WO2013129345A1 - Composition à base de (méth)acrylate, résine, et article moulé - Google Patents

Composition à base de (méth)acrylate, résine, et article moulé Download PDF

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Publication number
WO2013129345A1
WO2013129345A1 PCT/JP2013/054832 JP2013054832W WO2013129345A1 WO 2013129345 A1 WO2013129345 A1 WO 2013129345A1 JP 2013054832 W JP2013054832 W JP 2013054832W WO 2013129345 A1 WO2013129345 A1 WO 2013129345A1
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Prior art keywords
meth
group
component
acrylate
composition
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PCT/JP2013/054832
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English (en)
Japanese (ja)
Inventor
寛 小幡
猛 岩崎
大地 小川
勇人 山崎
東洋藏 藤岡
智明 武部
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出光興産株式会社
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Priority claimed from JP2012044740A external-priority patent/JP2013181075A/ja
Priority claimed from JP2012044744A external-priority patent/JP2013181077A/ja
Priority claimed from JP2012044743A external-priority patent/JP2013181076A/ja
Application filed by 出光興産株式会社 filed Critical 出光興産株式会社
Priority to KR20147023953A priority Critical patent/KR20140130686A/ko
Priority to CN201380011729.2A priority patent/CN104136471A/zh
Publication of WO2013129345A1 publication Critical patent/WO2013129345A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/343—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate in the form of urethane links
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/22—Esters containing nitrogen
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • the present invention relates to a (meth) acrylate composition, a resin obtained by polymerizing the composition, and a molded body obtained by molding the resin.
  • a (meth) acrylate-based composition that is a resin raw material composition for optical parts, including a (meth) acrylate compound having an adamantyl group, a resin for optical parts obtained by polymerizing the composition, and the resin
  • the present invention relates to an optical component formed by molding.
  • transparent resin polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, alicyclic olefin polymer, epoxy resin and the like are known. These transparent resins are produced in large quantities industrially and are used in large quantities in various fields by taking advantage of their good transparency.
  • transparency resin In addition to its good transparency, transparency resin is used as a substitute for glass by taking advantage of its light weight and formability, and it can be applied to lenses for camera modules mounted on camera phones. It has been. Here, reflecting the recent miniaturization and reduction in the number of parts, a transparent resin that can withstand the solder reflow process is desired. To that end, in addition to optical characteristics such as light transmittance, extremely high heat resistance Sex is required. However, the above-described transparent resin does not necessarily have sufficient heat resistance. For example, among the above transparent resins, even the polycarbonate resin, which is the most heat-resistant resin, has a glass transition temperature of about 150 ° C., which is an index of heat resistance, and development of a new transparent resin having higher heat resistance. Is desired.
  • Polymethyl acrylate which is known as a transparent resin, is inferior in performance such as heat resistance, heat stability, and solvent resistance, and has high water absorption and poor water resistance. It cannot be used in certain fields. Polymethylmethacrylate is used for a resin material for optical parts, but cannot be applied to fields that require extremely high heat resistance and heat stability that can withstand a solder reflow process.
  • Patent Document 1 A method using a resin composition for an optical material containing a copolymer has been proposed (see, for example, Patent Document 1).
  • the material disclosed in Patent Document 1 is excellent in heat resistance while maintaining excellent transparency.
  • Such an optical component is produced through a manufacturing process in which a liquid composition at room temperature is placed in a mold and cured by heating, pressurizing, or the like. At this time, if the viscosity of the liquid composition used as the raw material of the optical component is small, the composition leaks from the clearance between the mold and the tool when the composition is injected into the mold and pressurized. May end up. Such an adverse effect can be prevented by using a mold having a special structure. However, there is a demand for a method of manufacturing an optical component that can prevent the phenomenon that the composition leaks from the clearance without using such a special mold.
  • the present invention has been made in view of the above problems, and is a molded article having excellent heat resistance and high refractive index while maintaining excellent optical performance such as transparency and shape stability due to thermal history.
  • An object of the present invention is to provide a (meth) acrylate-based composition that has high workability because of its high viscosity, a resin obtained from the composition, and a molded body obtained by molding the resin. To do.
  • the present inventors have found that a (meth) acrylate-based composition containing a (meth) acrylate compound having a specific structure together with a (meth) acrylate compound having an adamantyl group can solve the above-mentioned problems.
  • a (meth) acrylate-based composition containing a (meth) acrylate compound having a specific structure together with a (meth) acrylate compound having an adamantyl group can solve the above-mentioned problems. was completed.
  • a (meth) acrylate-based composition comprising a (meth) acrylate compound (B) having one or more of the following structures:
  • each R 1 independently represents a hydrogen atom or a methyl group
  • each X independently represents a single bond, an alkylene group having 1 to 4 carbon atoms, or 4 represents an oxyalkylene group
  • U represents an alkyl group having 1 to 4 carbon atoms, a halogen group, a hydroxyl group, or ⁇ O formed by combining two U.
  • k represents an integer of 0 to 15
  • m Represents an integer of 1 to 4.
  • Y a represents a divalent organic group
  • each R 6 independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon number.
  • 1 to 6 and R 7 each independently represents a divalent organic group
  • p represents an integer of 0 to 4
  • q represents an integer of 0 to 3
  • * represents a bonding portion.
  • each R 2 independently represents a hydrogen atom or a methyl group
  • Y 1 represents a substituted or unsubstituted acyclic hydrocarbon group having 5 to 30 carbon atoms and —R From the group represented by '(OR') L- (wherein R 'independently represents a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, and L is an integer of 1 to 20).
  • the component (B) is a (meth) acrylate compound (B1) having an isocyanurate structure represented by the general formula (bI) and a general formula (B-2) )
  • each G independently represents a single bond, an alkylene group having 1 to 4 carbon atoms, or an oxyalkylene group having 1 to 4 carbon atoms
  • each R 4 independently represents Each represents a hydrogen atom or a methyl group
  • each R 5 independently represents an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 4 carbon atoms substituted with a hydroxy group
  • a represents an integer of 2 to 8
  • each b is independently a positive number from 1 to 4.
  • Z represents the following general formulas (b-II-1) to (b-II-6) and the above general formula (b-III) ) To any one of the organic groups represented by (b-VII).)
  • each R 6 independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
  • each R 7 independently represents a divalent organic group, p represents an integer of 0 to 4, q represents an integer of 0 to 3, and * represents a bonding portion.
  • component (B1) is a (meth) acrylate compound having an isocyanurate structure represented by the following general formula (B-1).
  • each R 3 independently represents a hydrogen atom or a methyl group, and D 1 to D 3 each independently represents a divalent organic group.
  • component (D) a compound selected from a reaction compound (D1) of an epoxy compound and (meth) acrylic acid and a urethane (meth) acrylate compound (D2) other than the compound corresponding to component (B)
  • the component (B1) is included as the component (B), and the content of the component (B1) is 20 to 80% by mass based on the total amount of the components (A) to (C).
  • the component (B1) and the component (B2) are included as the component (B), and the content of the component (B2) is 5 to 40% by mass with respect to the total amount of the components (A) to (C).
