メタ）アタリレート、 1, 4 ブタンジオールジ (メタ )アタリレート、ネオペンチルグリコールジ (メタ）アタリレート、 1, 6 へキサンジオール ジ (メタ）アタリレート、 1, 9ーノナンジオールジメタタリレート、グリセリンジメタタリレート などのアルキレングリコールジ (メタ）アタリレート類、ジエチレングリコールジ（メタ）ァク リレート、トリエチレングリコールジ (メタ）アタリレート、ジプロピレングリコールジ (メタ） アタリレート、ポリエチレングリコールジ (メタ）アタリレート、ポリプロピレングリコールジ（ メタ）アタリレートなどのポリオキシアルキレングリコールジ (メタ）アタリレート類、ジイソ シァネート化合物と 2個以上のアルコール性水酸基含有化合物を予め反応させて得 られる末端イソシァネート基含有化合物〖こ、さらにアルコール性水酸基含有 (メタ)ァ タリレート類を反応させて得られる分子内に 2個の (メタ)アタリロイルォキシ基を有す るウレタン変性ジ (メタ)アタリレート類、カルボン酸成分としてアクリル酸またはメタタリ ル酸および多価カルボン酸とアルコール成分として 2価以上の多価アルコールとを反 応させて得られるオリゴエステルジ (メタ)アタリレート類などがある。 Other active photopolymerizable compounds having two photopolymerizable double bonds in the molecule include, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1, 3 butanediol di (Meth) Atarylate, 1, 4 Butanediol Di (Meth) Atarylate, Neopentyl Glycol Di (Meth) Atarylate, 1, 6 Hexanediol Di (Meth) Atarylate, 1,9-Nonanediol Dimetatalylate , Alkylene glycol di (meth) acrylates such as glycerin dimetatalylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, polypropylene glycol di ( Data) polyoxyalkylene glycol di (meth) Atari rate such as Atari rate, reacted in advance diisopropyl Shianeto compound and at least two alcoholic hydroxyl group-containing compound to give Urethane-modified di (meth) having two (meth) atallylooxy groups in the molecule obtained by reacting a terminal isocyanate group-containing compound, which is obtained by further reacting with an alcoholic hydroxyl group-containing (meth) atalylate Atalylates, such as oligoester di (meth) acrylates obtained by reacting acrylic acid or metathallic acid as a carboxylic acid component and a polyvalent carboxylic acid with a polyhydric alcohol having a valence of 2 or more as an alcohol component .
[0047] また、分子内に 3個以上の光重合性二重結合を有するその他の活性光線重合性ィ匕 合物としては、トリメチロールプロパントリ（メタ）アタリレート、テトラメチロールメタントリ（ メタ）アタリレート、テトラメチロールェタントリ（メタ）アタリレート、テトラメチロールメタン テトラ (メタ)アタリレート、エチレンオキサイド変性トリメチロールプロパン (メタ)アタリレ ート、ジペンタエリスリトールへキサ (メタ）アタリレートなどがある。  [0047] Other active photopolymerizable compounds having three or more photopolymerizable double bonds in the molecule include trimethylolpropane tri (meth) acrylate and tetramethylolmethanetri (meth). Atalylate, tetramethylol ethane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, ethylene oxide modified trimethylol propane (meth) acrylate, dipentaerythritol hex (meth) acrylate .
[0048] 上記活性光線重合性化合物は、必要に応じて、活性光線硬化型ハイパーブランチ ポリマーに対して 50重量％以下で配合される。配合量は各々の使用用途条件により 適性量が異なるが 50重量％を越えると UV硬化反能性は飽和状態となり更に添加し ても硬化性は向上せず、むしろ不飽和結合の反応率が低下する。また低分子量成 分が過剰となり、硬化塗膜の耐久性が悪化する。  [0048] The actinic ray polymerizable compound is blended in an amount of 50% by weight or less based on the actinic ray curable hyperbranched polymer, if necessary. The compounding amount varies depending on the application conditions, but if it exceeds 50% by weight, the UV curing reactivity becomes saturated and further curing does not improve the curability, but rather the reaction rate of unsaturated bonds decreases. To do. In addition, the low molecular weight component becomes excessive, and the durability of the cured coating film deteriorates.
[0049] 本発明の活性光線硬化型ハイパーブランチボリマーを用いた榭脂粗成物は室温ま たは必要により加温下で攪拌混合することにより容易に製造される。製造時の熱重合 や貯蔵中の暗反応を防止するために、ハイドロキノン、ハイドロキノンモノメチルエー テル、 1ーブチルーカテコール、 p—べンゾキノン、 2, 5— tーブチルーハイドロキノン 、フエノチアジンなどの公知の熱重合防止剤を添加するのが望ましい。その添加量は 本発明のポリエステルを共重合成分として含む活性光線重合性オリゴマー (A) 100 重量部に対して、好ましくは 0. 001重量部以上、より好ましくは 0. 005重量部以上 であり、上限は好ましくは 0. 1重量部以下、より好ましくは 0. 05重量部以下である。 0 . 001重量部未満では効果が得られないことがあり、 0. 1重量部を越えて配合しても 効果が飽和し、経済的でない。  [0049] A crude resin composition using the actinic ray curable hyperbranched polymer of the present invention is easily produced by stirring and mixing at room temperature or, if necessary, heating. In order to prevent thermal polymerization during production and dark reaction during storage, known hydroquinone, hydroquinone monomethyl ether, 1-butyl-catechol, p-benzoquinone, 2,5-tert-butyl-hydroquinone, phenothiazine, etc. It is desirable to add a thermal polymerization inhibitor. The addition amount is preferably 0.001 part by weight or more, more preferably 0.005 part by weight or more, with respect to 100 parts by weight of the actinic ray-polymerizable oligomer (A) containing the polyester of the present invention as a copolymerization component, The upper limit is preferably 0.1 parts by weight or less, more preferably 0.05 parts by weight or less. If it is less than 0.001 part by weight, the effect may not be obtained, and if it exceeds 0.1 part by weight, the effect is saturated and it is not economical.
[0050] 上記光開始剤、増感剤、活性光線重合性化合物の他にエポキシ榭脂、フエノール榭 脂などの別の榭脂成分をブレンド使用する事も出来る。これら榭脂成分は本発明の ハイパーブランチポリマーの特性を損ねな 、範囲で任意の割合で配合して良 、。 [0051] 更に、本発明の活性光線硬化型ハイパーブランチボリマーを用いた榭脂粗成物は、 用途に応じて、エポキシ榭脂、液状ポリブタジエン、ポリウレタンポリマー、シリコン系 オリゴマー等の非反応性ィ匕合物や、酸化珪素、タルク、シリカ、炭酸カルシウム、ベン トナイト、カオリン、ガラス繊維、雲母等の充填剤、その他、消泡剤、難燃剤、カツプリ ング剤、粘着付与剤、レべリング剤、可塑剤、酸化防止剤、紫外線吸収剤、難燃剤、 染料などを適宜使用することもできる。 [0050] In addition to the photoinitiator, sensitizer, and actinic ray polymerizable compound, other resin components such as epoxy resin and phenol resin can be blended. These resin components may be blended at an arbitrary ratio within the range without impairing the properties of the hyperbranched polymer of the present invention. [0051] Further, the coarse resin composition using the actinic ray curable hyperbranched polymer of the present invention is non-reactive such as epoxy resin, liquid polybutadiene, polyurethane polymer, silicon oligomer, etc., depending on the application. Compound, fillers such as silicon oxide, talc, silica, calcium carbonate, bentonite, kaolin, glass fiber, mica, etc., antifoaming agent, flame retardant, cutting agent, tackifier, leveling agent Plasticizers, antioxidants, ultraviolet absorbers, flame retardants, dyes, and the like can be used as appropriate.
[0052] 本発明の活性光線硬化型ハイパーブランチポリマーを用いた硬化性榭脂組成物に おいては、反応を促進させる必要がある場合はさらに反応促進剤の添加が効果的で ある。反応促進剤としては、例えば、 2—メチルイミダゾール、 2—ェチルイミダゾール 、 2—ェチルー 4ーメチルイミダソール、 1一べンジルー 2—メチルイミダゾールなどの イミダゾール類、ベンジルジメチルァミン、トリエタノールァミン、トリエチルァミン、 n- ブチルァミン、ジ—n—ブチルァミン、 N, N—ジメチルァミノエタノール、 N, N—ジェ チルァミノエタノール、 N, N—ジプロピルアミノエタノールなどの第 3級ァミン類、トリ ジメチルァミノメチルフエノールのトリアセテートおよびトリべンゾエートなどの第 3級ァ ミン塩類、ァリルチオ尿素、 o—トリルチオ尿素などの尿素類、 s—ベンジル—イソチウ 口-ムー p—トルエンスルフィネートなどのィォゥ化合物、トリー n—ブチルホスフィン、 ナトリウムジェチルジチォホスフェートなどのリン化合物などがあり、単独にまたは 2種 以上併用して使用される。  [0052] In the curable resin composition using the actinic ray curable hyperbranched polymer of the present invention, addition of a reaction accelerator is more effective when the reaction needs to be accelerated. Examples of the reaction accelerator include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-methylimidazole, benzyldimethylamine, and triethanolamine. Tertiary amines such as amine, triethylamine, n-butylamine, di-n-butylamine, N, N-dimethylaminoethanol, N, N-dimethylaminoethanol, N, N-dipropylaminoethanol , Tertiary amine salts such as triacetate and tribenzoate of tridimethylaminomethylphenol, ureas such as allylthiourea and o-tolylthiourea, s-benzyl-isothiuol-mu p-toluenesulfinate N-butylphosphine, sodium jetyl dithiophosphate Phosphorus compounds such as these are used alone or in combination of two or more.
[0053] これら反応促進剤の添加量は、本発明の活性光線硬化型ハイパーブランチポリマー と必要に応じて使用される活性光線重合性ィ匕合物の合計量を 100重量部としたとき に対して、好ましくは 0. 05重量部以上、より好ましくは 0. 1重量部以上である。上限 は、好ましくは 5重量部以下、より好ましくは 3. 5重量部以下である。 0. 05重量部未 満だと反応促進の効果が得られないことがあり、 3. 5重量部を越えると保存安定性が 悪くなる場合がある。  [0053] The addition amount of these reaction accelerators is compared with the case where the total amount of the actinic radiation curable hyperbranched polymer of the present invention and the actinic radiation polymerizable compound used as necessary is 100 parts by weight. The amount is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more. The upper limit is preferably 5 parts by weight or less, more preferably 3.5 parts by weight or less. If it is less than 0.05 parts by weight, the effect of promoting the reaction may not be obtained, and if it exceeds 3.5 parts by weight, the storage stability may be deteriorated.
