Classifications

• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
  • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/14—Polycondensates modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1515—Three-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers

Definitions

• the present invention relates to a curable resin composition.
• the present invention also relates to coating layers and films formed using the curable resin composition.
• Optical semiconductor devices such as LEDs consume low power and have a long life, so they are widely used for backlights of liquid crystal display devices, lighting fixtures, and the like.
• An optical semiconductor element deteriorates when it comes into contact with moisture or gas in the atmosphere, and the light extraction efficiency decreases.
• a method for protecting and sealing optical semiconductor elements without using a cover glass or the like it has been studied to form a coating layer on the surface of the optical semiconductor element using a hard coating agent (for example, Patent Document 1 etc).
• the organic-inorganic hybrid hard coating agent disclosed in Cited Document 1 has difficulty in achieving both adhesion (especially adhesion to glass) and hardness (surface hardness) of the cured product.
• An object of the present invention is to provide a curable resin composition having excellent adhesiveness and hardness of the cured product.
• Another object of the present invention is to provide a coating layer and a film formed using the curable resin composition.
• the present disclosure 1 is a curable resin composition containing a curable resin and a photopolymerization initiator, wherein the curable resin includes polysilsesquioxane having a cationic polymerizable group, an alicyclic epoxy compound, and a curable resin composition containing a compound having a hydrogen-bonding functional group and a cationically polymerizable group and having a hydrogen-bonding functional group value of 1.0 ⁇ 10 ⁇ 3 mol/g or more.
• the present disclosure 2 is the curable resin composition of the present disclosure 1, wherein the photopolymerization initiator includes a photocationic polymerization initiator.
• the present disclosure 3 is a coating layer formed using the curable resin composition of the present disclosure 1 or 2.
• the present disclosure 4 is a film formed using the curable resin composition of the present disclosure 1 or 2. The present invention will be described in detail below.
• the present inventor has, as a curable resin, a polysilsesquioxane having a cationic polymerizable group, an alicyclic epoxy compound, a hydrogen-bonding functional group and a cationic polymerizable group, and a hydrogen-bonding functional group
• a curable resin composition having excellent adhesiveness and hardness of the cured product can be obtained, and have completed the present invention.
• the curable resin composition of the present invention is also excellent in low outgassing properties by using polysilsesquioxane having a cationic polymerizable group.
• the curable resin composition of the present invention contains a curable resin.
• the curable resin has a polysilsesquioxane having a cationic polymerizable group, an alicyclic epoxy compound, a hydrogen-bonding functional group and a cationic polymerizable group, and has a hydrogen-bonding functional group value of 1.5. Including compounds that are 0 ⁇ 10 ⁇ 3 mol/g or more.
• the polysilsesquioxane having the cationically polymerizable group is also referred to as “cationically polymerizable polysilsesquioxane”, and has the hydrogen-bonding functional group and the cationically-polymerizable group, and has a hydrogen-bonding functional group value.
• the curable resin composition of the present invention has adhesiveness. (especially adhesion to glass) and hardness of the cured product.
• the above-mentioned “polysilsesquioxane” is a compound having a repeating structure of RSiO 1.5 (R is a hydrogen atom or an organic group) unit, and a silicon atom is added with an alkoxy group or the like. It is a compound having a network structure derived from a silane compound in which three decomposable groups are bonded.
• a compound having a hydrogen-bonding functional group and an alicyclic epoxy skeleton and having a hydrogen-bonding functional group value of 1.0 ⁇ 10 ⁇ 3 mol/g or more is not the above alicyclic epoxy compound. It is treated as the above-mentioned hydrogen-bonding functional group-containing cationically polymerizable compound.
• the cationically polymerizable polysilsesquioxane and the cationically polymerizable compound containing a hydrogen-bonding functional group have a cationically polymerizable group.
• Examples of the cationic polymerizable group include an epoxy group, an oxetanyl group, and a vinyl ether group. Among them, an epoxy group and an oxetanyl group are preferable.
• the cationically polymerizable group possessed by the cationically polymerizable polysilsesquioxane and the cationically polymerizable group possessed by the cationically polymerizable compound containing a hydrogen-bonding functional group may be the same or different.