  • each X 1 independently represents a single bond, an alkylene group having 1 to 4 carbon atoms, or an oxyalkylene group having 1 to 4 carbon atoms;
  • a represents a divalent organic group
  • R 22 and R 23 each independently represents an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 4 carbon atoms substituted with a hydroxy group
  • R 4a , R 4b each independently represents a hydrogen atom or a methyl group
  • R 6 to R 13 each independently represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 5 carbon atoms.
  • a and b each represent an added mole number of alkylene oxide, each being a positive number, and an average value of a + b is 2 to 4.
  • c represents an integer of 1 to 5
  • d represents 1 to 5
  • e represents an integer of 1 to 5.
  • the organic group Y a in the general formula (B-3a) or (B-3b) is —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, —SO 2 —, —CH 2
  • R 16 and R 17 each independently represents a hydrogen atom or a methyl group, and f and g represent the number of added moles of alkylene oxide, each being a positive number, and the average value of f + g is 2-4.)
  • the mass ratio of the content of the component (B3) to the content of the component (B2 ′) [(B3) component / (B2 ′) component] is 15/85 to 40/60 above.
  • the present invention is classified into three inventions (first to third inventions) depending on the component (B) used.
  • Examples of the first aspect of the present invention include the following [1a] to [13a].
  • a (meth) acrylate-based composition comprising the (meth) acrylate compound (C) represented by the general formula (C-1).
  • [2a] The (meth) acrylate composition according to [1a] above, wherein the component (B1) is a (meth) acrylate compound having an isocyanurate structure represented by the general formula (B-1).
  • [3a] The (meth) acrylate composition according to [1a] or [2a], further including a (meth) acrylate compound (B2) represented by the above general formula (B-2) as the component (B) object.
  • [4a] The (meth) acrylate composition according to [3a] above, wherein the content of the component (B2) is 5 to 40% by mass with respect to the total amount of the components (A) to (C).
  • [5a] The content of the component (B1) according to any one of the above [1a] to [4a], wherein the content of the component (B1) is 20 to 80% by mass with respect to the total amount of the components (A) to (C). ) Acrylate composition.
  • a compound selected from a reaction compound (C1) of an epoxy compound and (meth) acrylic acid and a urethane (meth) acrylate compound (D2) other than the compound corresponding to the component (B) The (meth) acrylate composition according to any one of the above [1a] to [5a], comprising at least seeds.
  • [7a] The (meth) acrylate composition as described in [6a] above, wherein the content of the component (D) is 2 to 50 parts by mass with respect to 100 parts by mass in total of the components (A) to (C) object.
  • [8a] The (meth) acrylate composition according to any one of the above [1a] to [7a], wherein the viscosity of the (meth) acrylate composition at 25 ° C. is 1000 to 50000 mPa ⁇ s.
  • [9a] A resin obtained by polymerizing the (meth) acrylate composition according to any one of [1a] to [8a].
  • a (meth) acrylate-based composition containing the (meth) acrylate compound (C) represented by the general formula (C-1) and a molded product obtained by molding a resin obtained by polymerization.
  • examples of the second aspect of the present invention include the following [1b] to [10b].
  • [1b] including a (meth) acrylate compound (A) having an adamantyl group represented by the general formula (A-1) and a (meth) acrylate compound (B2) represented by the general formula (B-2)
  • a (meth) acrylate-based composition comprising a (meth) acrylate compound (B) and a (meth) acrylate compound (C) represented by the general formula (C-1).
  • component (D) a compound selected from a reaction compound (D1) of an epoxy compound and (meth) acrylic acid and a urethane (meth) acrylate compound (D2) other than the compound corresponding to component (B)
  • the (meth) acrylate composition according to the above [1b] or [2b] which contains seeds or more.
  • [1c] A (meth) acrylate compound (A) having an adamantyl group represented by the general formula (A-1) and a phenyl group represented by the general formula (B-3a) or (B-3b)
  • [2c] The (meth) acrylate composition according to [1c] above, wherein one or more of R 6 to R 13 in the general formula (B-3a) or (B-3b) is a bromine atom.
  • [7c] The content of the component (A) in any one of the above [1c] to [6c], wherein the content of the component (A) is 5 to 40% by mass relative to the total amount of the components (A) to (C) ) Acrylate composition.
  • [8c] The above-mentioned [1c] to [7c], wherein the total content of the components (A) to (C) is 60 to 100% by mass with respect to the total amount of the (meth) acrylate compound contained in the composition.
  • the (meth) acrylate type composition in any one of.
  • [9c] The (meth) acrylate composition according to any one of [1c] to [8c] above, having a viscosity at 25 ° C.
  • the (meth) acrylate composition of the present invention can be a molded article having excellent heat resistance and high refractive index while maintaining shape stability due to excellent optical performance such as transparency and thermal history, and high refractive index. Excellent workability due to viscosity. Therefore, by using the above composition, it is possible to produce a molded body such as an optical component excellent in optical performance by improving productivity without using a special mold or the like.
  • the (meth) acrylate compound is used to mean both an acrylate compound and a methacrylate compound (and other synonymous terms are also the same).
  • the molecular weight of each component means a number average molecular weight, and is the value computed from the polystyrene conversion measured with the following apparatus and conditions by the gel permeation chromatography (GPC) method.
  • ⁇ GPC measurement device Column: TOSO GMHHR-H (S) HT ⁇ Detector: RI detector for liquid chromatogram WATERS 150C ⁇ Measurement conditions> Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C ⁇ Flow rate: 1.0 ml / min ⁇ Sample concentration: 2.2 mg / ml ⁇ Injection volume: 160 ⁇ l -Calibration curve: Universal Calibration ⁇ Analysis program: HT-GPC (Ver.1.0)
  • composition includes a (meth) acrylate compound (A) having an adamantyl group represented by the general formula (A-1), and A (meth) acrylate compound (B) having one or more of the structures represented by the above general formulas (bI) to (b-VII) is included in the molecule.
  • the composition of the present invention can further contain a (meth) acrylate compound (C) represented by the above general formula (C-1) as an optional component, and a molded body is produced from the composition. From the viewpoint of suppressing the occurrence of cracks, it is preferable to include the component (C).
  • the composition of the present invention is a reaction compound of an epoxy compound and (meth) acrylic acid other than the compound corresponding to the component (B) as the component (D) ( It is preferable that 1 or more types chosen from D1) and a urethane (meth) acrylate compound (D2) are included.
  • the composition of the present invention may contain other additives such as an antioxidant, a polymerization initiator, and a light stabilizer, if necessary.
  • the viscosity of the composition of the present invention at 25 ° C. is preferably 300 to 50000 mPa ⁇ s, more preferably 400 to 40000 mPa ⁇ s, still more preferably 450 to 20000 mPa ⁇ s.
  • the value of the viscosity in 25 degreeC of said composition means the value measured based on the method as described in an Example.
  • the composition of the present invention is classified into the following three compositions (first to third compositions) depending on the difference in the structure of the component (B) contained in the composition.
  • the first composition of the present invention contains a (meth) acrylate compound (B1) having an isocyanate structure represented by the above general formula (bI) as the component (B).
  • B1 a (meth) acrylate compound having an isocyanate structure represented by the above general formula (bI) as the component (B).
  • the 2nd composition of this invention contains the (meth) acrylate compound (B2) represented by the said general formula (B-2) as (B) component.