[0054] 本発明の活性光線硬化型ハイパーブランチボリマーを電子材料等のレジスト用榭脂 として使用する際には用途に応じ、種々顔料が分散配合される。例えば導電性粒子 としては金、白金、銀、パラジウム、ロジウム、亜鉛、銅、ニッケル、鉄、及びこれら金 属の合金、或いはグラフアイト、カーボンナノチューブ、導電性カーボンブラック等、ま たは絶縁性粒子としてはシリカやアルミナの酸ィ匕物、ゼォライト等の無機粒子、或い は有機ポリマー粒子等が挙げられる。更に着色剤としてはフタロシアニン等の有機顔 料、チタンホワイト、酸化鉄等の無機顔料、或いはァゾ染料等の種々有機染料が分 散配合される。 [0054] When the actinic ray curable hyperbranched polymer of the present invention is used as a resin grease for electronic materials or the like, various pigments are dispersed and blended depending on the application. For example, the conductive particles include gold, platinum, silver, palladium, rhodium, zinc, copper, nickel, iron, and alloys of these metals, graphite, carbon nanotubes, conductive carbon black, and the like. Examples of the insulating particles include silica and alumina oxides, inorganic particles such as zeolite, and organic polymer particles. Further, organic pigments such as phthalocyanine, inorganic pigments such as titanium white and iron oxide, and various organic dyes such as azo dyes are dispersed and blended as colorants.
実施例  Example
[0055] 以下実施例により本発明を具体的に例示する。実施例中に単に部とあるのは重量 部を示す。得られた榭脂の分析評価は次の方法により実施した。  [0055] The present invention is specifically illustrated by the following examples. In the examples, “parts” means “parts by weight”. Analysis and evaluation of the obtained rosin were carried out by the following method.
[0056] (数平均分子量）  [0056] (Number average molecular weight)
テトラヒドロフランを溶離液としたウォーターズ社製ゲル浸透クロマトグラフィー（GPC ) 150cを用いて、カラム温度 30°C、流量 lmlZ分にて GPC測定を行なった結果から 計算して、ポリスチレン換算の測定値を得た。ただしカラムは昭和電工 (株） shodex KF— 802、 804、 806を用いた。解析はウォーターズ社製-レニアム 32を用い、ピ ーク全体 (ピークの立ち上がりからベースラインと同じ高さになる位置まで)を解析範 囲とした。  Using polystyrene gel permeation chromatography (GPC) 150c with tetrahydrofuran as the eluent, a GPC measurement was performed at a column temperature of 30 ° C and a flow rate of 1 ml Zmin. It was. However, Showa Denko Co., Ltd. shodex KF-802, 804, 806 was used for the column. The analysis used Waters-Renium 32, and the entire peak (from the peak rise to the same height as the baseline) was used as the analysis range.
[0057] (組成分析及び不飽和結合基濃度、芳香環濃度の定量）  [0057] (Composition analysis and determination of unsaturated bond group concentration and aromatic ring concentration)
DMSO— d溶媒中でヴアリアン社製核磁気共鳴分析計 (NMR)ジヱミ- - 200を  DMSO—Varian Nuclear Magnetic Resonance Analyzer (NMR) in a d-solvent-200
6  6
用いて、1 H— NMR分析を行なつてその積分比より決定した。 The 1 H-NMR analysis was performed and determined from the integration ratio.
[0058] (ガラス転移温度） [0058] (Glass transition temperature)
サンプル 5mgをアルミニウム製サンプルパンに入れて密封し、セイコーインスツルメ ンッ (株)製示差走査熱量分析計 DSC— 220を用いて、 200°Cまで、昇温速度 20°C Place 5 mg of sample in an aluminum sample pan, seal it, and use a differential scanning calorimeter DSC-220 manufactured by Seiko Instruments Inc. up to 200 ° C and a heating rate of 20 ° C.
Z分にて測定し、ガラス転移温度以下のベースラインの延長線と遷移部における最 大傾斜を示す接線との交点の温度で求めた。 Measured at Z minutes, it was determined at the temperature of the intersection of the extension of the baseline below the glass transition temperature and the tangent indicating the maximum slope at the transition.
[0059] (酸価） [0059] (Acid value)
榭脂 0. 2gを 20cm3のクロ口ホルムに溶解し、 0. 1Nの水酸化カリウムエタノール溶 液で滴定し、榭脂 106g当たりの当量 (eq/106g)を求めた。指示薬はフエノールフタ レインを用いた。 The榭脂0. 2 g was dissolved in black port Holm 20 cm 3, and titrated with potassium hydroxide ethanol solvent solution of 0. 1N, was determined equivalents per榭脂 10 6 g (eq / 10 6 g). As the indicator, phenolphthalein was used.
[0060] 以下、表中及び本文中の略号を示す。 [0060] Abbreviations in the table and text are shown below.
PETH：ペンタエリスリトール DMBA：ジメチロールブタン酸 PETH: Pentaerythritol DMBA: dimethylol butanoic acid
DMPA:ジメチロールプロピオン酸  DMPA: dimethylolpropionic acid
TMP：トリメチロールプロパン  TMP: Trimethylolpropane
T:テレフタル酸  T: terephthalic acid
I：イソフタル酸  I: Isophthalic acid
EG :エチレングリコール  EG: Ethylene glycol
NPG：ネオペンチノレグリコーノレ  NPG: Neo-Pentinore Gliconole
TMA:無水トリメリット酸  TMA: trimellitic anhydride
MAN ：無水マレイン酸  MAN: Maleic anhydride
BTDA:ベンゾフエノンテトラカルボン酸二無水物  BTDA: benzophenone tetracarboxylic dianhydride
DSA：ドデセ-ル無水コハク酸  DSA: Dodecyl succinic anhydride
THPA：テトラヒドロ無水フタル酸  THPA: Tetrahydrophthalic anhydride
OSA：オタテニル無水コハク酸  OSA: Otatenyl succinic anhydride
SA:無水コハク酸  SA: Succinic anhydride
PA:無水フタル酸  PA: phthalic anhydride
NDA:ナフタレン 2, 3 ジカルボン酸無水物  NDA: Naphthalene 2,3 dicarboxylic anhydride
HBAGE： 4 ヒドロキシブチルアタリレートグリシジルエーテル  HBAGE: 4 Hydroxybutyl talylate glycidyl ether
GMA：グリシジルメタタリレート  GMA: Glycidylmetatalylate
PGE：フエニルダリシジルエーテル  PGE: Phenyldaricidyl ether
MGE：メチルダリシジルエーテル  MGE: Methyldaricidyl ether
TBPGE ： p - tert -ブチルフエ-ルグリシジルエーテル  TBPGE: p-tert-butylphenol glycidyl ether
PETA:ペンタエリスリトールとアクリル酸の縮合物 PETA: Condensate of pentaerythritol and acrylic acid
MDI :4, 4'ージフエ-ルメタンジイソシァネート MDI: 4,4'-diphenylmethane diisocyanate
PGMEA:プロピレングリコールモノメチルエーテル =アセテート PGMEA: Propylene glycol monomethyl ether = acetate
実施例（1)  Example (1)
ノヽィパーブランチポリマー A1の合成  Synthesis of Noyperbranch polymer A1
パーシャルコンデンサー、温度計、攪拌棒を具備した反応釜にトリメチロールプロパ ン 67部、ジメチロールプロピオン酸 3660部、パラトルエンスルホン酸（以下 PTSと略 す） 20部を仕込み 100°C下に攪拌し、均一な液状混合溶融物とした。次いでトルェ ン 100部を注入後 140°Cに昇温し、トルエンを還流しつつ発生する水を共沸により系 外に溜去した。同条件で 5時間反応を継続した後、系外へトルエンを留去し、ハイパ 一ブランチポリマー A1を得た。得られた重縮合物の酸価は 143eqZton、数平均分 子量は 3500であった。 In a reaction kettle equipped with a partial condenser, thermometer and stirring rod, 67 parts of trimethylolpropan, 3660 parts of dimethylolpropionic acid, paratoluenesulfonic acid (hereinafter abbreviated as PTS) 20 parts were charged and stirred at 100 ° C to obtain a uniform liquid mixed melt. Next, 100 parts of toluene was injected, the temperature was raised to 140 ° C., and water generated while refluxing toluene was distilled out of the system by azeotropic distillation. After continuing the reaction for 5 hours under the same conditions, toluene was distilled off from the system to obtain a hyperbranched polymer A1. The acid value of the obtained polycondensate was 143 eqZton, and the number average molecular weight was 3,500.
[0062] 次いで、このハイパーブランチポリマー（A1) 1000部とプロピレングリコールモノメ チルエーテル =アセテート（以下 PGMEAと略す） 1000部、トルエン 1000部を仕込 み、溶解後 145度まで加熱して系内の水分を溜去、トルエンを完全に溜去した。無 水マレイン酸 760部、触媒としてトリェチルァミン（以下 TEAと略す） 5. 5部を添加し、 80°C、窒素雰囲気下で 5時間反応させた後、 p— tert—ブチルフエ-ルグリシジルェ 一テル 1400部、触媒としてトリフ ニルホスフィン (以下 TPPと略す） 27部を添加し、 さらに 80°Cにおいて 7時間反応させた。続いて、 PGMEA5170部をカ卩ぇ希釈した後 、無水フタル酸を 954部添加し、さらに 80°Cにおいて 7時間反応を継続させ、活性光 線硬化型ハイパーブランチポリマー（1)を得た。得られた活性光線硬化型ハイパー ブランチポリマー（1)の数平均分子量は 4700、酸価は 1800eqZton、ガラス転移 温度は 3°C、不飽和結合基濃度は 1900eqZton、芳香環濃度は 3200eqZtonで あった。これら結果を表 2、 3に示した。  [0062] Next, 1000 parts of this hyperbranched polymer (A1), 1000 parts of propylene glycol monomethyl ether = acetate (hereinafter abbreviated as PGMEA) and 1000 parts of toluene are charged, and after dissolution, heated to 145 degrees C. The toluene was distilled off completely. 760 parts of anhydrous maleic acid, triethylamine (hereinafter abbreviated as TEA) as catalyst 5. Add 5 parts, react at 80 ° C under nitrogen atmosphere for 5 hours, and then 1400 parts of p-tert-butylphenol-glycidyl ester Then, 27 parts of triphenylphosphine (hereinafter abbreviated as TPP) was added as a catalyst, and further reacted at 80 ° C. for 7 hours. Subsequently, after 5170 parts of PGMEA was diluted, 954 parts of phthalic anhydride was added, and the reaction was continued at 80 ° C. for 7 hours to obtain an actinic radiation curable hyperbranched polymer (1). The obtained actinic ray curable hyperbranched polymer (1) had a number average molecular weight of 4700, an acid value of 1800 eqZton, a glass transition temperature of 3 ° C, an unsaturated bond group concentration of 1900 eqZton, and an aromatic ring concentration of 3200 eqZton. These results are shown in Tables 2 and 3.
