Classifications

• • 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
• • 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

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 present disclosure 1 is a curable resin composition containing a curable resin, a photopolymerization initiator and a dye, wherein the curable resin comprises an organic silane compound having a cationically polymerizable group and the cationically polymerizable group.
• the absorption peak wavelength of the photopolymerization initiator and the absorbance ratio photopolymerization It is a curable resin composition in which the absorbance of the initiator/the absorbance of the dye) is 0.8 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 the curable resin composition of the present disclosure 1 or 2, further containing an ultraviolet absorber.
• Disclosure 4 is the curable resin composition of Disclosure 1, 2 or 3 further comprising a leveling agent.
• the present disclosure 5 is the curable resin composition of the present disclosure 1, 2, 3 or 4 further comprising a thixotropic agent.
• the present disclosure 6 is a coating layer formed using the curable resin composition of the present disclosure 1, 2, 3, 4 or 5.
• the present disclosure 7 is a film formed using the curable resin composition of the present disclosure 1, 2, 3, 4 or 5. The present invention will be described in detail below.
• the present inventors studied coloring by blending a dye instead of a pigment in the curable resin composition, but the resulting curable resin The composition sometimes resulted in poor deep-section curability. Therefore, the present inventors have used a combination of a specific cationic polymerizable compound, a photopolymerization initiator and a dye, and further, the photopolymerization initiator and the dye at the absorption peak wavelength of the photopolymerization initiator. (absorbance of photopolymerization initiator/absorbance of dye) to a specific value or more. As a result, the present inventors have found that a curable resin composition having excellent colorability, cured product hardness, and deep-part curability can be obtained, and have completed the present invention.
• the curable resin composition of the present invention contains a curable resin.
• the curable resin includes an organosilane compound having a cationically polymerizable group (hereinafter also referred to as a "cationically polymerizable organosilane compound”) and a cationically polymerizable compound other than the organosilane compound having the cationically polymerizable group. .
• a curable resin composition of the present invention becomes excellent in coatability and hardness of the cured product.
• the cationically polymerizable organic silane compound and the other cationically polymerizable compound 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 of the cationically polymerizable organosilane compound and the cationically polymerizable group of the other cationically polymerizable compound may be the same or different.
• the cationically polymerizable organosilane compound preferably has one or more hydrolyzable alkoxy groups in its molecule.
• cationic polymerizable organic silane compound examples include 3-glycidoxypropyltrimethoxysilane, 2-(3,4 epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxyoctyltrimethoxysilane and the like.
• 3-glycidoxypropyltrimethoxysilane, 2-(3,4 epoxycyclohexyl)ethyltrimethoxysilane, and 3-glycidoxypropyldiethoxysilane are preferable from the viewpoint of improving reactivity and hardness of the cured product. .
• a preferable lower limit of the content of the cationic polymerizable organic silane compound in 100 parts by weight of the curable resin is 40 parts by weight, and a preferable upper limit thereof is 90 parts by weight.
• the resulting curable resin composition is excellent in siloxane bond network formation.
• the content of the cationically polymerizable organic silane compound is 90 parts by weight or less, the resulting curable resin composition is excellent in forming a copolymer of the cationically polymerizable organic silane compound and other cationically polymerizable compounds. becomes.
• a more preferable lower limit to the content of the cationic polymerizable organic silane compound is 60 parts by weight, and a more preferable upper limit is 80 parts by weight.
• Examples of the other cationic polymerizable compounds include 3,4-epoxycyclohexylmethyl(3,4-epoxy)cyclohexane carboxylate, 4,4′-bis(1,2-epoxycyclohexane), tetrahydroindene diepoxide, Bis(3,4-epoxycyclohexylmethyl)ether, bis(3,4-epoxycyclohexan-1-ylmethyl)adipate, 1,2-epoxy-4- of 2,2-bis(hydroxymethyl)-1-butanol (2-oxiranyl) cyclohexane adduct, [(3,4-epoxycyclohexane)-1-yl]methyl methacrylate, fluorene type epoxy compound, 1,7-octadiene diepoxide, neopentyl glycol diglycidyl ether, ethylene glycol Diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidy
• alicyclic epoxy compounds are preferred, and 3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxy 4,4′-bis(1,2-epoxycyclohexane), tetrahydroindene diepoxide, bis(3,4-epoxycyclohexylmethyl)ether are more preferred.