  • the third composition of the present invention contains a (meth) acrylate compound having a phenyl group represented by the above general formula (B-3a) or (B-3b) as the component (B).
  • (B3) component in a composition, the refractive index of the molded object obtained from this composition can be raised.
  • the composition of this invention may correspond to several types, such as the structure of (B) component to contain, and the case where it contains 2 or more types of (B) component.
  • the composition of the present invention contains a (meth) acrylate compound having an adamantyl group represented by the following general formula (A-1) as the component (A).
  • the component (A) mainly becomes a hard segment when the composition of the present invention is polymerized to form a resin, and becomes a site having low mobility between molecules.
  • the heat resistance of the molded object obtained from this composition can be improved by containing (A) component.
  • each R 1 independently represents a hydrogen atom or a methyl group.
  • Each X independently represents a single bond, an alkylene group having 1 to 4 carbon atoms, or an oxyalkylene group having 1 to 4 carbon atoms.
  • the alkylene group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a butylene group, and a 2-methyltrimethylene group.
  • the oxyalkylene group having 1 to 4 carbon atoms include an oxymethylene group, an oxyethylene group, an oxypropylene group, and an oxybutylene group.
  • a single bond is preferable from the viewpoint of improving the heat resistance of a molded product obtained from the composition.
  • U represents an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, or ⁇ O formed by combining two U together.
  • the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group and the like.
  • a halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.
  • K represents the number of substituents U in the adamantyl skeleton, and represents an integer of 0 to 15, preferably an integer of 0 to 10.
  • m represents an integer of 1 to 4, preferably an integer of 1 to 2.
  • examples of the compound in which m is 1 include adamantylmethanol (meth) acrylate and adamantylethanol (meth) acrylate.
  • examples of the compound in which m is 2 include adamantyl dimethanol di (meth) acrylate and adamantyl diethanol di (meth) acrylate.
  • Examples of the compound in which m is 3 include adamantyltrimethanol tri (meth) acrylate and adamantyltriethanol tri (meth) acrylate.
  • Examples of the compound in which m is 4 include adamantyl tetramethanol tetra (meth) acrylate and adamantyl tetraethanol tetra (meth) acrylate.
  • components (A) may be used alone or in combination of two or more.
  • the content of the component (A) in the composition of the present invention is preferably 5 to 60% by mass, more preferably 7 to 40% by mass, and further preferably 9 to 30% by mass with respect to the total amount of the composition. It is.
  • composition of the present invention comprises, as component (B), a (meth) acrylate compound (B) having one or more of the structures represented by the following general formulas (bI) to (b-VII) in one molecule including.
  • Y a represents a divalent organic group
  • R 6 each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon number 1 to 6 alkoxy groups
  • each R 7 is independently a divalent organic group.
  • P represents an integer of 0 to 4
  • q represents an integer of 0 to 3. * Represents a binding moiety.
  • Examples of the divalent organic group represented by Y a include —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, —SO 2 —, —CH 2 —, —O—, —CO— and the like.
  • -C (CH 3 ) 2 - is preferred from the viewpoint of increasing the refractive index of the molded product obtained from the composition.
  • Examples of the halogen atom represented by R 6 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the alkyl group having 1 to 6 carbon atoms represented by R 6 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, pentyl group, hexyl group and the like. It is done.
  • Examples of the alkoxy group having 1 to 6 carbon atoms represented by R 6 include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group and the like.
  • Examples of the divalent organic group represented by R 7 include divalent aliphatic groups such as linear or branched alkylene groups, oxyalkylene groups, alkylidene groups, alkenylene groups, phenylene groups, and biphenylene groups. And arylene groups such as a naphthylene group.
  • R 7 is an alkylene group, an oxyalkylene group, an alkylidene group, or an alkenylene group
  • the number of carbon atoms in these groups is preferably 1-18, more preferably 1-12, still more preferably 1-6, and more. More preferably, it is 1 to 3.
  • R 7 is an arylene group
  • the carbon number of the arylene group is preferably 6 to 24, more preferably 6 to 18, and still more preferably 6 to 12.
  • components (B) may be used alone or in combination of two or more.
  • the content of the component (B) in the composition of the present invention is preferably 25 to 95% by mass, more preferably 30 to 92% by mass, and still more preferably 40 to 88% by mass with respect to the total amount of the composition. It is.
  • the component (B) preferably contains one or more kinds obtained from the above-mentioned component (B1), component (B2), and component (B3).
  • the components (B1) to (B3) may be used alone or in combination of two or more.
  • a composition containing the component (B1) and the component (B2) is preferable as the component (B).
  • the component (B) the components (B3) and (B2 ) Component is preferred. Details of the components (B1) to (B3) will be described below.
  • the composition of the present invention preferably contains a (meth) acrylate compound (B1) having an isocyanurate structure represented by the above general formula (bI) as the component (B).
  • (B1) component in a composition, the viscosity of the said composition can be raised and the workability of a composition can be improved. Moreover, the optical characteristic of the molded object obtained from a composition also becomes favorable.
  • the component (B1) is preferably a (meth) acrylate compound having an isocyanurate structure represented by the following general formula (B-1) from the viewpoint of increasing the viscosity of the composition and improving the processability of the composition.
  • R 3 each independently represents a hydrogen atom or a methyl group
  • D 1 to D 3 each independently represents a divalent organic group.
  • Examples of the divalent organic group represented by D in the formula (B-1) include divalent aliphatic groups such as a linear or branched alkylene group, an oxyalkylene group, an alkylidene group, and an alkenylene group.
  • arylene groups such as a phenylene group, a biphenylene group, and a naphthylene group.
  • the number of carbon atoms in the alkylene group, oxyalkylene group, alkylidene group, and alkenylene group is preferably 1-18, more preferably 1-12, still more preferably 1-6, and still more preferably 1-3.
  • the number of carbon atoms of the arylene group is preferably 6 to 24, more preferably 6 to 18, and still more preferably 6 to 12.
  • examples of the divalent organic group represented by D also include a group represented by the following formula (B-1a).
  • R 11 and R 12 each independently represents an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms.
  • D represents an integer of 1 to 10, preferably an integer of 1 to 4. * Represents a binding moiety.
  • divalent organic groups from the viewpoint of increasing the viscosity of the composition, an alkylene group having 1 to 6 carbon atoms, an oxyalkylene group having 1 to 6 carbon atoms, and a group represented by the above formula (B-1a) Is preferred.
  • These divalent organic groups D 1 to D 3 may be all the same or different from each other.
  • These components (B1) may be used alone or in combination of two or more.
  • composition of the present invention preferably contains a (meth) acrylate compound (B) represented by the following general formula (B-2) as the component (B).
  • B2 component By containing (B2) component in a composition, the refractive index of the molded object obtained from the said composition can be raised, raising the viscosity of the said composition and improving the workability of a composition.
  • each G independently represents a single bond, an alkylene group having 1 to 4 carbon atoms, or an oxyalkylene group having 1 to 4 carbon atoms
  • R 4 each independently represents hydrogen.
  • R 5 represents an atom or a methyl group
  • each R 5 independently represents an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 4 carbon atoms substituted with a hydroxy group.