[0063] 実施例（2)  [0063] Example (2)
実施例 1で作製したハイパーブランチ（A1) 1000部と PGMEA1000部、トルエン 1 000部を仕込み、溶解後 145度まで加熱して系内の水分を溜去、トルエンを完全に 溜去した。無水トリメリット酸 1200部、触媒として TEA5. 5部を添加し、 80°C、窒素 雰囲気下で 5時間反応させた後、フエ-ルグリシジルエーテル 1540部、触媒として T PP27部を添加し、さらに 80°Cにおいて 7時間反応させた。続いて、 PGMEA5150 部を加え希釈した後、無水マレイン酸を 362部添加し、さらに 80°Cにおいて 7時間反 応を継続させ、活性光線硬化型ハイパーブランチポリマー（2)を得た。 数平均分子 量は 6600、酸価は 1420eqZton、ガラス転移温度は 30°C、不飽和結合基濃度は 9 00eqZton、芳香環濃度は 4000eqZtonであった。これら結果を表 2、 3に示した。  1000 parts of the hyperbranch (A1) prepared in Example 1, 1000 parts of PGMEA, and 1,000 parts of toluene were charged. After dissolution, the mixture was heated to 145 ° C. to distill off the water in the system, and the toluene was completely distilled off. Add 1200 parts of trimellitic anhydride, 5.5 parts of TEA as a catalyst, react for 5 hours at 80 ° C in a nitrogen atmosphere, add 1540 parts of glycidyl ether, and 27 parts of TPP as a catalyst. The reaction was carried out at 80 ° C for 7 hours. Subsequently, 5150 parts of PGMEA was added for dilution, 362 parts of maleic anhydride was added, and the reaction was continued at 80 ° C. for 7 hours to obtain an actinic ray curable hyperbranched polymer (2). The number average molecular weight was 6600, the acid value was 1420 eqZton, the glass transition temperature was 30 ° C, the unsaturated bond group concentration was 900 eqZton, and the aromatic ring concentration was 4000 eqZton. These results are shown in Tables 2 and 3.
[0064] 実施例（3) 実施例 1で作製したハイパーブランチ（Al) 1000部と PGMEA1000部、トルエン 5 000部を仕込み、溶解後 145度まで加熱して系内の水分を溜去、トルエンを完全に 溜去した。無水トリメリット酸 750部、無水フタル酸 411部、触媒として TEA5. 5部を 添加し、 80°C、窒素雰囲気下で 5時間反応させた後、フエニルダリシジルエーテル 1 320部、触媒として TPP27部を添加し、さらに 80°Cにおいて 7時間反応させた。続い て、 PGMEA4830部をカ卩ぇ希釈した後、無水マレイン酸を 404部添カ卩し、さらに 80 °Cにおいて 7時間反応を継続させ、活性光線硬化型ハイパーブランチポリマー（3)を 得た。得られた活性光線硬化型ハイパーブランチポリマー（3)の数平均分子量は 55 00、酸価は 1510eqZton、ガラス転移温度は 15°C、不飽和結合基濃度は l lOOeq /ton,芳香環濃度は 4000eqZtonであった。これら結果を表 2、 3に示した。 Example (3) 1000 parts of hyperbranch (Al) prepared in Example 1, 1000 parts of PGMEA, and 5,000 parts of toluene were charged, heated to 145 ° C. after dissolution, and water in the system was distilled off, and toluene was distilled off completely. 750 parts of trimellitic anhydride, 411 parts of phthalic anhydride, 5.5 parts of TEA as a catalyst, reacted at 80 ° C under nitrogen atmosphere for 5 hours, and then 320 parts of phenyl daricidyl ether, TPP27 as a catalyst Part was added and further reacted at 80 ° C for 7 hours. Subsequently, after 4830 parts of PGMEA was diluted, 404 parts of maleic anhydride was added, and the reaction was further continued at 80 ° C. for 7 hours to obtain an actinic ray curable hyperbranched polymer (3). The resulting actinic radiation curable hyperbranched polymer (3) has a number average molecular weight of 5500, an acid value of 1510 eqZton, a glass transition temperature of 15 ° C, an unsaturated bond group concentration of l lOOeq / ton, and an aromatic ring concentration of 4000 eqZton. Met. These results are shown in Tables 2 and 3.
[0065] 実施例 (4) [0065] Example (4)
実施例 1で作製したハイパーブランチ（A1) 1000部と PGMEA1000部、トルエン 1 000部を仕込み、溶解後 145度まで加熱して系内の水分を溜去、トルエンを完全に 溜去した。無水トリメリット酸 1433部、触媒として TEA5. 5部を添加し、 80°C、窒素 雰囲気下で 5時間反応させた後、 4ーヒドロキシブチルアタリレートグリシジルエーテ ル 360部、フエ-ルグリシジルエーテル 621部、触媒として TPP27部を添カ卩し、さら に 80°Cにおいて 7時間反応させた。続いて、 PGMEA4480部をカ卩ぇ希釈した後、 オタテニル無水コハク酸を 240部添加し、さらに 80°Cにおいて 7時間反応を継続させ 、活性光線硬化型ノ、ィパーブランチポリマー (4)を得た。得られた活性光線硬化型 ハイパーブランチポリマー（4)の数平均分子量は 4800、酸価は 2680eqZton、ガラ ス転移温度は 18°C、不飽和結合基濃度は 750eqZton、芳香環濃度は 3200eqZt onであった。これら結果を表 2、 3に示した。  1000 parts of the hyperbranch (A1) prepared in Example 1, 1000 parts of PGMEA, and 1,000 parts of toluene were charged. After dissolution, the mixture was heated to 145 ° C. to distill off the water in the system, and the toluene was completely distilled off. 1433 parts of trimellitic anhydride and 5.5 parts of TEA as a catalyst were added and reacted for 5 hours at 80 ° C in a nitrogen atmosphere. Then, 360 parts of 4-hydroxybutyl talidate glycidyl ether, glyceryl ether 621 Then, 27 parts of TPP was added as a catalyst, and further reacted at 80 ° C for 7 hours. Subsequently, after 4480 parts of PGMEA were diluted, 240 parts of octenyl succinic anhydride was added, and the reaction was continued at 80 ° C for 7 hours to obtain an actinic ray curable polymer, iperbranched polymer (4). It was. The actinic ray curable hyperbranched polymer (4) obtained had a number average molecular weight of 4800, an acid value of 2680 eqZton, a glass transition temperature of 18 ° C, an unsaturated bond group concentration of 750 eqZton, and an aromatic ring concentration of 3200 eqZton. It was. These results are shown in Tables 2 and 3.
[0066] 実施例（5) [0066] Example (5)
実施例 1で作製したハイパーブランチ（A1) 1000部と PGMEA1000部、トルエン 1 000部を仕込み、溶解後 145度まで加熱して系内の水分を溜去、トルエンを完全に 溜去した。無水トリメリット酸 1563部、触媒として TEA5. 5部を添加し、 80°C、窒素 雰囲気下で 5時間反応させた後、フエ-ルグリシジルエーテル 2340部、触媒として T PP27部を添加し、さらに 80°Cにおいて 7時間反応させた。続いて、 PGMEA6700 部を加え希釈した後、テトラヒドロ無水フタル酸を 230添加し、さらに 80°Cにおいて 7 時間反応を継続させ、活性光線硬化型ハイパーブランチポリマー（5)を得た。得られ た活性光線硬化型ハイパーブランチポリマー（5)の数平均分子量は 7300、酸価は 4 20eqZton、ガラス転移温度は 35°C、不飽和結合基濃度は 300eqZton、芳香環 濃度は 4500eqZtonであった。これら結果を表 2、 3に示した。 1000 parts of the hyperbranch (A1) prepared in Example 1, 1000 parts of PGMEA, and 1,000 parts of toluene were charged. After dissolution, the mixture was heated to 145 ° C. to distill off the water in the system, and the toluene was completely distilled off. Add 1563 parts of trimellitic anhydride, 5.5 parts of TEA as a catalyst, react for 5 hours at 80 ° C in a nitrogen atmosphere, add 2340 parts of glycidyl ether, and 27 parts of TPP as a catalyst. The reaction was carried out at 80 ° C for 7 hours. Next, PGMEA6700 After adding and diluting, 230 parts of tetrahydrophthalic anhydride was added, and the reaction was further continued at 80 ° C. for 7 hours to obtain an actinic ray curable hyperbranched polymer (5). The actinic ray curable hyperbranched polymer (5) obtained had a number average molecular weight of 7300, an acid value of 4 20 eqZton, a glass transition temperature of 35 ° C, an unsaturated bond group concentration of 300 eqZton, and an aromatic ring concentration of 4500 eqZton. . These results are shown in Tables 2 and 3.
[0067] 実施例（6) [0067] Example (6)
ハイパーブランチポリマー A2の合成  Synthesis of hyperbranched polymer A2
パーシャルコンデンサー、温度計、攪拌棒を具備した反応釜にペンタエリスリトール 136部、ジメチロールブタン酸 8000部、パラトルエンスルホン酸（以下 PTSと略す） 4 0部を仕込み 100°C下に攪拌し、均一な液状混合溶融物とした。次いでトルエン 100 部を注入後 140°Cに昇温し、トルエンを還流しつつ発生する水を共沸により系外に 溜去した。同条件で 5時間反応を継続した後、系外へトルエンを留去し、ハイパーブ ランチポリマー A2を得た。得られた重縮合物の酸価は 214eqZton、数平均分子量 は 3800であった。  A reaction kettle equipped with a partial condenser, thermometer, and stirring rod was charged with 136 parts of pentaerythritol, 8000 parts of dimethylolbutanoic acid, and 40 parts of paratoluenesulfonic acid (hereinafter abbreviated as PTS), and stirred at 100 ° C and homogeneous. A liquid mixed melt was obtained. Next, 100 parts of toluene was injected, the temperature was raised to 140 ° C, and water generated while refluxing toluene was distilled out of the system by azeotropic distillation. After continuing the reaction for 5 hours under the same conditions, toluene was distilled off from the system to obtain hyperbranched polymer A2. The resulting polycondensate had an acid value of 214 eqZton and a number average molecular weight of 3800.
