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WO2007119714A1 - Polymere hyper-ramifie durcissable par rayon actif - Google Patents

Polymere hyper-ramifie durcissable par rayon actif 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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English (en)
Japanese (ja)
Inventor
Tetsuo Kawakusu
Hirotoshi Kizumoto
Ryo Hamasaki
Original Assignee
Toyo Boseki Kabushiki Kaisha
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Priority to JP2007529294A priority Critical patent/JPWO2007119714A1/ja
Publication of WO2007119714A1 publication Critical patent/WO2007119714A1/fr

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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

La présente invention concerne une résine qui est excellente lorsqu'elle est utilisée en tant que résist. Cette résine est excellente en termes de dispersibilité de pigment et permet d'obtenir un motif de développement objet à un taux élevé comme étant suffisamment durci dans une partie exposée même lorsqu'il est irradié par un rayon actif de faible énergie. La présente invention concerne spécifiquement un polymère hyper-ramifié durcissable par rayon actif qui est obtenu par la réaction d'un polyester, qui possède une structure hyper-ramifiée où un monomère aliphatique est contenu sous la forme d'un motif répétitif tout en ayant une masse moléculaire moyenne en nombre non inférieure à 2000 mais inférieure à 4000, avec un composé aromatique monocyclique possédant un groupe glycidyle ou un groupe anhydride d'acide et un composé contenant une liaison insaturée possédant un groupe glycidyle ou un groupe anhydride d'acide. La concentration des cycles aromatiques introduits par le composé aromatique monocyclique n'est pas inférieure à 3000 eq/tonne mais inférieure à 5000 eq/tonne dans la totalité du polymère hyper-ramifié.
PCT/JP2007/057880 2006-04-12 2007-04-10 Polymere hyper-ramifie durcissable par rayon actif WO2007119714A1 (fr)

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JP2012047903A (ja) * 2010-08-25 2012-03-08 Jsr Corp 感光性組成物及びカラーフィルタ
KR101315510B1 (ko) 2008-12-30 2013-10-07 주식회사 엘지화학 하이퍼 브랜치 폴리머 및 이의 제조방법
JP2013541616A (ja) * 2010-10-08 2013-11-14 ピーピージー・インダストリーズ・オハイオ・インコーポレイテッド 硬化性組成物および化学反応を触媒する方法
WO2016006190A1 (fr) * 2014-07-08 2016-01-14 Canon Kabushiki Kaisha Composition de couche d'adhésion, procédé de formation de film par nano-impression, procédés de fabrication de composant optique, carte de circuit imprimé et appareil électronique
CN116376413A (zh) * 2023-03-01 2023-07-04 太行城乡建设集团有限公司 一种抗滑耐久的高性能沥青路面养护封层材料及制备方法

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CN103497319A (zh) * 2013-08-16 2014-01-08 立邦工业涂料(上海)有限公司 一种超支化聚酯树脂颜料分散剂、制备方法及其色浆和色浆的应用

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KR101315510B1 (ko) 2008-12-30 2013-10-07 주식회사 엘지화학 하이퍼 브랜치 폴리머 및 이의 제조방법
JP2012047903A (ja) * 2010-08-25 2012-03-08 Jsr Corp 感光性組成物及びカラーフィルタ
JP2013541616A (ja) * 2010-10-08 2013-11-14 ピーピージー・インダストリーズ・オハイオ・インコーポレイテッド 硬化性組成物および化学反応を触媒する方法
WO2016006190A1 (fr) * 2014-07-08 2016-01-14 Canon Kabushiki Kaisha Composition de couche d'adhésion, procédé de formation de film par nano-impression, procédés de fabrication de composant optique, carte de circuit imprimé et appareil électronique
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CN116376413A (zh) * 2023-03-01 2023-07-04 太行城乡建设集团有限公司 一种抗滑耐久的高性能沥青路面养护封层材料及制备方法
CN116376413B (zh) * 2023-03-01 2024-02-23 太行城乡建设集团有限公司 一种抗滑耐久的高性能沥青路面养护封层材料及制备方法

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