  • a represents an integer of 2 to 8
  • each b is independently a positive number of 1 to 4, preferably 1 to 3, more preferably 1 to 2.
  • the values of b each independently represent an average value of the number of added moles of alkylene oxide.
  • Examples of the alkylene group having 1 to 4 carbon atoms in G include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a butylene group, and a 2-methyltrimethylene group.
  • Examples of the oxyalkylene group 4 include an oxymethylene group, an oxyethylene group, an oxypropylene group, and an oxybutylene group.
  • Examples of the alkylene group having 1 to 4 carbon atoms in R 5 include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a butylene group, and a 2-methyltrimethylene group.
  • alkylene group having 1 to 4 carbon atoms substituted with a hydroxy group examples include groups in which a hydrogen atom in the groups listed as the alkylene group having 1 to 4 carbon atoms is substituted with a hydroxy group.
  • Groups represented by formulas (a) to (c) are preferred.
  • Z represents any one of organic groups represented by the following general formulas (b-II-1) to (b-II-6) and the general formulas (b-III) to (b-VII).
  • each R 6 is independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
  • Each R 7 independently represents a divalent organic group.
  • P represents an integer of 0 to 4
  • q represents an integer of 0 to 3.
  • * represents a bonding part, but the organic groups represented by the above general formulas (b-II-1) to (b-II-6) are preferably bonded at the para position.
  • Examples of the alkyl group and alkoxy group represented by R 6 and the divalent organic group represented by R 7 include the groups exemplified for R 6 and R 7 in the general formulas (bI) to (b-VII). Can be mentioned.
  • Z in the general formula (B-2) is an organic group represented by the general formula (b-II-1).
  • a (meth) acrylate compound is preferred.
  • Examples of the (meth) acrylate compound in which Z is an organic group represented by the general formula (b-II-1) include (meth) acrylic acid adducts of bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl.
  • Examples include (meth) acrylic acid adducts of ethers, and examples of commercially available products include epoxy esters 3002M, 3002A, 3000M, 3000MK, and 3000A (manufactured by Kyoeisha Chemical Co., Ltd.). These components (B2) may be used alone or in combination of two or more.
  • composition of the present invention preferably contains a (meth) acrylate compound having a phenyl group represented by the following general formula (B-3a) or (B-3b) as the component (B).
  • (B3) component in a composition, the refractive index of the molded object obtained from the said composition can be raised.
  • X 1 is independently a single bond, an alkylene group, or an oxyalkylene group having 1 to 4 carbon atoms having 1 to 4 carbon atoms
  • Y a Represents a divalent organic group
  • R 22 and R 23 each independently represents an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 4 carbon atoms substituted with a hydroxy group
  • R 4a , R 4b independently represents a hydrogen atom or a methyl group
  • R 6 to R 13 each independently represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 5 carbon atoms.
  • Examples of the alkylene group having 1 to 4 carbon atoms represented by X 1 , R 22 , and R 23 include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a butylene group, and a 2-methyltrimethylene group. Can be mentioned.
  • a hydrogen atom in the above-mentioned groups listed as the alkylene group having 1 to 4 carbon atoms is substituted with a hydroxy group.
  • a group is exemplified, but a group represented by the following formula is preferred.
  • R 6 to R 13 each independently represent a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 5 carbon atoms.
  • the halogen atom represented by R 6 to R 13 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the linear or branched alkyl group having 1 to 5 carbon atoms represented by R 6 to R 13 include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group , T-butyl, n-pentyl group and the like.
  • R 6 to R 13 are preferably bromine atoms, and R 6 , R 8 , R 11 , and R 13 are t- A butyl group is preferred.
  • Y represents a divalent organic group.
  • —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, —SO 2 —, —CH 2 —, —O—, —CO— and the like can be mentioned, and —C (CH 3 ) 2 — is preferable from the viewpoint of increasing the refractive index of a molded article obtained from the composition.
  • a and b represent the number of added moles of alkylene oxide, each being a positive number, and the average value of a + b is 2 to 4.
  • c represents an integer of 1 to 5, preferably 1 to 3.
  • d represents an integer of 1 to 5, preferably 1 to 3.
  • e represents an integer of 1 to 5, preferably 1 to 3.
  • X is a single bond
  • e represents an integer of 2 to 5, preferably 2 to 3.
  • the component (B3) and the component (B2) are preferably contained as the component (B), and together with the component (B3), the following general formula (B-2a) It is more preferable to contain the represented (meth) acrylate compound (B2 ′).
  • the refractive index of the composition can be increased and a composition having a high viscosity can be obtained even if the content of the component (B3) is suppressed.
  • R 14 and R 15 each independently represents an alkylene group having 1 to 4 carbon atoms, such as a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, Examples include butylene group and 2-methyltrimethylene group.
  • R 16 and R 17 each independently represent a hydrogen atom or a methyl group.
  • f and g represent the number of added moles of alkylene oxide, each being a positive number, and the average value of f + g is 2-4.
  • Z represents a divalent organic group represented by the following general formula (b-III).
  • the composition of the present invention contains a (meth) acrylate compound represented by the following general formula (C-1) as the component (C).
  • C When the composition of the present invention is polymerized into a resin, the component (C) is mainly a soft segment, which is a site having many flexible sites, and the mobility of the polymer chain is increased in the molecule. It becomes a flexible part. Moreover, generation
  • each R 2 independently represents a hydrogen atom or a methyl group.
  • Y 1 represents a substituted or unsubstituted acyclic hydrocarbon group having 5 to 30 carbon atoms and a group represented by —R ′ (OR ′) L — (wherein R ′ is independently substituted Or an unsubstituted alkylene group having 1 to 4 carbon atoms, and L is an integer of 1 to 20).
  • R ′ is independently substituted Or an unsubstituted alkylene group having 1 to 4 carbon atoms, and L is an integer of 1 to 20.
  • a substituent of the said acyclic hydrocarbon group and an alkylene group a halogen atom, a hydroxyl group, an amino group etc. are mentioned, for example.
  • Examples of the alkylene group having 1 to 4 carbon atoms represented by R ′ include the groups described above.
  • L is an integer of 1 to 20, preferably 2 to 15, and more preferably 2 to 10.
  • n represents an integer of 1 to 8, and is preferably an integer of 2 to 7, more preferably an integer of 3 to 6, from the viewpoint of improving the crosslinking density of the resin obtained from the composition of the present invention.
  • acyclic organic group having 5 to 30 carbon atoms and a group represented by —R ′ (OR ′) L — represented by Y 1 in the above formula (C-1)
  • the above acyclic organic group may have an ether bond, and may further include a linear hydrocarbon group having less than 5 carbon atoms, a branched hydrocarbon group, or the like.
  • the above group represented by Y 1 is a site corresponding to the soft segment in the resin obtained from the composition, and the mobility of the polymer chain is increased in the molecule, which becomes a flexible site.
  • Y 1 in the above formula (C-1) is a substituted or unsubstituted acyclic hydrocarbon group having 5 to 30 carbon atoms
  • the component (C) is represented by the following general formula (C—
  • the (meth) acrylate compound (C1) represented by 1a) is preferred.
  • R 2 and n are the same as in the formula (C-1).