• a preferable lower limit of the content of the other cationic polymerizable compound in 100 parts by weight of the curable resin is 10 parts by weight, and a preferable upper limit thereof is 60 parts by weight.
• the content of the other cationically polymerizable compound is 10 parts by weight or more, the resulting curable resin composition becomes excellent in curability and hardness of the cured product.
• the content of the other cationically polymerizable compound is 60 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 other cationic polymerizable compound is 15 parts by weight, and a more preferable upper limit thereof is 40 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-110P, CPI-200K, CPI-210S and CPI-310FG.
• 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 invention contains a dye. By containing the dye, the curable resin composition of the present invention becomes excellent in colorability.
• Cationic dyes and anionic dyes can be used as the above dyes, and examples thereof include azine dyes, oxazine dyes, allylmethane dyes, and azo dyes. Among them, the above-mentioned azine-based dyes are preferred, and nigrosine-based dyes are more preferred.
• the preferred lower limit is 0.1 parts by weight and the preferred upper limit is 5 parts by weight with respect to 100 parts by weight of the curable resin.
• the content of the dye is 0.1 parts by weight or more, the resulting curable resin composition is more excellent in colorability.
• the content of the dye is 5 parts by weight or less, the obtained curable resin composition has excellent deep-part curability.
• a more preferable lower limit of the dye content is 0.5 parts by weight, and a more preferable upper limit is 2 parts by weight.
• the absorbance ratio between the photopolymerization initiator and the dye at the absorption peak wavelength of the photopolymerization initiator is 0. 8 or more.
• the absorbance ratio between the photopolymerization initiator and the dye is 0.8 or more, the photopolymerization initiator effectively acts and the curing reaction is initiated, so that the curable resin composition of the present invention
• the product has excellent deep-part curability.
• the absorbance ratio between the photopolymerization initiator and the dye at the absorption peak wavelength of the photopolymerization initiator is preferably 1.0 or more.
• the absorbance can be measured using a spectrophotometer under the condition of an optical path length of 1 cm. Examples of the spectrophotometer include U-3900 (manufactured by Hitachi High-Tech Science).
• 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 curing retarders, reinforcing agents, viscosity modifiers and antioxidants, if necessary.
• the curable resin composition of the present invention preferably has a lower limit of 5 mPa ⁇ s and a preferred upper limit of viscosity measured at 25° C. using an E-type viscometer of 5000 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 10 mPa ⁇ s, and a more preferable upper limit is 100 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 at a rotational speed of 1 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 coloring property, the hardness of hardened
• Examples 1 to 11 and Comparative Examples 1 and 2 The curable resin compositions of Examples 1 to 11 and Comparative Examples 1 and 2 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.
• the absorbance of the photopolymerization initiator and the absorbance of the dye are measured at the absorption peak wavelength (365 nm) of the photopolymerization initiator, and the absorbance ratio (absorbance of the photopolymerization initiator / dye absorbance) was derived. Table 1 shows the results.
• Each curable resin composition obtained in Examples and Comparative Examples was coated on a glass substrate provided with a gap using a Kapton tape using a bar coater No. 1. 5 (manufactured by AS ONE) to a thickness of 30 ⁇ m, and then irradiated with ultraviolet rays (wavelength: 365 nm) of 100 mW/cm 2 for 30 seconds using a metal halide lamp to photocure the curable resin composition. let me Then, by heating in an oven at 100° C. for 30 minutes, dehydration condensation was allowed to proceed, and a test piece was obtained.
• the optical density (OD value) of the obtained test piece was measured using an optical densitometer (manufactured by X-rite, "Spectrometer”).
• the OD value of the curable resin composition obtained in Comparative Example 1 was not measured because the curing was insufficient.
• the curable resin composition which is excellent in coloring property, the hardness of hardened

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Citations (8)

• 2022
  • 2022-09-29 WO PCT/JP2022/036374 patent/WO2023054560A1/ja not_active Ceased
  • 2022-09-29 JP JP2022562744A patent/JPWO2023054560A1/ja not_active Withdrawn
  • 2022-09-30 TW TW111137234A patent/TW202321381A/zh unknown

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