[0068] 次!、で、このハイパーブランチポリマー（A2) 1000部と PGMEA1000部、トルエン 1000部を仕込み、溶解後 145度まで加熱して系内の水分を溜去、トルエンを完全に 溜去した。無水トリメリット酸 1299部、無水コハク酸 110部、触媒として TEA5. 5部を 添加し、 80°C、窒素雰囲気下で 5時間反応させた後、グリシジルメタタリレート 330部 、 p—tert—ブチルフエ-ルグリシジルエーテル 1400部、触媒として TPP27部を添 加し、さらに 80°Cにおいて 7時間反応させた。続いて、 PGMEA6300部をカ卩ぇ希釈 した後、ドデセニル無水コハク酸を 210部添加し、さらに 80°Cにおいて 7時間反応を 継続させ、活性光線硬化型ハイパーブランチポリマー（6)を得た。得られた活性光線 硬化型ハイパーブランチポリマー（6)の数平均分子量は 7800、酸価は 780eqZto n、ガラス転移温度は 28°C、不飽和結合基濃度は 650eqZton、芳香環濃度は 350 OeqZtonであった。これら結果を表 2、 3に示した。  [0068] Next !, 1000 parts of this hyperbranched polymer (A2), 1000 parts of PGMEA, and 1000 parts of toluene were charged. After dissolution, the mixture was heated to 145 ° C to distill off the water in the system, and the toluene was completely distilled off. . Add 1299 parts of trimellitic anhydride, 110 parts of succinic anhydride, 5.5 parts of TEA as a catalyst, react at 80 ° C for 5 hours under nitrogen atmosphere, then 330 parts of glycidyl metatalylate, p-tert-butylphenol -1400 parts of luglycidyl ether and 27 parts of TPP were added as a catalyst, and the mixture was further reacted at 80 ° C for 7 hours. Subsequently, 6300 parts of PGMEA was diluted in a cup, 210 parts of dodecenyl succinic anhydride was added, and the reaction was further continued at 80 ° C. for 7 hours to obtain an actinic ray curable hyperbranched polymer (6). The actinic ray curable hyperbranched polymer (6) obtained had a number average molecular weight of 7800, an acid value of 780 eqZton, a glass transition temperature of 28 ° C, an unsaturated bond group concentration of 650 eqZton, and an aromatic ring concentration of 350 OeqZton. It was. These results are shown in Tables 2 and 3.
[0069] 実施例（7)  [0069] Example (7)
ハイパーブランチポリマー A3の合成  Synthesis of hyperbranched polymer A3
パーシャルコンデンサー、温度計、攪拌棒を具備した反応釜にトリメチロールプロパ ン 134部、ジメチロールブタン酸 7000部、パラトルエンスルホン酸（以下 PTSと略す） 40部を仕込み 100°C下に攪拌し、均一な液状混合溶融物とした。次いでトルエン 10 0部を注入後 140°Cに昇温し、トルエンを還流しつつ発生する水を共沸により系外に 溜去した。同条件で 5時間反応を継続した後、系外へトルエンを留去し、ハイパーブ ランチポリマー A3を得た。得られた重縮合物の酸価は 304eqZton、数平均分子量 は 3500であった。 Trimethylol properties in a reaction kettle equipped with a partial condenser, thermometer, and stir bar 134 parts, dimethylolbutanoic acid 7000 parts, and paratoluenesulfonic acid (hereinafter abbreviated as PTS) 40 parts were charged and stirred at 100 ° C. to obtain a uniform liquid mixed melt. Subsequently, 100 parts of toluene was injected, the temperature was raised to 140 ° C., and water generated while refluxing toluene was distilled out of the system by azeotropic distillation. After continuing the reaction for 5 hours under the same conditions, toluene was distilled off from the system to obtain a hyperbranched polymer A3. The resulting polycondensate had an acid value of 304 eqZton and a number average molecular weight of 3,500.
[0070] 次!、で、このハイパーブランチポリマー（A3) 1000部と PGMEA1000部、トルエン 1000部を仕込み、溶解後 145度まで加熱して系内の水分を溜去、トルエンを完全に 溜去した。無水トリメリット酸 908部、無水マレイン酸 189部、触媒としてトリェチルアミ ン（以下 TEAと略す） 5. 5部を添加し、 80°C、窒素雰囲気下で 5時間反応させた後、 4ーヒドロキシブチルアタリレートグリシジルエーテル 149部、フエ-ルグリシジルエー テル 922部、触媒としてトリフエ-ルホスフィン (以下 TPPと略す） 27部を添加し、さら に 80°Cにおいて 7時間反応させた。続いて、 PGMEA3830部をカ卩ぇ希釈した後、 ベンゾフエノンテトラカルボン酸二無水物を 52部添カ卩し、さらに 80°Cにおいて 7時間 反応を継続させ、活性光線硬化型ハイパーブランチポリマー（7)を得た。得られた活 性光線硬化型ハイパーブランチポリマー（7)の数平均分子量は 5400、酸価は 1500 eq/ton,ガラス転移温度は 32°C、不飽和結合基濃度は 850eqZton、芳香環濃 度は 3600eqZtonであった。これら結果を表 2、 3に示した。  [0070] In the next step, 1000 parts of this hyperbranched polymer (A3), 1000 parts of PGMEA, and 1000 parts of toluene were charged, and after dissolution, heated to 145 ° C to distill off the water in the system, and the toluene was completely distilled off. . 908 parts of trimellitic anhydride, 189 parts of maleic anhydride, 5. 5 parts of triethylamine (hereinafter abbreviated as TEA) as a catalyst, and after 5 hours of reaction at 80 ° C in a nitrogen atmosphere, 4-hydroxybutyl 149 parts of attalylate glycidyl ether, 922 parts of phenylglycidyl ether and 27 parts of triphenylphosphine (hereinafter abbreviated as TPP) were added as a catalyst, and the mixture was further reacted at 80 ° C. for 7 hours. Subsequently, after 3830 parts of PGMEA was diluted, 52 parts of benzophenone tetracarboxylic dianhydride was added, and the reaction was further continued at 80 ° C for 7 hours to obtain an actinic ray curable hyperbranched polymer ( 7) was obtained. The obtained active photocurable hyperbranched polymer (7) has a number average molecular weight of 5400, an acid value of 1500 eq / ton, a glass transition temperature of 32 ° C, an unsaturated bond group concentration of 850 eqZton, and an aromatic ring concentration of It was 3600eqZton. These results are shown in Tables 2 and 3.
[0071] 実施例（8)  [0071] Example (8)
ハイパーブランチポリマー A4の合成  Synthesis of hyperbranched polymer A4
パーシャルコンデンサー、温度計、攪拌棒を具備した反応釜にトリメチロールプロパ ン 134部、ジメチロールプロピオン酸 3500部、パラトルエンスルホン酸（以下 PTSと 略す） 20部を仕込み 100°C下に攪拌し、均一な液状混合溶融物とした。次いでトル ェン 100部を注入後 140°Cに昇温し、トルエンを還流しつつ発生する水を共沸により 系外に溜去した。同条件で 3時間反応を継続した後、系外へトルエンを留去し、ハイ パーブランチポリマー A4を得た。得られた重縮合物の酸価は 232eq/ton、数平均 分子量は 2300であった。  A reaction kettle equipped with a partial condenser, thermometer, and stirring rod was charged with 134 parts of trimethylolpropan, 3500 parts of dimethylolpropionic acid, and 20 parts of paratoluenesulfonic acid (hereinafter abbreviated as PTS), and stirred at 100 ° C. A uniform liquid mixed melt was obtained. Next, 100 parts of toluene was injected, the temperature was raised to 140 ° C, and water generated while refluxing toluene was distilled out of the system by azeotropic distillation. After continuing the reaction for 3 hours under the same conditions, toluene was distilled off from the system to obtain a hyperbranched polymer A4. The resulting polycondensate had an acid value of 232 eq / ton and a number average molecular weight of 2300.
[0072] 次!、で、このハイパーブランチポリマー（A4) 1000部と PGMEA1000部、トルエン 1000部を仕込み、溶解後 145度まで加熱して系内の水分を溜去、トルエンを完全に 溜去した。無水トリメリット酸 1325部、触媒として TEA5. 5部を添加し、 80°C、窒素 雰囲気下で 5時間反応させた後、フエ-ルグリシジルエーテル 1743部、触媒として T PP27部を添加し、さらに 80°Cにおいて 7時間反応させた。続いて、 PGMEA5700 部を加え希釈した後、無水マレイン酸を 403部添加し、さらに 80°Cにおいて 7時間反 応を継続させ、活性光線硬化型ハイパーブランチポリマー（8)を得た。得られた活性 光線硬化型ハイパーブランチポリマー（8)の数平均分子量は 3800、酸価は 1400e qZton、ガラス転移温度は 27°C、不飽和結合基濃度は 900eqZton、芳香環濃度 は 4100eqZtonであった。これら結果を表 2、 3に示した。 [0072] Next! In this hyperbranched polymer (A4) 1000 parts and PGMEA 1000 parts, toluene After 1000 parts were charged and dissolved, the system was heated to 145 ° C. to remove water in the system, and toluene was completely distilled off. Add 1325 parts of trimellitic anhydride, 5 parts of TEA as a catalyst, and react for 5 hours at 80 ° C in a nitrogen atmosphere. Then add 1743 parts of glycidyl ether and 27 parts of TPP as a catalyst. The reaction was carried out at 80 ° C for 7 hours. Subsequently, after adding 5700 parts of PGMEA and diluting, 403 parts of maleic anhydride was added, and the reaction was further continued at 80 ° C. for 7 hours to obtain an actinic ray curable hyperbranched polymer (8). The actinic ray-curable hyperbranched polymer (8) obtained had a number average molecular weight of 3800, an acid value of 1400 eqZton, a glass transition temperature of 27 ° C, an unsaturated bond group concentration of 900 eqZton, and an aromatic ring concentration of 4100 eqZton. . These results are shown in Tables 2 and 3.