  • Q 1 is one or more organic groups selected from a linear hydrocarbon group having 1 to 30 carbon atoms and a branched hydrocarbon group having 3 to 30 carbon atoms, and these organic groups include an ether bond. It may be substituted with a halogen atom, a hydroxyl group, an amino group or the like.
  • Y 2 is an acyclic hydrocarbon group having 5 to 30 carbon atoms, may contain an ether bond, and may be substituted with a halogen atom, a hydroxyl group, an amino group, or the like.
  • Examples of the linear hydrocarbon group having 1 to 30 carbon atoms in Q 1 in the general formula (C-1a) include, for example, a methylene group, an ethylene group, an n-propylene group, an n-butylene group, and an n-pentylene group.
  • Examples of the branched hydrocarbon group having 3 to 30 carbon atoms in Q 1 in the general formula (C-1a) include isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, and neopentyl group. Group, t-pentyl group, isohexyl group and the like.
  • the acyclic hydrocarbon group having 5 to 30 carbon atoms of Y 2 in the general formula (C-1a) is represented by, for example, — (CH 2 ) r1 — or — (CH 3 CH) r1 —.
  • An alkylene group (r1 is an integer of 5 to 30)
  • examples of the compound in which n is 2 include 1,5-pentanediol di (meth) acrylate and 1,6-hexane.
  • examples include diol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,12-dodecanediol dimethacrylate, polybutadiene di (meth) acrylate, and hydrogenated polybutadiene di (meth) acrylate.
  • examples of the compound having n of 3 or more include, for example, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, multifunctional Examples include polyester (meth) acrylate.
  • Y 1 in the above formula (C-1) is an acyclic organic group containing a group represented by —R ′ (OR ′) L —
  • the component (C) is represented by the following general formula A (meth) acrylate compound (C2) represented by the formula (C-1b) is preferable.
  • R 2 and n are the same as in the formula (C-1), and Y 2 is an acyclic carbon atom having 5 to 30 carbon atoms as in the formula (C-1a). It is a hydrogen group, may contain an ether bond, and may be substituted with a halogen atom, a hydroxyl group, an amino group or the like.
  • R ′ each independently represents a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms.
  • L is an integer of 1 to 20, preferably 2 to 15, more preferably 2 to 10.
  • examples of the compound where n is 2 include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, L 2-20 polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, alkoxylated neopentyl glycol diacrylate, tetraethylene
  • examples include glycol di (meth) acrylate and alkoxylated cyclohexanediol diacrylate (manufactured by Sartomer Japan, Inc.).
  • polyethylene glycol di (meth) acrylate polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate having L of 2 to 20 are preferable.
  • examples of compounds in which n is 3 or more include, for example, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated triphenyl Methylolpropane tri (meth) acrylate, alkoxylated trimethylolpropane tri (meth) acrylate with L 2-20, ethoxylated glyceryl tri (meth) acrylate, propoxylated glyceryl tri (meth) acrylate, alkoxylated glyceryl tri (meth) Acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, propoxylated pentaerythritol tetra (meth) acrylate, alkylated trimethylolpropane tri (meth) acrylate, alkoxylated pentaerythr
  • the number average molecular weight of the component (C) is preferably 140 to 50000, more preferably 250 to 40000, and still more preferably 350 to 10000, from the viewpoint of adjusting the viscosity of the composition and suppressing shape change after heat history. .
  • components (C) may be used alone or in combination of two or more.
  • the content of the component (C) in the composition of the present invention is preferably 0 to 50% by mass, more preferably 3 to 40% by mass, and still more preferably 6 to 35% by mass with respect to the total amount of the composition. It is.
  • Component (D) Reaction compound (D1) of epoxy compound and (meth) acrylic acid other than the compound corresponding to component (B), urethane (meth) acrylate compound (D2)]
  • the composition of the present invention further comprises, as component (D), a reaction compound (D1) of an epoxy compound and (meth) acrylic acid other than the compound corresponding to component (B) and a urethane (meth) acrylate compound (D2). It is preferable that 1 or more types chosen from are included.
  • component (D1) due to the influence of hydrogen bonding between the oxygen atom of the carbonyl group and the hydrogen atom of the hydroxyl group formed by ring opening of the epoxy group of the epoxy compound, in component (D2), oxygen in the urethane bond Due to the influence of hydrogen bonding between atoms and hydrogen atoms, the viscosity of the composition containing these components can be increased.
  • the content of the component (D) (the total content of the components (D1) and (D2)) is preferably 2 to 50 parts by mass with respect to the total of 100 parts by mass of the components (A) to (C).
  • the amount is more preferably 4 to 42 parts by mass, more preferably 6 to 40 parts by mass, still more preferably 8 to 38 parts by mass, and still more preferably 9 to 25 parts by mass. If the said content is 2 mass parts or more, the viscosity of a composition can fully be raised and the workability of a composition can be improved. On the other hand, if the said content is 50 mass parts or less, the viscosity of a composition will not become high too much and it can be set as the appropriate viscosity optimal for workability.
  • the component (D1) is a compound other than the compound corresponding to the component (B), and is generated by the ring opening of the epoxy group of the epoxy compound and the reaction with (meth) acrylic acid.
  • the epoxy compound include alkyl glycidyl ether and allyl glycidyl ether.
  • an epoxy compound the compound which has a 2 or more epoxy group is preferable.
  • a reaction compound of an epoxy compound having two or more epoxy groups and (meth) acrylic acid for example, a (meth) acrylic acid adduct of propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether ( (Meth) acrylic acid adduct, (meth) acrylic acid adduct of ethylene glycol diglycidyl ether, (meth) acrylic acid adduct of 1,4-butanediol diglycidyl ether, (1,5-pentanediol diglycidyl ether ( Of (meth) acrylic acid adduct, (meth) acrylic acid adduct of 1,6-hexanediol diglycidyl ether, (meth) acrylic acid adduct of 1,9-nonanediol diglycidyl ether, neopenty
  • (D1) component epoxy ester 40EM, 70PA, 200PA, 80MFA (above, Kyoeisha Chemical Co., Ltd.) etc. are mentioned, for example. In addition, you may use these (D1) components individually or in combination of 2 or more types.
  • the urethane (meth) acrylate compound (D2) is preferably a compound synthesized from a polyol component, an isocyanate component, and a hydroxy group-containing (meth) acrylate component.
  • the number of functional groups of the component (D2) is preferably 2 or more, more preferably 2 to 4, and still more preferably, from the viewpoint of improving the high hardness, high elastic modulus, and heat distortion resistance of the molded product obtained from the composition. Is 2 to 3.