• the cationically polymerizable polysilsesquioxane may have any one of a random structure, a ladder structure, and a cage structure, or may be a mixture of structures having these structures.
• a preferable lower limit of the content of the cationic polymerizable polysilsesquioxane in 100 parts by weight of the curable resin is 20 parts by weight, and a preferable upper limit is 80 parts by weight.
• the content of the cationically polymerizable polysilsesquioxane is 20 parts by weight or more, the obtained curable resin composition becomes excellent in hardness of the cured product.
• the content of the cationically polymerizable polysilsesquioxane is 80 parts by weight or less, the resulting curable resin composition has excellent coatability and adhesiveness (especially adhesiveness to glass).
• a more preferable lower limit to the content of the cationic polymerizable polysilsesquioxane is 40 parts by weight, and a more preferable upper limit is 70 parts by weight.
• alicyclic epoxy compounds examples include 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexane carboxylate, 4,4′-bis(1,2-epoxycyclohexane), tetrahydroindene diepoxide, Cyclic epoxy-modified silicone compound, bis(3,4-epoxycyclohexylmethyl)ether, bis(3,4-epoxycyclohexan-1-ylmethyl)adipate, 1 of 2,2-bis(hydroxymethyl)-1-butanol , 2-epoxy-4-(2-oxiranyl)cyclohexane adduct, [(3,4-epoxycyclohexane)-1-yl]methyl methacrylate, and the like.
• 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexane carboxylate, 4,4'-bis (1,2-epoxycyclohexane), tetrahydroindene diepoxide, alicyclic epoxy-modified silicone compounds, and bis(3,4-epoxycyclohexylmethyl) ether are more preferred.
• a preferable lower limit of the content of the alicyclic epoxy compound in 100 parts by weight of the curable resin is 5 parts by weight, and a preferable upper limit thereof is 50 parts by weight.
• the content of the alicyclic epoxy compound is 5 parts by weight or more and 50 parts by weight or less, the resulting curable resin composition is excellent in curability and hardness of the cured product.
• a more preferable lower limit for the content of the alicyclic epoxy compound is 10 parts by weight, and a more preferable upper limit is 30 parts by weight.
• Examples of the hydrogen-bonding functional group possessed by the cationically polymerizable compound containing a hydrogen-bonding functional group include a hydroxyl group, an amino group, an amide group, a carboxyl group, and a thiol group. Among them, a hydroxyl group is preferred. Further, when the cationically polymerizable compound containing a hydrogen-bonding functional group has a hydroxyl group generated by a ring-opening reaction of an epoxy group, the cationically polymerizable compound containing a hydrogen-bonding functional group is further subjected to a ring-opening reaction of the epoxy group. It is preferable to have a hydrogen-bonding functional group other than the resulting hydroxyl group.
• the practical upper limit is six.
• the cationically polymerizable compound containing a hydrogen-bonding functional group has a hydroxyl group generated by the ring-opening reaction of the epoxy group
• one hydrogen-bonding functional group other than the hydroxyl group generated by the ring-opening reaction of the epoxy group is contained in one molecule. It is preferable to have one or more.
• the hydrogen-bonding functional group-containing cationically polymerizable compound has a hydrogen-bonding functional group value with a lower limit of 1.0 ⁇ 10 ⁇ 3 mol/g. Since the hydrogen-bonding functional group-containing cationically polymerizable compound has a hydrogen-bonding functional group value of 1.0 ⁇ 10 ⁇ 3 mol/g or more, the curable resin composition of the present invention exhibits adhesiveness (especially glass (adhesiveness to) will be excellent.
• a preferable lower limit of the hydrogen-bonding functional group value of the cationically polymerizable compound containing a hydrogen-bonding functional group is 2.0 ⁇ 10 ⁇ 3 mol/g, and a more preferable lower limit is 3.0 ⁇ 10 ⁇ 3 mol/g.
• hydrogen-bonding functional group value of the cationically polymerizable compound containing a hydrogen-bonding functional group
• practical upper limit is 3.0 ⁇ 10 ⁇ 2 mol/g.
• hydrogen-bonding functional group value is a value obtained by dividing the number of hydrogen-bonding functional groups in one molecule of a compound by the molecular weight of the compound.