[0073] 比較例（9)  [0073] Comparative Example (9)
実施例 1で作製したハイパーブランチ（A1) 1000部と PGMEA1000部、トルエン 1 000部を仕込み、溶解後 145度まで加熱して系内の水分を溜去、トルエンを完全に 溜去した。無水コハク酸 738部、触媒として TEA5. 5部を添加し、 80°C、窒素雰囲 気下で 5時間反応させた後、フエ-ルグリシジルエーテル 788部、触媒として TPP27 部を添カ卩し、さらに 80°Cにおいて 7時間反応させた。続いて、 PGMEA3165部を加 え希釈した後、無水マレイン酸を 250部添加し、さらに 80°Cにおいて 7時間反応を « 続させ、活性光線硬化型ハイパーブランチポリマー（9)を得た。得られた活性光線硬 化型ハイパーブランチポリマー（9)の数平均分子量は 4100、酸価は 1700eqZton 、ガラス転移温度は 12°C、不飽和結合基濃度は 900eqZton、芳香環濃度は 1900 eqZtonであった。これら結果を表 2、 3に示した。  1000 parts of the hyperbranch (A1) prepared in Example 1, 1000 parts of PGMEA, and 1,000 parts of toluene were charged. After dissolution, the mixture was heated to 145 ° C. to distill off the water in the system, and the toluene was completely distilled off. Add 738 parts of succinic anhydride and 5.5 parts of TEA as a catalyst, react for 5 hours at 80 ° C in a nitrogen atmosphere, add 788 parts of glycidyl ether and 27 parts of TPP as a catalyst. The mixture was further reacted at 80 ° C for 7 hours. Subsequently, 3165 parts of PGMEA was added for dilution, 250 parts of maleic anhydride was added, and the reaction was further continued at 80 ° C. for 7 hours to obtain an actinic ray curable hyperbranched polymer (9). The actinic ray curable hyperbranched polymer (9) obtained had a number average molecular weight of 4100, an acid value of 1700 eqZton, a glass transition temperature of 12 ° C, an unsaturated bond group concentration of 900 eqZton, and an aromatic ring concentration of 1900 eqZton. It was. These results are shown in Tables 2 and 3.
[0074] 比較例（10)  [0074] Comparative Example (10)
実施例 1で作製したハイパーブランチ（A1) 1000部と PGMEA1000部、トルエン 1 000部を仕込み、溶解後 145度まで加熱して系内の水分を溜去、トルエンを完全に 溜去した。無水トリメリット酸 938部、テトラヒドロ無水フタル酸 433部、触媒として TEA 5. 5部を添加し、 80°C、窒素雰囲気下で 5時間反応させた後、メチルダリシジルエー テル 983部、触媒として TPP27部を添加し、さらに 80°Cにおいて 7時間反応させた。 続いて、 PGMEA4375部をカ卩ぇ希釈した後、無水マレイン酸を 229部添カ卩し、さら に 80°Cにお 、て 7時間反応を継続させ、活性光線硬化型ハイパーブランチポリマー (10)を得た。得られた活性光線硬化型ノ、ィパーブランチポリマー（10)の数平均分 子量は 4300、酸価は 1050eqZton、ガラス転移温度は 38°C、不飽和結合基濃度 は 1500eqZton、芳香環濃度は 1400eqZtonであった。これら結果を表 2、 3に示 した。 1000 parts of the hyperbranch (A1) prepared in Example 1, 1000 parts of PGMEA, and 1,000 parts of toluene were charged. After dissolution, the mixture was heated to 145 ° C. to distill off the water in the system, and the toluene was completely distilled off. Add 938 parts trimellitic anhydride, 433 parts tetrahydrophthalic anhydride, 5.5 parts TEA as a catalyst, react at 80 ° C under nitrogen atmosphere for 5 hours, then 983 parts methyldaricidyl ether as catalyst 27 parts of TPP was added, and the mixture was further reacted at 80 ° C for 7 hours. Subsequently, 4375 parts of PGMEA was diluted in a cup, and then added with 229 parts of maleic anhydride, and the reaction was further continued at 80 ° C for 7 hours to obtain an actinic ray curable hyperbranched polymer. (10) was obtained. The number average molecular weight of the obtained actinic radiation curable polymer, iperbranched polymer (10) is 4300, acid value is 1050eqZton, glass transition temperature is 38 ° C, unsaturated bond group concentration is 1500eqZton, aromatic ring concentration is 1400 eq Zton. These results are shown in Tables 2 and 3.
[0075] 比較例（11)  [0075] Comparative Example (11)
ハイパーブランチポリマー A5の合成  Synthesis of hyperbranched polymer A5
パーシャルコンデンサー、温度計、攪拌棒を具備した反応釜にペンタエリスリトール 136部、ジメチロールブタン酸 1776部、 PTS21部を仕込み 100°C下に攪拌し、均 一な液状混合溶融物とした。次いでトルエン 100部を注入後 140°Cに昇温し、トルェ ンを還流しつつ発生する水を共沸により系外に溜去した。同条件で 2時間反応を «I 続した後、系外へトルエンを留去し、ハイパーブランチポリマー A5を得た。得られた 重縮合物の酸価は 250eqZton、数平均分子量は 1500であった。  A reaction vessel equipped with a partial condenser, a thermometer, and a stirring rod was charged with 136 parts of pentaerythritol, 1776 parts of dimethylolbutanoic acid and 21 parts of PTS, and stirred at 100 ° C to obtain a uniform liquid mixed melt. Next, 100 parts of toluene was injected, the temperature was raised to 140 ° C., and water generated while refluxing toluene was distilled out of the system by azeotropic distillation. After the reaction was continued for 2 hours under the same conditions, toluene was distilled out of the system to obtain hyperbranched polymer A5. The polycondensate obtained had an acid value of 250 eqZton and a number average molecular weight of 1500.
[0076] 次!、で、このハイパーブランチポリマー（A5) 1000部と PGMEA1000部、トルエン 1000部を仕込み、溶解後 145度まで加熱して系内の水分を溜去、トルエンを完全に 溜去した。無水トリメリット酸 1302部、触媒として TEA5. 5部を添加し、 80°C、窒素 雰囲気下で 5時間反応させた後、フエ-ルグリシジルエーテル 1743部、触媒として T PP27部を添加し、さらに 80°Cにおいて 7時間反応させた。続いて、 PGMEA5638 部を加え希釈した後、無水マレイン酸を 380部添加し、さらに 80°Cにおいて 7時間反 応を継続させ、活性光線硬化型ハイパーブランチポリマー（11)を得た。得られた活 性光線硬化型ハイパーブランチポリマー（11)の数平均分子量は 3200、酸価は 124 Oeq/ton,ガラス転移温度は 24°C、不飽和結合基濃度は 900eqZton、芳香環濃 度は 4100eqZtonであった。これら結果を表 2、 3に示した。  [0076] Next !, 1000 parts of this hyperbranched polymer (A5), 1000 parts of PGMEA, and 1000 parts of toluene were charged, and after dissolution, heated to 145 ° C to distill off the water in the system and toluene was completely distilled off. . Add 1302 parts of trimellitic anhydride, 5 parts of TEA as a catalyst, react for 5 hours at 80 ° C in a nitrogen atmosphere, add 1743 parts of glycidyl ether, and 27 parts of TPP as a catalyst. The reaction was carried out at 80 ° C for 7 hours. Subsequently, after adding 5638 parts of PGMEA and diluting, 380 parts of maleic anhydride was added, and the reaction was further continued at 80 ° C. for 7 hours to obtain an actinic ray curable hyperbranched polymer (11). The resulting photocured hyperbranched polymer (11) has a number average molecular weight of 3200, an acid value of 124 Oeq / ton, a glass transition temperature of 24 ° C, an unsaturated bond group concentration of 900 eqZton, and an aromatic ring concentration of 4100 eq Zton. These results are shown in Tables 2 and 3.
[0077] 比較例（12)  [0077] Comparative Example (12)
実施例 1で作製したハイパーブランチ（A1) 1000部と PGMEA1000部、トルエン 1 000部を仕込み、溶解後 145度まで加熱して系内の水分を溜去、トルエンを完全に 溜去した。無水トリメリット酸 1248部、触媒として TEA5. 5部を添加し、 80°C、窒素 雰囲気下で 5時間反応させた後、 p—tert—ブチルフエ-ルグリシジルエーテル 180 9部、触媒として TPP27部を添加し、さらに 80°Cにおいて 7時間反応させた。その後 PGMEA5085部をカ卩ぇ希釈し、ハイパーブランチポリマー（12)を得た。得られたハ ィパーブランチポリマー（12)の数平均分子量は 4700、酸価は 1020eqZton、ガラ ス転移温度は 35°C、不飽和結合基濃度は OeqZton、芳香環濃度は 3800eqZton であった。これら結果を表 2、 3に示した。 1000 parts of the hyperbranch (A1) prepared in Example 1, 1000 parts of PGMEA, and 1,000 parts of toluene were charged. After dissolution, the mixture was heated to 145 ° C. to distill off the water in the system, and the toluene was completely distilled off. Add 1248 parts of trimellitic anhydride and 5.5 parts of TEA as a catalyst, react at 80 ° C under nitrogen atmosphere for 5 hours, and then add 9 parts of p-tert-butylphenol glycidyl ether 180 and 27 parts of TPP as a catalyst. Then, the mixture was further reacted at 80 ° C for 7 hours. afterwards 5085 parts of PGMEA was diluted with a cake to obtain a hyperbranched polymer (12). The number average molecular weight of the obtained hyperbranched polymer (12) was 4700, the acid value was 1020 eqZton, the glass transition temperature was 35 ° C, the unsaturated bond group concentration was OeqZton, and the aromatic ring concentration was 3800 eqZton. These results are shown in Tables 2 and 3.
[0078] 比較例（13)  [0078] Comparative Example (13)
比較例 11で得られたハイパーブランチポリマー（A5) 1000部、 PGMEA1000部、 トルエン 1000部を仕込み、溶解後、 145度まで加熱して系内の水分を溜去、トルェ ンを完全に溜去した。無水マレイン酸 794部、触媒として TEA5. 5部を添カ卩し、 80 °C、窒素雰囲気下で 3時間反応させた後、 4ーヒドロキシブチルアタリレートグリシジル エーテル 1350部、触媒として TPP27部を添加し、更に 115°Cにおいて 4時間反応 を継続させた。続いて PGMEA3900部、ベンゾフエノンテトラカルボン酸二無水物を 120部添加し、更に 115°Cにて反応を継続させ、ノ、ィパーブランチポリマー（13)を 得た。得られたハイパーブランチポリマー（13)の平均分子量は 4700、酸価は 600e qZtonガラス転移温度は 5°C、不飽和結合基濃度は 4500eqZton、芳香環濃度は 200eqZtonであった。  The hyperbranched polymer (A5) obtained in Comparative Example 11 (1000 parts), PGMEA (1000 parts), and toluene (1000 parts) were charged. After dissolution, the mixture was heated to 145 ° C. to distill off water in the system, and toluene was completely distilled off. . Add 794 parts of maleic anhydride and 5.5 parts of TEA as a catalyst, react at 80 ° C for 3 hours under nitrogen atmosphere, add 1350 parts of 4-hydroxybutyl acrylate diglycidyl ether and 27 parts of TPP as a catalyst. The reaction was further continued at 115 ° C for 4 hours. Subsequently, 3900 parts of PGMEA and 120 parts of benzophenonetetracarboxylic dianhydride were added, and the reaction was further continued at 115 ° C. to obtain a hyperperbranched polymer (13). The average molecular weight of the obtained hyperbranched polymer (13) was 4700, the acid value was 600 eqZton, the glass transition temperature was 5 ° C, the unsaturated bond group concentration was 4500 eqZton, and the aromatic ring concentration was 200 eqZton.