  • bifunctional urethane (meth) acrylate compound examples include U-108A, UA-112P, UA-5201, UA-512, UA-412A, UA-4200, UA-4400, UA-340P, UA-2235PE, UA-160TM, UA-122P, UA-512, UA-W2, UA-7000, UA-7100 (above, trade name, manufactured by Shin-Nakamura Chemical Industry); CN962, CN963, CN964, CN965, CN980, CN981, CN982, CN983, CN996, CN9001, CN9002, CN9788, CN9873, CN978, CN9782, CN9783 (trade names, manufactured by Sartomer Japan, Inc.); M-1100, M-1200, M-1210, M-1310, M- 1600 (above, product name, UN-9000PEP, UN-9200A, UN-7600, UN-333, UN-1255, UN-6060PTM, UN-6060PTM
  • trifunctional urethane (meth) acrylate compounds for example, CN929, CN944B85, CN989, CN9008 (above, trade name, manufactured by Sartomer Japan, Inc.); EVERCRYL 294 / 25HD, EVERCRYL 4820 (trade name, manufactured by Daicel-Cytec);
  • Examples of the tetrafunctional or higher functional urethane (meth) acrylate compound include U-6HA, U-6H, U-15HA, UA-32P, U-324A, UA-7200 (above, trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) CN968, CN9006, CN9010 (above, trade name, manufactured by Sartomer Japan, Inc.); UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, UN-904, UN-901T, UN-905, UN -952 (trade name, manufactured by Negami Kogyo Co., Ltd.); These components (D2) may be used alone or in combination of two or more.
  • the composition of the present invention may contain a (meth) acrylate compound that does not fall under the components (A) to (D) as long as the effects of the present invention are not impaired.
  • the total content of the components (A) to (D) is preferably 60 to 100% by mass, more preferably 75 to 100%, based on the total amount of the (meth) acrylate compound contained in the composition of the present invention. % By mass, more preferably 90 to 100% by mass, and still more preferably 95 to 100% by mass.
  • the composition of this invention can contain antioxidant as needed.
  • antioxidants include hindered phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, thioether antioxidants, vitamin antioxidants, lactone antioxidants, and amine antioxidants. Etc.
  • hindered phenol antioxidants are preferable from the viewpoint of heat resistance and yellowing resistance.
  • the number average molecular weight of the antioxidant is preferably 300 to 1500, and more preferably 330 to 1300, from the viewpoints of heat resistance and yellowing resistance.
  • hindered phenol antioxidant examples include Irganox 1010, 1076, 1330, 3114, 3125 (all are trade names, manufactured by BASF), Adekastab AO-20, AO-50, AO-50 -60, AO-80, AO-30, AO-40 (all are trade names, manufactured by ADEKA Corporation), BHT (trade names, manufactured by Takeda Pharmaceutical Co., Ltd.), Cyanox 1790 (trade names, And commercially available products such as Sumilizer GP, GM, GS, and GA-80 (all are trade names, manufactured by Sumitomo Chemical Co., Ltd.).
  • Examples of phosphorus antioxidants include IRAGAFOS 168, 12, 38, P-EPQ, 126 (all are trade names, manufactured by BASF), ADKSTAB329K, PEP-36, PEP-8, Commercial products such as HP-10, 2112, 260, 522A (all are trade names, manufactured by ADEKA Corporation), Weston 618, 619G, 624 (all are trade names, manufactured by GE) Is mentioned.
  • sulfur-based antioxidants examples include DSTP “Yoshitomi”, DLTP “Yoshitomi”, DLTOIB, DMTP “Yoshitomi” (all of which are trade names, manufactured by Yoshitomi Co., Ltd.), Seenox 412S (trade name, Sipro Kasei Co., Ltd. ), Cyanox 1212 (trade name, manufactured by Cyanamid Co., Ltd.), TP-D, TPS, TPM, TPL-R (all of which are trade names, manufactured by Sumitomo Chemical Co., Ltd.).
  • thioether-based antioxidant examples include commercially available products such as ADK STAB AO-412S and AO-503 (all of which are trade names, manufactured by ADEKA Corporation).
  • vitamin antioxidants examples include commercially available products such as tocopherol (trade name, manufactured by Eisai Co., Ltd.) and Irganox E201 (trade name, manufactured by BASF).
  • lactone antioxidant examples include commercially available products such as compounds described in JP-A-7-233160 and JP-A-7-247278, and HP-136 (trade name, manufactured by BASF). .
  • amine-based antioxidant examples include commercially available products such as Irgastab FS042 (trade name, manufactured by BASF) and GENOX EP (trade name, manufactured by Crompton).
  • the blending amount of the antioxidant is preferably based on 100 parts by mass of the total of the components (A) to (C) from the viewpoint of improving the transparency of the molded product obtained from the composition and suppressing yellowing. Is 0.1 to 20 parts by mass, more preferably 1 to 18 parts by mass, and still more preferably 1.5 to 15 parts by mass.
  • the composition of this invention can mix
  • a polymerization initiator any one of a thermal polymerization initiator that is cleaved by heat to generate an initiation radical, and a photopolymerization initiator that generates an initiation radical by irradiation with active energy rays such as light, electron beam, and radiation can be used. it can.
  • a thermal polymerization initiator the polymerization reaction can be promoted by heating the composition containing the thermal polymerization initiator at 40 to 200 ° C.
  • the composition containing the photopolymerization initiator is irradiated with ultraviolet rays or the like with a cumulative amount of light of 50 to 2000 mJ / cm 2 using a mercury xenon lamp or the like as a light source, It can be polymerized.
  • thermal polymerization initiator examples include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide; 1,1,3,3-tetramethylbutyl Hydroperoxides such as hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide; diisobutyryl peroxide, bis-3,5,5-trimethylhexanol peroxide, lauroyl peroxide, benzoyl peroxide, and Diacyl peroxides such as m-toluylbenzoyl peroxide; dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxide Xyl) hexane, 1,3-bis (t-butylperoxyisopropyl) hexan
  • diacyl peroxides peroxyketals, alkyl peroxy esters, and 1,1-di (t-hexylperoxy) cyclohexane are preferable.
  • Lauroyl peroxide and 1,1-di-t-butylperoxycyclohexane are preferable.
  • T-butylperoxy-2-ethylhexanoate and 1,1-di (t-hexylperoxy) cyclohexane are more preferred.
  • photopolymerization initiator examples include benzoin ether, 2,2-dimethoxy-1,2-diphenylethane-1-one (commercially available product: “IRGACURE651 (trade name) manufactured by BASF)”, 1-hydroxy-cyclohexyl.
  • the blending amount of the polymerization initiator is preferably 0.01 to 12 parts by mass, more preferably 0 with respect to 100 parts by mass in total of the components (A) to (C), from the viewpoint of effectively promoting the polymerization reaction. 1-8 parts by mass, more preferably 0.3-5 parts by mass.
  • the composition of the present invention includes a light stabilizer, an ultraviolet absorber, a lubricant, a plasticizer, an antistatic agent, an inorganic filler, a colorant, an antistatic agent, a release agent, as long as the effects of the present invention are not impaired. You may mix
  • the content of the component (A) in the first composition of the present invention is based on the total amount of the components (A) to (C) from the viewpoint of improving the heat resistance of the molded product obtained from the composition.
  • the amount is preferably 5 to 60% by mass, more preferably 10 to 45% by mass, and still more preferably 15 to 35% by mass.
  • the total amount of the components (A) to (C) does not exceed 100% by mass (the same applies hereinafter).