• the hydrogen-bonding functional group-containing cationically polymerizable compound preferably has 4 or more of the above-described cationically polymerizable groups in one molecule from the viewpoint of further improving the hardness of the cured product of the curable resin composition obtained. .
• the substantial upper limit is six.
• the hydrogen-bonding functional group-containing cationically polymerizable compound has a hydrogen-bonding functional group and a cationically polymerizable group in its molecular structure, and has a hydrogen-bonding functional group value of 1.0 ⁇ 10 ⁇ 3 mol/g. It is not particularly limited as long as it is the above. Among these, polyglycerol polyglycidyl ether and sorbitol polyglycidyl ether are preferable from the viewpoint of the curability of the resulting curable resin composition and the hardness of the cured product.
• a preferable lower limit of the content of the cationically polymerizable compound containing a hydrogen-bonding functional group in 100 parts by weight of the curable resin is 2 parts by weight, and a preferable upper limit thereof is 30 parts by weight.
• the content of the cationically polymerizable compound containing a hydrogen-bonding functional group is 2 parts by weight or more, the obtained curable resin composition has excellent adhesiveness (especially adhesiveness to glass).
• the content of the cationically polymerizable compound containing a hydrogen-bonding functional group is 30 parts by weight or less, the obtained curable resin composition becomes excellent in hardness of the cured product.
• a more preferable lower limit of the content of the cationically polymerizable compound containing a hydrogen-bonding functional group is 4 parts by weight, and a more preferable upper limit thereof is 20 parts by weight.
• the curable resin composition of the present invention contains a photopolymerization initiator.
• the photopolymerization initiator preferably contains a photocationic polymerization initiator.
• the photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid-generating type or a nonionic photoacid-generating type. may
• anion portion of the ionic photoacid-generating photocationic polymerization initiator examples include BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , (BX 4 ) ⁇ (wherein X is at least two or more fluorine or a phenyl group substituted with a trifluoromethyl group). Further, as the anion portion, PF m (C n F 2n+1 ) 6-m ⁇ (wherein m is an integer of 0 or more and 5 or less, and n is an integer of 1 or more and 6 or less), etc. mentioned.
• Examples of the ionic photoacid-generating photocationic polymerization initiator include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts, (2,4-cyclo pentadien-1-yl)((1-methylethyl)benzene)-Fe salts and the like.
• aromatic sulfonium salts include bis(4-(diphenylsulfonio)phenyl)sulfide bishexafluorophosphate, bis(4-(diphenylsulfonio)phenyl)sulfide bishexafluoroantimonate, bis(4-( diphenylsulfonio)phenyl)sulfide bistetrafluoroborate, bis(4-(diphenylsulfonio)phenyl)sulfidetetrakis(pentafluorophenyl)borate, diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate, diphenyl-4-( phenylthio)phenylsulfonium hexafluoroantimonate, diphenyl-4-(phenylthio)phenylsulfonium tetrafluoroborate, diphenyl
• triarylsulfonium tetrakis(pentafluorophenyl)borate such as triphenylsulfonium tetrakis(pentafluorophenyl)borate is preferable.
• aromatic iodonium salts include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis(pentafluorophenyl)borate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis (dodecylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrafluoroborate, bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexa fluorophosphate, 4-methylphenyl-4-(1-methylethyl)
• aromatic diazonium salts examples include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis(pentafluorophenyl)borate.
• aromatic ammonium salts examples include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl -2-cyanopyridinium tetrakis(pentafluorophenyl)borate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluorophosphate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluoroantimonate, 1-(naphthylmethyl) -2-cyanopyridinium tetrafluoroborate, 1-(naphthylmethyl)-2-cyanopyridinium tetrakis(pentafluorophenyl)borate and the like.
• Examples of the (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe salt include (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene )-Fe(II) hexafluorophosphate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II) hexafluoroantimonate, (2,4-cyclopentadiene-1 -yl)((1-methylethyl)benzene)-Fe(II) tetrafluoroborate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II) tetrakis(penta fluorophenyl)borate and the like.