[0079] 比較例（14)  [0079] Comparative Example (14)
比較例 11で得られたハイパーブランチポリマー（A5) 1000部、 PGMEA1000部、 トルエン 1000部を仕込み、溶解後 145度まで加熱して系内の水分を溜去、トルエン を完全に溜去した。ナフタレン—2, 3—ジカルボン酸無水物 1600部、触媒として TE Aを 5. 5部添カ卩し、 80°C、窒素雰囲気下で 3時間反応させた後、フニルグリシジルェ 一テル 400部、 4—ヒドロキシブチルアタリレートグリシジルエーテル 450部、触媒とし て TPP 17部を添カ卩し、さらに 115°Cにおいて 4時間反応を継続させ、 PGMEA417 5部で希釈して活性光線硬化型ノ、ィパーブランチポリマー（14)を得た。活性光線硬 化型ハイパーブランチポリマー（14)の数平均分子量は 4100、酸価は 1600eqZto n、ガラス転移温度は 28°C、不飽和結合基濃度は 650eqZton、芳香環濃度は 800 eqZtonであった。これら結果を表 2、 3にまとめた。  The hyperbranched polymer (A5) obtained in Comparative Example 11 (1000 parts), PGMEA (1000 parts), and toluene (1000 parts) were charged. After dissolution, the mixture was heated to 145 ° C. to distill off the water in the system, and the toluene was completely distilled off. 1600 parts of naphthalene-2,3-dicarboxylic anhydride, 5.5 parts of TE A as a catalyst, and reacted for 3 hours at 80 ° C in a nitrogen atmosphere, followed by 400 parts of funil glycidyl ether , 450 parts of 4-hydroxybutyl talidyl glycidyl ether and 17 parts of TPP as a catalyst were added, and the reaction was further continued at 115 ° C for 4 hours, diluted with 5 parts of PGMEA417, A perbranched polymer (14) was obtained. The number average molecular weight of the actinic ray curable hyperbranched polymer (14) was 4100, the acid value was 1600 eqZton, the glass transition temperature was 28 ° C, the unsaturated bond group concentration was 650 eqZton, and the aromatic ring concentration was 800 eqZton. These results are summarized in Tables 2 and 3.
[0080] 比較例（15)  [0080] Comparative Example (15)
比較例 11で得られたハイパーブランチポリマー（A5) 1000部、 PGMEA1000部、 トルエン 1000部を仕込み、溶解後 145度まで加熱して系内の水分を溜去、トルエン を完全に溜去した。無水コハク酸 810部、触媒として TEAを 5. 5部添加し、 105°C、 窒素雰囲気下で 3時間反応させた後、フエ-ルグリシジルエーテル 730部、触媒とし て TPP 17部を添カ卩し、さらに 115°Cにおいて 4時間反応を継続させ、 PGMEA281 0部で希釈してハイパーブランチポリマー（15)を得た。得られたノヽィパーブランチポ リマー（15)の数平均分子量は 3500、酸価は 1500eqZton、ガラス転移温度は 45 。C、芳香環濃度は 1900eqZtonであった。これら結果を表 2、 3にまとめた。 1000 parts of hyperbranched polymer (A5) obtained in Comparative Example 11, 1000 parts of PGMEA, 1000 parts of toluene was charged, and after dissolution, it was heated to 145 ° C. to distill off water in the system, and toluene was completely distilled off. Add 810 parts of succinic anhydride, 5.5 parts of TEA as a catalyst, react at 105 ° C in a nitrogen atmosphere for 3 hours, add 730 parts of glycidyl ether and 17 parts of TPP as a catalyst. The reaction was further continued at 115 ° C for 4 hours, and diluted with 10 parts of PGMEA281 to obtain a hyperbranched polymer (15). The obtained no-perbranched polymer (15) has a number average molecular weight of 3500, an acid value of 1500 eqZton, and a glass transition temperature of 45. C, aromatic ring concentration was 1900eqZton. These results are summarized in Tables 2 and 3.
[0081] 比較例（16)  [0081] Comparative Example (16)
実施例 1で作製したハイパーブランチ（A1) 1000部、 PGMEA1000部、トルエン 1 000部を仕込み、溶解後 145度まで加熱して系内の水分を溜去、トルエンを完全に 溜去した。無水トリメリット酸 1200部、触媒として TEA5. 5部を添加し、 80°C、窒素 雰囲気下で 5時間反応させた後、フエ-ルグリシジルエーテル 450部、触媒として TP P15部を添カ卩し、さらに 80°Cにおいて 7時間反応させた。続いて、 PGMEA3710部 を加え希釈した後、無水マレイン酸を 490部添加し、さらに 80°Cにおいて 7時間反応 を継続させ、活性光線硬化型ハイパーブランチポリマー（2)を得た。得られたハイパ 一ブランチポリマー（16)の数平均分子量は 5200、酸価は 750eqZton、ガラス転 移温度は 32°C、不飽和結合基濃度は 1500eqZton、芳香環濃度は 2800eqZton であった。これら結果を表 2、 3にまとめた。  1000 parts of hyperbranch (A1) prepared in Example 1, 1000 parts of PGMEA, and 1000 parts of toluene were charged, and after melting, the water in the system was distilled off by heating to 145 ° C., and toluene was distilled off completely. After adding 1200 parts of trimellitic anhydride and 5.5 parts of TEA as a catalyst and reacting at 80 ° C in a nitrogen atmosphere for 5 hours, 450 parts of glycidyl ether and 15 parts of TPP as a catalyst were added. The mixture was further reacted at 80 ° C for 7 hours. Subsequently, 3710 parts of PGMEA was added for dilution, 490 parts of maleic anhydride was added, and the reaction was further continued at 80 ° C. for 7 hours to obtain an actinic ray curable hyperbranched polymer (2). The hyper-branched polymer (16) obtained had a number average molecular weight of 5200, an acid value of 750 eqZton, a glass transition temperature of 32 ° C, an unsaturated bond group concentration of 1500 eqZton, and an aromatic ring concentration of 2800 eqZton. These results are summarized in Tables 2 and 3.
[0082] 比較例（17)  [0082] Comparative Example (17)
ポリエステル榭脂 A6の合成  Synthesis of polyester resin A6
リービッヒ冷却管、温度計、攪拌棒を具備したフラスコにテレフタル酸ジメチル 194 部イソフタル酸ジメチル 194部、ネオペンチルグリコール 146部、エチレングリコール 160部、重合触媒としてテトラブトキシチタネート 0. 2部を仕込み 200〜225°Cで 3時 間エステル交換反応を進めた後、 250°C、減圧下に 30分間重合反応を行ない、温 度を 220°Cに下げ、 N雰囲気下常圧に戻した。ついで無水トリメリット酸 5. 8部添カロ  A flask equipped with a Liebig condenser, thermometer and stir bar is charged with 194 parts of dimethyl terephthalate, 194 parts of dimethyl isophthalate, 146 parts of neopentyl glycol, 160 parts of ethylene glycol, and 0.2 part of tetrabutoxy titanate as a polymerization catalyst. After proceeding the transesterification reaction at 225 ° C for 3 hours, the polymerization reaction was carried out at 250 ° C under reduced pressure for 30 minutes, the temperature was lowered to 220 ° C, and the pressure was returned to normal pressure under N atmosphere. Then trimellitic anhydride
2  2
し、同温度、 N雰囲気下で 30分撹拌を継続し、生成物を取り出した。得られたポリエ  Then, stirring was continued for 30 minutes under the same temperature and N atmosphere, and the product was taken out. The obtained polyester
2  2
ステル樹脂 (A6)の数平均分子量は 5000、酸価は 250eqZtonであった。  The number average molecular weight of the steal resin (A6) was 5000, and the acid value was 250 eqZton.
[0083] 次いで上記ポリエステル (A6) 1000部を PGMEA750部〖こ溶解し、 4ーヒドロキシ ブチルアタリレートグリシジルエーテル 43部、反応触媒として TPP1. 5部を添カ卩し、 1 30°Cで 5時間反応させ、比較合成例（17)のポリマーを得た。数平均分子量は 5500 、酸価は 50eqZton、ガラス転移温度は 55°C、不飽和結合基濃度は 200eqZton、 芳香環濃度は 3500eqZtonであった。これら結果を表 2、 3に示した。 [0083] Next, 1000 parts of the above polyester (A6) was dissolved in 750 parts of PGMEA, and 4-hydroxy 43 parts of butyl acrylate diglycidyl ether and 1.5 parts of TPP as a reaction catalyst were added and reacted at 130 ° C. for 5 hours to obtain a polymer of Comparative Synthesis Example (17). The number average molecular weight was 5,500, the acid value was 50 eqZton, the glass transition temperature was 55 ° C, the unsaturated bond group concentration was 200 eqZton, and the aromatic ring concentration was 3500 eqZton. These results are shown in Tables 2 and 3.
[0084] 比較例（18) [0084] Comparative Example (18)
ポリエステル榭脂 A7の合成  Synthesis of polyester resin A7
リービッヒ冷却管、温度計、攪拌棒を具備したフラスコにテレフタル酸ジメチル 194 部イソフタル酸ジメチル 194部、ネオペンチルグリコール 146部、エチレングリコール 160部、重合触媒としてテトラブトキシチタネート 0. 2部を仕込み 200〜225°Cで 3時 間エステル交換反応を進めた後、 250°C、減圧下に 20分間重合反応を行ない、生 成物を取り出した。得られたポリエステル榭脂 (A7)の数平均分子量は 2000、酸価 1 8eq/ tonでめった。  A flask equipped with a Liebig condenser, thermometer and stir bar is charged with 194 parts of dimethyl terephthalate, 194 parts of dimethyl isophthalate, 146 parts of neopentyl glycol, 160 parts of ethylene glycol, and 0.2 part of tetrabutoxy titanate as a polymerization catalyst. After proceeding the transesterification reaction at 225 ° C for 3 hours, a polymerization reaction was carried out at 250 ° C under reduced pressure for 20 minutes, and the product was taken out. The number average molecular weight of the obtained polyester resin (A7) was 2000, and the acid value was 18 eq / ton.