  • the content of the component (B1) in the first composition of the present invention is (A) from the viewpoint of appropriately increasing the viscosity of the composition and suppressing the influence by hydrolysis under high temperature and high humidity. It is preferably 20 to 80% by mass, more preferably 25 to 77% by mass, and still more preferably 30 to 75% by mass with respect to the total amount of the component (C). If the said content is 20 mass% or more, the viscosity of the composition obtained can be raised moderately and the workability of a composition can be improved. On the other hand, if the said content is 80 mass% or less, the phenomenon that (C) component itself hydrolyzes under high temperature and high humidity and the molded object which consists of this composition discolors can be suppressed.
  • the content of the component (B1) when the component (B2) is not contained is more preferably 40 to 77 mass with respect to the total amount of the components (A) to (C). %, More preferably 50 to 75% by mass.
  • the content of the component (B1) is more preferably 25 to 70% by mass with respect to the total amount of the components (A) to (C). More preferably, it is 30 to 60% by mass, and still more preferably 35 to 55% by mass.
  • (B) component when using together (B1) component and (B2) component, as content of (B2) component, improving the viscosity of a composition
  • (B1) component and (B2) component as content of (B2) component, improving the viscosity of a composition
  • it is preferably 5 to 40% by mass, more preferably 7 to 30% by mass, and still more preferably based on the total amount of the components (A) to (C). 10 to 25% by mass.
  • the said content is 30 mass% or more, it can improve a viscosity and can be set as the composition excellent in workability.
  • the said content is 85 mass% or less, the viscosity of a composition will not rise too much and the moldability of the composition obtained can be made favorable.
  • the mass ratio of the content of the component (B1) and the content of the component (B2) [(B1) component / (B2) component] is preferably 40/60 to 95/5, more preferably from the viewpoint of increasing the refractive index of the molded article obtained from the composition while improving the viscosity of the composition. Is 55/45 to 90/10, more preferably 60/40 to 85/15, and still more preferably 65/35 to 80/20.
  • the content of the component (C) in the first composition of the present invention is based on the total amount of the components (A) to (C) from the viewpoint of suppressing deformation and discoloration of the molded product obtained from the composition against heat.
  • the content is preferably 0 to 50% by mass, more preferably 3 to 50% by mass, still more preferably 5 to 40% by mass, and still more preferably 7 to 30% by mass.
  • the viscosity at 25 ° C. of the first composition of the present invention is preferably 1000 to 50000 mPa ⁇ s, more preferably 1100 to 40000 mPa ⁇ s, still more preferably 1200 to 5000 mPa ⁇ s, and still more preferably, from the viewpoint of processability. Is 1400-3500 mPa ⁇ s.
  • the value of the viscosity in 25 degreeC of said composition is a value measured based on the method as described in an Example.
  • compositions of components (A) to (C) in the second composition of the present invention and the viscosity of the composition are from the viewpoint of improving the heat resistance of the molded product obtained from the composition, with respect to the total amount of the components (A) to (C),
  • the amount is preferably 5 to 60% by mass, more preferably 8 to 45% by mass, and still more preferably 12 to 30% by mass.
  • the content of the component (B2) in the second composition of the present invention is (A) to (C) from the viewpoint of increasing the refractive index of the molded product obtained from the composition while improving the viscosity of the composition. ) It is preferably 30 to 85% by mass, more preferably 40 to 80% by mass, and still more preferably 45 to 70% by mass, based on the total amount of components. If the said content is 30 mass% or more, it can improve a viscosity and can be set as the composition excellent in workability. On the other hand, if the said content is 85 mass% or less, the viscosity of a composition will not rise too much and the moldability of the composition obtained can be made favorable.
  • the content of the component (C) in the second composition of the present invention is from the viewpoint of suppressing deformation and discoloration of the molded product obtained from the composition with respect to the total amount of the components (A) to (C).
  • the content is preferably 0 to 50% by mass, more preferably 5 to 50% by mass, still more preferably 10 to 45% by mass, and still more preferably 18 to 40% by mass.
  • the viscosity of the second composition of the present invention at 25 ° C. is preferably 500 to 50000 mPa ⁇ s, more preferably 700 to 40000 mPa ⁇ s, still more preferably 800 to 5000 mPa ⁇ s, and still more preferably, from the viewpoint of processability. Is 1000 to 2000 mPa ⁇ s.
  • compositions of components (A) to (C) in the third composition of the present invention and the viscosity of the composition are preferably relative to the total amount of the components (A) to (C) from the viewpoint of improving the heat resistance of the molded product obtained from the composition. Is 5 to 40% by mass, more preferably 10 to 35% by mass, and still more preferably 15 to 30% by mass.
  • the content of the component (B3) in the composition of the present invention is preferably 10 to 95 with respect to the total amount of the components (A) to (C) from the viewpoint of increasing the refractive index of the molded article obtained from the composition.
  • the mass is more preferably 15 to 90 mass%, still more preferably 20 to 85 mass%.
  • the content of the component (B3) when the component (B2 ′) and the component (C) are not contained is preferably 60 to 95% by mass with respect to the total amount of the components (A) to (C).
  • it is 65 to 90% by mass, more preferably 70 to 85% by mass.
  • the content of the component (B3) when containing at least one of the component (B2 ′) and the component (C) is preferably 10 to 80 relative to the total amount of the components (A) to (C).
  • the mass is more preferably 15 to 75 mass%, still more preferably 20 to 70 mass%.
  • the third composition of the present invention includes the component (B2 ′) together with the component (B3), thereby increasing the refractive index of the composition even when the content of the component (B3) is suppressed. it can.
  • the content of the component (B2 ′) is preferably 10 to 85% by mass, more preferably 30 to 80% by mass, still more preferably 50 to 70% by mass, based on the total amount of the components (A) to (C) is there.
  • the mass ratio of the content of the component (B3) to the content of the component (B2 ′) [(B3) component / (B2 ′) component] is preferably 15/85 to 40/60, more preferably 20 / 80 to 35/65, more preferably 25/75 to 30/70.
  • the 3rd composition of this invention can suppress generation
  • the content of the component (C) in the third composition of the present invention is appropriately determined within a range that does not impair the effect of the present invention to achieve a high refractive index, but the total amount of the components (A) to (C)
  • the content is preferably 0 to 50% by mass, more preferably 5 to 45% by mass, and still more preferably 10 to 40% by mass.
  • the mass ratio of the content of the component (B) and the content of the component (C) [(B) component / (C) component] is preferably 100/0 to 60/40, more preferably 85/15. To 65/35, more preferably 90/10 to 70/30.
  • the viscosity at 25 ° C. of the third composition of the present invention is preferably 300 to 50000 mPa ⁇ s, more preferably 400 to 40000 mPa ⁇ s, and further preferably 450 to 20000 mPa ⁇ s from the viewpoint of moldability.
  • the resin of the present invention can be obtained by polymerizing the above-described composition of the present invention.
  • the molded object of this invention is a molded object formed by shape
  • the polymerization and molding method the same method as that for molding a normal thermosetting resin can be used. Examples thereof include a method of proceeding simultaneously with the polymerization and molding steps in injection molding, compression molding, transfer molding, insert molding, and the like of the liquid composition.
  • a molded object can also be obtained by a potting process, a coating process, etc., and a molded object can also be obtained by the method similar to shaping
  • Liquid resin molding methods include liquid resin injection molding in which a liquid raw material composition or its prepolymer is injected into a high-temperature mold and cured by heating, and the liquid raw material composition is placed in a mold and pressed by a press Examples thereof include compression molding for pressing and curing, transfer molding for curing the raw material composition by applying pressure to the heated liquid raw material composition and press-fitting it into a mold.