• nonionic photoacid-generating photocationic polymerization initiator examples include nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid esters, phenolsulfonic acid esters, diazonaphthoquinone, and N-hydroxyimide sulfonates.
• Examples of commercially available photocationic polymerization initiators include, for example, a photocationic polymerization initiator manufactured by Midori Chemical Co., Ltd., a photocationic polymerization initiator manufactured by Union Carbide, a photocationic polymerization initiator manufactured by ADEKA, Photocationic polymerization initiators manufactured by 3M, photocationic polymerization initiators manufactured by BASF, photocationic polymerization initiators manufactured by Solvay, and photocationic polymerization initiators manufactured by San-Apro. Examples of the photocationic polymerization initiator manufactured by Midori Kagaku Co., Ltd. include DTS-200 and the like. Examples of photo cationic polymerization initiators manufactured by Union Carbide include UVI6990 and UVI6974.
• Examples of photo cationic polymerization initiators manufactured by ADEKA include SP-150 and SP-170. Examples of photo cationic polymerization initiators manufactured by 3M include FC-508 and FC-512. Examples of photo cationic polymerization initiators manufactured by BASF include IRGACURE261 and IRGACURE290. Examples of photo cationic polymerization initiators manufactured by Solvay include PI2074. Examples of photo cationic polymerization initiators manufactured by San-Apro include CPI-100P, CPI-200K, CPI-210S and the like.
• a preferred lower limit to the content of the photopolymerization initiator is 1 part by weight, and a preferred upper limit is 20 parts by weight with respect to 100 parts by weight of the curable resin.
• a preferred lower limit to the content of the photopolymerization initiator is 1 part by weight, and a preferred upper limit is 20 parts by weight with respect to 100 parts by weight of the curable resin.
• the resulting curable resin composition is more excellent in curability and storage stability.
• a more preferable lower limit to the content of the photopolymerization initiator is 3 parts by weight, and a more preferable upper limit is 15 parts by weight.
• the curable resin composition of the present invention preferably further contains an ultraviolet absorber.
• Examples of the ultraviolet absorber include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, bisanilide 2-ethoxy-2'-ethyloxalate, and dimethyl-1-(2-hydroxyethyl) succinate.
• -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-4'-n- octoxyphenyl)benzotriazole, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, phenyl salicylate, pt-butylphenyl salicylate, 2-ethylhexyl 2-cyano-3,3- diphenyl acrylate, 2-ethoxy-2'-ethyl oxalic acid bisanilide, dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpipe
• the content of the ultraviolet absorber has a preferable lower limit of 0.001 parts by weight and a preferable upper limit of 5 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the ultraviolet absorber is within this range, the resulting curable resin composition is more excellent in light resistance.
• a more preferable lower limit to the content of the ultraviolet absorber is 0.1 part by weight, and a more preferable upper limit is 1 part by weight.
• the curable resin composition of the present invention preferably further contains a leveling agent.
• leveling agent examples include silicone leveling agents, fluorine leveling agents, and acrylic leveling agents.
• the content of the leveling agent has a preferable lower limit of 0.01 parts by weight and a preferable upper limit of 10 parts by weight with respect to 100 parts by weight of the curable resin.
• the content of the leveling agent is within this range, the resulting curable resin composition is more excellent in coatability and flatness of the coating film.
• a more preferable lower limit to the content of the leveling agent is 0.03 parts by weight, and a more preferable upper limit is 1 part by weight.
• the curable resin composition of the present invention preferably further contains a thixotropic agent.
• thixotropic agent examples include polysiloxane, polyacryl, polyamide, polyvinyl alcohol, polyetherester, alkyl-modified cellulose, peptide, polypeptide, silica and the like.
• the preferable lower limit of the content of the thixotropic agent is 0.1 parts by weight, and the preferable upper limit thereof is 5 parts by weight with respect to 100 parts by weight of the curable resin.
• the content of the thixotropy-imparting agent is within this range, the resulting curable resin composition is more excellent in coatability.
• a more preferable lower limit to the content of the thixotropic agent is 1 part by weight, and a more preferable upper limit is 3 parts by weight.
• the curable resin composition of the present invention preferably contains no solvent. By not containing the solvent, the resulting curable resin composition is excellent in low outgassing properties and does not require a solvent removal step.