[0085] つ!、で上記ポリエステル (A7) 1000部を PGMEA2140部に溶解し、 NKエステル A—TMM— 3L (ペンタエリスリトールとアクリル酸の縮合物） 150部、ネオペンチル グリコール 40部を添加、均一に溶解した。 MDI235部、反応触媒としてジブチル錫 ジラウレート、 0. 25部添カ卩し、 70°Cで 8時間反応させ、比較例（18)のポリエステルゥ レタンアタリレート榭脂を得た。数平均分子量は 11, 000、ガラス転移温度は 54°C、 酸価は 20eqZton、不飽和結合基濃度は 1000eqZton、芳香環濃度は 3900eq Ztonであった。 これら結果を表 2、 3に示した。  [0085] In 1 !, 1000 parts of the above polyester (A7) was dissolved in 2140 parts of PGMEA, 150 parts of NK ester A-TMM-3L (condensate of pentaerythritol and acrylic acid) and 40 parts of neopentyl glycol were added uniformly. Dissolved. 235 parts of MDI, 0.25 part of dibutyltin dilaurate as a reaction catalyst were added, and the mixture was reacted at 70 ° C. for 8 hours to obtain a polyester urethane acrylate resin of Comparative Example (18). The number average molecular weight was 11,000, the glass transition temperature was 54 ° C, the acid value was 20 eqZton, the unsaturated bond group concentration was 1000 eqZton, and the aromatic ring concentration was 3900 eq Zton. These results are shown in Tables 2 and 3.
[0086] 上記比較例（9)、 （10)、 （16)はハイパーブランチ構造を有している力 分子内に 芳香環が不足している例、比較例（11)はハイパーブランチ構造及び、分子内に十 分な芳香族炭化水素残基を有しているがベースとなる脂肪族ハイパーブランチコア 構造の数平均分子量が不足している例、比較例（12)は、ハイパーブランチ構造、及 び、分子内に十分な芳香族炭化水素残基を有して 、るが不飽和結合基を有さな ヽ 例、比較合成例（13)、 （14)は、ハイパーブランチ構造は有しているものの、ハイパ 一ブランチのコア構造の分子量が不足し、かつ芳香環が不足している例、比較合成 例（15)はハイパーブランチ構造は有しているものの、ハイパーブランチコア構造の 分子量が不足し、かつ芳香環が不足している、さらに不飽和結合基をも有さない例、 また比較例（ 17) （ 18)はハイパーブランチ構造を有さな!/、例である。 [0086] The comparative examples (9), (10), (16) are examples of a force molecule having a hyperbranch structure, the aromatic ring is deficient in the molecule, the comparative example (11) is a hyperbranch structure, Examples that have sufficient aromatic hydrocarbon residues in the molecule but lack the number-average molecular weight of the base aliphatic hyperbranched core structure, and Comparative Example (12) are hyperbranched structures and In addition, examples of comparative synthesis examples (13) and (14) having a sufficient aromatic hydrocarbon residue in the molecule but not having an unsaturated bond group have a hyperbranched structure. However, the molecular weight of the hyperbranched core structure is insufficient, the aromatic ring is insufficient, and the comparative synthesis example (15) has a hyperbranched structure, but the molecular weight of the hyperbranched core structure is insufficient. In addition, it lacks an aromatic ring and has an unsaturated bond group. Unusual, Comparative examples (17) and (18) are examples that do not have a hyper-branch structure! /.
[0087] 上記得られたベースとなるハイパーブランチポリマー（コア)等の組成、物性を表 1 に、そこ力 合成した本発明のハイパーブランチポリマーの組成、物性を比較例の組 成、物性と共に表 2 3に示した。 [0087] The composition and physical properties of the above-obtained hyperbranched polymer (core) and the like are shown in Table 1, and the composition and physical properties of the hyperbranched polymer of the present invention synthesized therewith are shown together with the composition and physical properties of the comparative examples. Shown in 2 3.
[0088] [表 1] [0088] [Table 1]
Figure imgf000029_0001
Figure imgf000029_0001
[0089] [表 2] [0089] [Table 2]
脂肪族ポリエステル 単環式芳香族化合物 不飽和結合含有化合物 その他無水酸 Aliphatic polyesters Monocyclic aromatic compounds Compounds containing unsaturated bonds Other anhydrides
ハイパーブランチポリ その他の化合物 無水酸基含 グリシジル基 無水酸基含 グリシジル基 /グリシジル  Hyperbranched poly Other compounds Hydroxyl-free glycidyl group Hydroxyl-free glycidyl group / glycidyl
(比較例で使用） マー 有タイプ 含有タイプ 有タイプ 含有タイプ 化合物 (Used in the comparative example) Mer Yes Type Contain Type Yes Type Contain Type Compound
A1 PA A1 PA
1 TBPGE MAN  1 TBPGE MAN
1000部 954部 1400部 760部  1000 parts 954 parts 1400 parts 760 parts
AI TMA PGE MAN  AI TMA PGE MAN
2  2
1000部 1200咅 [5 1540部 362咅 [5  1000 parts 1200 咅 [5 1540 parts 362 咅 [5
TMA  TMA
Al 750部 PGE MAN  Al 750 parts PGE MAN
3  Three
1000部 PA 1320部 404部  1000 parts PA 1320 parts 404 parts
実 Fruit
411部  411 copies
施 Out
A1 T A PGE OSA HBAGE  A1 T A PGE OSA HBAGE
例 4 Example 4
1000部 1433部 621部 240部 360部  1000 parts 1433 parts 621 parts 240 parts 360 parts
A1 TMA PGE THPA  A1 TMA PGE THPA
5  Five
1000部 1563部 2340部 230部  1000 parts 1563 parts 2340 parts 230 parts
A2 T A TBPGE DSA G A SA  A2 T A TBPGE DSA G A SA
6  6
1000部 1299咅 [5 1918部 210部 330部 110部  1000 parts 1299 mm (5 1918 parts 210 parts 330 parts 110 parts
A3 T A PGE MAN HBAGE BTDA A3 T A PGE MAN HBAGE BTDA
7 7
1000部 908部 922部 189部 149部 52部  1000 parts 908 parts 922 parts 189 parts 149 parts 52 parts
A4 TMA PGE MAN  A4 TMA PGE MAN
8  8
1000部 1325咅 [1 1743部 403部  1000 parts 1325 咅 [1 1743 parts 403 parts
A1 PGE MAN SA  A1 PGE MAN SA
9  9
1000部 フ 88部 250咅 [！  1000 copies 88 copies 250 咅 [!
MAN  MAN
A1 TMA 229部 MGE A1 TMA 229 parts MGE
10 Ten
1000部 938部 THPA 983部  1000 parts 938 parts THPA 983 parts
433部  433 copies
A5 TMA PGE MAN  A5 TMA PGE MAN
11  11
1000部 1302咅 [1 1743部 380部 S o  1000 parts 1302 咅 [1 1743 parts 380 parts S o
A1 TMA TBPGE  A1 TMA TBPGE
12  12
1000部 1248咅 [1 1809部  1000 parts 1248 咅 [1 1809 parts
MAN HBAGE BTDA  MAN HBAGE BTDA
比 13 Ratio 13
1000部 1350部 120咅|5  1000 parts 1350 parts 120 咅 | 5
較 A5 Comparison A5
14 PGE HBAGE NDA  14 PGE HBAGE NDA
例 1000部 400部 450部 1600部 Example 1000 parts 400 parts 450 parts 1600 parts
A5 PGE SA  A5 PGE SA
15  15
1000部 730部 810部  1000 parts 730 parts 810 parts
A1 TMA PGE MAN  A1 TMA PGE MAN
16  16
■0部 1200部 450部 490部  ■ 0 parts 1200 parts 450 parts 490 parts
A6  A6
17 HBAGE  17 HBAGE
(ハイパーブランチでない  (Not hyperbranch
43部  43 parts
ポリエステル） 1000部  Polyester) 1000 parts
A7  A7
PETA NPG MD1 PETA NPG MD1
18 (ノヽィパ一ブランチでない 18 (not a noise branch
150咅 [i 40部 235部 ポリエステル） 71000部 3] 特性値  150 咅 [i 40 parts 235 parts polyester) 71000 parts 3] Characteristic value
ガラス 不飽和  Glass unsaturated
数平均 方食 is;辰度 転移温度 口口  Number average bite is;
分子量 (eq/ton) Molecular weight (eq / ton)
(。c) (eq/ton)(.C) (eq / ton)
1 3 4700 1800 1900 32001 3 4700 1800 1900 3200
2 30 6600 1420 900 4000 実 3 15 5500 1510 1100 4000 施 4 18 4800 2680 750 3200 例 5 35 7300 420 300 45002 30 6600 1420 900 4000 Actual 3 15 5500 1510 1100 4000 Out 4 18 4800 2680 750 3200 Example 5 35 7300 420 300 4500
6 28 7800 780 650 35006 28 7800 780 650 3500
7 32 5400 1500 850 36007 32 5400 1500 850 3600
8 27 3800 1400 900 41008 27 3800 1400 900 4100
9 12 4100 1700 900 19009 12 4100 1700 900 1900
10 38 4300 1050 1500 140010 38 4300 1050 1500 1400
11 24 3200 1240 900 410011 24 3200 1240 900 4100
12 35 4700 1020 0 3800 比 12 35 4700 1020 0 3800 ratio
13 5 4700 600 4500 200 較  13 5 4700 600 4500 200 Comparison
14 28 4100 1600 650 800 例  14 28 4100 1600 650 800 Example
15 45 3500 1500 0 1900 15 45 3500 1500 0 1900
16 32 5200 750 1500 280016 32 5200 750 1500 2800
17 55 5500 50 200 350017 55 5500 50 200 3500
18 54 11000 20 1000 3900 配合例 1 18 54 11000 20 1000 3900 Formulation Example 1
顔料分散性、分散後安定性の評価  Evaluation of pigment dispersibility and stability after dispersion
上記実施例（1)で得られた活性光線硬化型ハイパーブランチポリマーの 30wt%PG MEA溶液を調製し、以下配合処方により感光性組成物を調製した。 A 30 wt% PG MEA solution of the actinic ray curable hyperbranched polymer obtained in Example (1) above was prepared, and a photosensitive composition was prepared by the following formulation.
(配合処方）  (Combination prescription)
カーボンブラック 45重量部 45 parts by weight of carbon black
(平均粒径 = 16nm, BET= 200m g, DBP吸油量 = 70ml/100g) ハイパーブランチポリマー（1) (固形分 30%) 45重量部（固形分）  (Average particle size = 16nm, BET = 200mg, DBP oil absorption = 70ml / 100g) Hyperbranched polymer (1) (solid content 30%) 45 parts by weight (solid content)
トリメチロールプロパントリアタリレート 90重量部 90 parts by weight of trimethylolpropane tritalylate
開始剤 (ィルガキュア一 907) 10重量部 Initiator (Irgacure 907) 10 parts by weight
増感剤 (ミヒラーズケトン） 2. 2重量部 Sensitizer (Michler's ketone) 2. 2 parts by weight
PGMEA 255重量部  PGMEA 255 parts by weight
上記組成物を混練処理した後、ペイントシェーカーにて分散を行い、カーボンブラッ ク分散塗料を作製した。 The composition was kneaded and then dispersed with a paint shaker to prepare a carbon black dispersion paint.
次に、得られたカーボンブラック分散塗料を 25ミクロン厚の二軸延伸 PETフィルムに 乾燥後塗膜厚みが 1ミクロンになるように塗布し、塗膜を 120°C、 10分間熱風乾燥さ せた。次いで 50mj/cm2で UV照射処理し、硬化済みのカーボンブラック分散塗膜 を得た。活性光線硬化型ハイパーブランチポリマーの分散性能は、作製した塗膜の 表面光沢を測定し評価した。カーボンブラック分散塗膜の光沢は 45度光沢を測定し た。結果を表 4に示す。 Next, the obtained carbon black-dispersed paint was applied to a 25 micron thick biaxially stretched PET film so that the coating thickness was 1 micron after drying, and the coating was dried with hot air at 120 ° C for 10 minutes. . Subsequently, UV irradiation treatment was performed at 50 mj / cm 2 to obtain a cured carbon black dispersed coating film. The dispersion performance of the actinic ray curable hyperbranched polymer was evaluated by measuring the surface gloss of the prepared coating film. The gloss of the carbon black-dispersed coating film was measured at 45 degrees. The results are shown in Table 4.
また、塗膜作製前のカーボンブラック分散塗料の初期分散時の塗料状態を観測したIn addition, the state of the paint at the initial dispersion of the carbon black dispersion paint before the coating film preparation was observed.
。また塗膜作製前のカーボンブラック分散塗料を 40度 X 2週間保存した後の塗料状 態を観察する加熱促進試験を行うことにより塗料の保存安定性を評価した。塗料状 態の程度を以下の 4段階で示した。結果を表 4に示す。 . In addition, the storage stability of the paint was evaluated by conducting a heating acceleration test to observe the paint state after storing the carbon black-dispersed paint before preparation of the coating film at 40 degrees X for 2 weeks. The degree of paint state is shown in the following four stages. The results are shown in Table 4.
◎:凝集起こらず、増粘無し  A: No aggregation occurs and no thickening occurs
〇：わずかに凝集、増粘有り  ◯: Slightly aggregated and thickened
△:凝集、増粘目立つ  Δ: Conspicuous aggregation and thickening
X：凝集、増粘顕著に目立つ [0092] 紫外線硬化性の評価 X: Conspicuous noticeable aggregation and thickening [0092] Evaluation of UV Curability
上記合成例（1)で得られた活性光線硬化型ノ、ィパーブランチポリマーの 30wt%P GMEA溶液を調製し、以下配合処方により塗工液を作製し、 25ミクロン厚のニ軸延 伸 PETフィルムに乾燥後塗膜厚みが 2ミクロンになるように塗布し、塗膜を 120°C、 1 0分間熱風乾燥させた。次いで 50miZcm2で UV照射処理し、得られた硬化フィル ムを PGMEAに 1時間浸漬した。 Prepare a 30 wt% P GMEA solution of the actinic radiation curable polymer and hyperbranched polymer obtained in Synthesis Example (1) above, and prepare a coating solution according to the following formulation. A 25-micron thick biaxially stretched PET After drying, the film was applied to a thickness of 2 microns, and the film was dried with hot air at 120 ° C for 10 minutes. Next, UV irradiation treatment was performed at 50 miZcm 2 , and the obtained cured film was immersed in PGMEA for 1 hour.
浸漬前後でのフィルム重量変化力 未溶解残存硬化塗膜の重量％を計算し、 UV硬 化性能を比較した。結果を表 4に示す。  Film weight change before and after immersion The weight% of undissolved residual cured coating was calculated and the UV curing performance was compared. The results are shown in Table 4.
(配合処方）  (Compound formulation)
ハイパーブランチポリマー（1) (固形分 30%) 80重量部（固形分）  Hyperbranched polymer (1) (solid content 30%) 80 parts by weight (solid content)
トリメチロールプロパントリアタリレート 20重量部  20 parts by weight of trimethylolpropane tritalylate
開始剤 (ィルガキュア一 907) 4重量部  Initiator (Irgacure 907) 4 parts by weight
増感剤 (ミヒラーズケトン） 1重量部  Sensitizer (Michler's ketone) 1 part by weight
[0093] 配合例 2〜8、比較配合例 9〜18  [0093] Formulation Examples 2-8, Comparative Formulation Examples 9-18
実施例（2)〜（8)、比較例（9)〜（18)のポリマーを用いて、配合例 1と同様にして 評価を行った。結果を表 4に示す。  Evaluation was performed in the same manner as in Formulation Example 1 using the polymers of Examples (2) to (8) and Comparative Examples (9) to (18). The results are shown in Table 4.
[0094] [表 4] [0094] [Table 4]
ポリマ一 塗膜表面光沢（％) Polymer surface gloss (%)
塗料状態 保存安定性 硬化性（％) (分散性）  Paint state Storage stability Curability (%) (Dispersibility)
1 実施例 1 160 ◎ ◎ 96  1 Example 1 160 ◎ ◎ 96
2 実施例 2 175 ◎ ◎ 94  2 Example 2 175 ◎ ◎ 94
3 実施例 3 170  3 Example 3 170
酉己 ◎ ◎ 99 酉 ◎ ◎ 99
4 実施例 4 166 4 Example 4 166
例 ◎ ◎ 96 Example ◎ ◎ 96
5 実施例 5 172 ◎ ◎ 96 5 Example 5 172 ◎ ◎ 96
6 実施例 6 163 ◎ ◎ 97  6 Example 6 163 ◎ ◎ 97
7 実施例 7 171 ◎ ◎ 94  7 Example 7 171 ◎ ◎ 94
8 実施例 8 170 ◎ △~〇 94  8 Example 8 170 ◎ △ ~ 〇 94
9 比較例 9 123 Δ X 57  9 Comparative Example 9 123 Δ X 57
10 比較例 1 0 105 Δ X 66  10 Comparative Example 1 0 105 Δ X 66
1 1 比較例 1 1 170 ◎ X 90 比 12 比較例 1 2 168 ◎ X 92 1 1 Comparative example 1 1 170 ◎ X 90 ratio 12 Comparative example 1 2 168 ◎ X 92
13 比較例 1 3 52 X X 0 13 Comparative Example 1 3 52 X X 0
ム  Mu
14 比較例 1 4 78 X X 45 例  14 Comparative Example 1 4 78 X X 45 Example
15 比較例 1 5 120 Δ X 0  15 Comparative Example 1 5 120 Δ X 0
16 比較例 1 6 146 Δ-Ο X 69  16 Comparative Example 1 6 146 Δ-Ο X 69
1 7 比較例 1 7 78 X X 45  1 7 Comparative Example 1 7 78 X X 45
18 比較例 1 8 92 X X 58  18 Comparative Example 1 8 92 X X 58
[0095] 表 4の結果より明らかに本発明のハイパーブランチポリマーは優れた顔料分散性、 低エネルギー UV照射で高い硬化反応性が得られる。 [0095] From the results in Table 4, the hyperbranched polymer of the present invention clearly exhibits excellent pigment dispersibility and high curing reactivity when irradiated with low energy UV.
産業上の利用可能性  Industrial applicability
[0096] 本発明は、紫外線などの活性光線の照射により、極めて低エネルギーで硬化塗膜を 形成し得る活性光線硬化型ハイパーブランチポリマーを見出すと共に、電子材料用 途等に用いられるレジスト材料として優れた特性を発揮する活性光線硬化型榭脂組 成物を提供することを目的とする。  [0096] The present invention finds an actinic ray curable hyperbranched polymer capable of forming a cured coating film with extremely low energy by irradiation with actinic rays such as ultraviolet rays, and is excellent as a resist material used for electronic materials. It is an object of the present invention to provide an actinic ray curable resin composition that exhibits excellent characteristics.

Claims

請求の範囲 The scope of the claims
[1] 脂肪族単量体を繰り返し単位とするハイパーブランチ構造を有し数平均分子量が 2 000以上 4000未満であるポリエステルに、グリシジル基或いは無水酸基を有する単 環式芳香族化合物、およびグリシジル基或!ヽは無水酸基を有する不飽和結合含有 化合物が反応して得られたハイパーブランチポリマーであり、ハイパーブランチポリマ 一全体における前記単環式芳香族化合物により導入された芳香環の濃度が 3000e qZton以上 5000eqZton未満である活性光線硬化型ハイパーブランチポリマー。  [1] A monocyclic aromatic compound having a glycidyl group or a non-hydroxyl group, and a glycidyl group on a polyester having a hyperbranch structure having an aliphatic monomer as a repeating unit and a number average molecular weight of 2 000 or more and less than 4000 Or is a hyperbranched polymer obtained by reacting a compound containing an unsaturated bond having no hydroxyl group, and the concentration of the aromatic ring introduced by the monocyclic aromatic compound in the entire hyperbranched polymer is 3000 eqZton. An actinic ray curable hyperbranched polymer that is less than 5000eqZton.
[2] 脂肪族単量体が下記化学式 1)で表される請求項 1に記載の活性線硬化型ハイパー ブランチポリマー。  [2] The actinic radiation curable hyperbranched polymer according to claim 1, wherein the aliphatic monomer is represented by the following chemical formula 1).
化学式 1) KR' [ (R) L]  Chemical formula 1) KR '[(R) L]
m n  m n
R：炭素数 20未満の 2価の脂肪族炭化水素基  R: Divalent aliphatic hydrocarbon group having less than 20 carbon atoms
R'：炭素数 20未満の (n+ 1)価の脂肪族炭化水素基、或いは R"N (R" :炭素 数 20未満の 2価の脂肪族炭化水素基)で示される基  R ′: an (n + 1) -valent aliphatic hydrocarbon group having less than 20 carbon atoms, or a group represented by R ″ N (R ”: a divalent aliphatic hydrocarbon group having less than 20 carbon atoms)
K、 L:互いに異なるエステル結合形成性官能基  K, L: different ester bond-forming functional groups
m: 0又は 1  m: 0 or 1
n : 2以上の整数  n: integer greater than or equal to 2
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