• the curable resin composition of the present invention may contain various known additives such as dyes, curing retarders, reinforcing agents, viscosity modifiers and antioxidants, if necessary.
• the curable resin composition of the present invention preferably has a lower limit of 500 mPa ⁇ s and a preferred upper limit of viscosity measured at 25° C. using an E-type viscometer of 50,000 mPa ⁇ s. When the viscosity is within this range, the resulting curable resin composition will have excellent coatability.
• a more preferable lower limit of the viscosity is 1000 mPa ⁇ s, and a more preferable upper limit is 10,000 mPa ⁇ s.
• the above viscosity can be measured, for example, by using VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) as an E-type viscometer. 1 rotor can be used and measured at a rotational speed of 1 rpm or 10 rpm.
• the curable resin composition of the present invention can be used for hard coating agents, sealing agents for displays, microlenses and the like. Among others, it is preferably used to protect and seal the optical semiconductor element or the like by forming a coating layer on the optical semiconductor element or the like, or by covering the optical semiconductor element or the like in a film form.
• a coating layer formed using the curable resin composition of the present invention is also one aspect of the present invention.
• a film formed using the curable resin composition of the present invention is also one aspect of the present invention.
• the coating layer of the present invention can be formed by applying the curable resin composition of the present invention onto an object to be coated such as an optical semiconductor element and then curing the composition.
• the film of the present invention can be formed by applying the curable resin composition of the present invention to a release film or the like and then curing the composition.
• Examples of methods for applying the curable resin composition of the present invention include a spin coating method, a bar coating method, an inkjet method, and the like.
• the curable resin composition of the present invention can be easily cured by light irradiation.
• Examples of the method of curing the curable resin composition of the present invention by light irradiation include a method of irradiating light with a wavelength of 300 nm or more and 400 nm or less and an integrated light amount of 300 mJ/cm 2 or more and 3000 mJ/cm 2 or less. .
• Examples of light sources for irradiating the curable resin composition of the present invention with light include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, excimer lasers, chemical lamps, black light lamps, microwave-excited mercury lamps, Examples include metal halide lamps, sodium lamps, halogen lamps, xenon lamps, LED lamps, fluorescent lamps, sunlight, and electron beam irradiation devices. These light sources may be used alone, or two or more of them may be used in combination. These light sources are appropriately selected according to the absorption wavelength of the photopolymerization initiator.
• Examples of means for irradiating the curable resin composition of the present invention with light include simultaneous irradiation with various light sources, sequential irradiation with a time lag, and combined irradiation of simultaneous and sequential irradiation. means may be used.
• the curable resin composition of the present invention may be cured by heating after the light irradiation.
• the curable resin composition which is excellent in adhesiveness and the hardness of hardened
• Examples 1 to 7 and Comparative Examples 1 to 4 The curable resin compositions of Examples 1 to 7 and Comparative Examples 1 to 4 were prepared by stirring and mixing each material using a stirring mixer according to the compounding ratio shown in Table 1.
• a stirring mixer Awatori Mixer ARE-310 (manufactured by Thinky Corporation) was used.
• Each curable resin composition obtained in Examples and Comparative Examples was coated on a glass substrate provided with a gap using a Kapton tape having a thickness of 30 ⁇ m using a bar coater No. 1. 5 (manufactured by AS ONE) was applied to a thickness of 30 ⁇ m. Next, a metal halide lamp was used to irradiate ultraviolet rays (wavelength: 365 nm) of 100 mW/cm 2 for 30 seconds to photo-cure the curable resin composition, thereby obtaining a test piece. The obtained test piece was cut in a grid pattern at intervals of 1 cm using a cutter to provide four test points. After affixing a tape ("Cellotape (registered trademark) No.
• the tape was peeled off, and the number of test points remaining on the substrate without being peeled off was counted. If the number of test points remaining on the substrate was 4, " ⁇ ", if there were 1 or more and 3 or less, " ⁇ ", and if there were 0, " ⁇ ", the adhesiveness was evaluated. evaluated.
• the curable resin composition which is excellent in adhesiveness and the hardness of hardened

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• 2022
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