  • the total light transmittance of the molded article of the present invention is preferably 85% or more, more preferably 88% or more, and still more preferably 90% or more.
  • the amount of decrease in light transmittance (absolute value of the light transmittance) at a wavelength of 440 nm between the molded body after thermal history left at 260 ° C. for 10 minutes and the molded body before thermal history is preferably 5. It is 0% or less, more preferably 3.0% or less, and still more preferably 2.5% or less.
  • the absolute value of the difference in light transmittance is preferably 5.0% or less, more preferably 4.0% or less, and still more preferably 3.0% or less.
  • decrease amount of the light transmittance in wavelength 440nm of the molded object after a heat history left to stand at 260 degreeC for 10 minute (s), and the molded object before a heat history.
  • the absolute value of the difference in light transmittance is preferably 5.0% or less, more preferably 3.0% or less, and still more preferably 1.5% or less.
  • the absolute value of the difference in the light transmittance is preferably 0.5% or less, more preferably 0.4% or less, and still more preferably 0.35% or less.
  • the refractive index of the molded product of the present invention at the d-line is preferably 1.45 or more, more preferably 1.50 or more, and further preferably 1.53 or more.
  • the refractive index at the d-line (wavelength: 589.3 nm) of the molded product obtained from the first composition of the present invention is preferably 1.45 to 1.65, more preferably 1.47 to 1. 60, more preferably 1.50 to 1.56.
  • the refractive index of the molded product obtained from the second composition of the present invention at the d-line is preferably 1.45 to 1.65, more preferably 1.50 to 1. 63, and more preferably 1.53 to 1.60.
  • the refractive index of the molded product of the present invention obtained from the third composition of the present invention at the d-line is preferably 1.55 or more, more preferably 1.55 to 1. 65, more preferably 1.55 to 1.60.
  • the Abbe number at the d-line (wavelength 589.3 nm) of the molded product of the present invention is preferably 60 or less, more preferably 55 or less, and still more preferably 50 or less.
  • the Abbe number at the d-line (wavelength 589.3 nm) of the molded product obtained from the first composition of the present invention is preferably 30 to 60, more preferably 35 to 52, and still more preferably 40 to 48. It is.
  • the Abbe number of the molded product obtained from the second composition of the present invention at the d-line (wavelength: 589.3 nm) is preferably 30 to 60, more preferably 33 to 52, still more preferably 36 to 45. It is.
  • the Abbe number at the d-line (wavelength: 589.3 nm) of the molded product obtained from the third composition of the present invention is preferably 40 or less, more preferably 25 to 40, still more preferably 30 to 40, More preferably, it is 35-40.
  • the linear expansion coefficient of the molded product of the present invention is preferably 110 ppm or less, more preferably 90 ppm or less, and still more preferably 80 ppm or less.
  • the flexural modulus of the molded article of the present invention is preferably 2.0 GPa or more, more preferably 2.4 GPa or more, and still more preferably 2.8 GPa or more.
  • the bending strength of the molded article of the present invention is preferably 50 MPa or more, more preferably 60 MPa or more, and further preferably 70 MPa or more.
  • the Shore D hardness of the molded article of the present invention is preferably 60 or higher, more preferably 70 or higher, and still more preferably 77 or higher.
  • the value of each said physical property of a molded object means the value measured by the method as described in an Example.
  • the molded article of the present invention is excellent in various optical performances, it is suitable as an optical component such as a lens used for various devices or a lens for optical communication.
  • Viscosity The viscosity of the obtained composition at 25 ° C. was measured using a viscometer (manufactured by Brooksfield, product name “LVDV-I +”) based on JIS K7117-1.
  • LVDV-I + a viscometer based on JIS K7117-1.
  • Total light transmittance As a test piece, using the obtained molded body having a thickness of 3 mm, based on JIS K7105, using a haze meter (product name “HGM-2DP” manufactured by Suga Test Instruments Co., Ltd.) The total light transmittance was measured.
  • thermo history 1 Amount of decrease in light transmittance at a wavelength of 440 nm after thermal history
  • a spectrophotometer product name “U-4100 Spectrometer, manufactured by Hitachi High-Tech Fielding Co., Ltd.
  • the light transmittance at a wavelength of 440 nm was measured with a meter ").
  • the test piece was placed on a stainless steel plate having a thickness of 1 mm and left at 260 ° C. for 10 minutes (hereinafter, this operation is also referred to as “thermal history 1”).
  • the light transmittance at a wavelength of 440 nm was measured in the same manner as described above, and the amount of decrease in light transmittance at a wavelength of 440 nm before and after heat history 1 (absolute value of the difference in light transmittance). (%) was calculated.
  • Refractive index, Abbe number As a test piece, a d-line at 20 ° C. was used for a molded article obtained with a thickness of 3 mm using a refractometer (manufactured by Metricon, product name “Model 2010 Prism Coupler”). The refractive index and Abbe number at a wavelength of 589.3 nm were measured.
  • the components shown in Tables 1 to 3 were added in the blending amounts (solid content ratios) shown in Tables 1 to 3 and mixed to obtain compositions.
  • two stainless steel plates (length 70mm x width 70mm x thickness 3mm)
  • two sheets of mirror-finished aluminum plates (length 70mm x width 70mm x
  • a container obtained by sandwiching a Teflon (registered trademark) spacer length 70 mm ⁇ width 70 mm ⁇ thickness 3 mm
  • the Teflon (registered trademark) spacer portion of the container is provided with a window of 30 mm length ⁇ 30 mm width ⁇ 3 mm thickness, and the composition can be poured into the container from the window.
  • the composition is poured from the window of the container, and the container is held so as not to leak. After performing polymerization and molding, a plate-like molded body was obtained by cooling to room temperature.
  • ⁇ (A) component> “AM” 1-adamantyl methacrylate (produced by Osaka Organic Chemical Industry Co., Ltd.) represented by the following formula (a1).
  • BPE-80N ethoxylated bisphenol A dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) represented by the following formula (b2).
  • Epoxy ester 3000MK Bisphenol A diglycidyl ether methacrylic acid adduct represented by the following formula (b3) (manufactured by Kyoeisha Chemical Co., Ltd.).
  • Epoxy ester 3000A Bisphenol A diglycidyl ether acrylic acid adduct represented by the following formula (b4) (manufactured by Kyoeisha Chemical Co., Ltd.).
  • SR-349 ethoxylated bisphenol A type diacrylate (manufactured by Sartomer Japan, Inc.) represented by the following formula (b5).
  • A-BPEF 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene represented by the following formula (b6) (manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • ⁇ (C) component> “SR-399” Dipentaerythritol pentaacrylate represented by the following formula (c1) (manufactured by Sartomer Japan KK, number average molecular weight 525).
  • SR-499 ethoxylated (6) trimethylolpropane triclarate represented by the following formula (c2) (manufactured by Sartomer Japan, Inc., number average molecular weight 560).
  • SR-295 Pentaerythritol tetraacrylate represented by the following formula (c3) (manufactured by Sartomer Japan KK, number average molecular weight 352).
  • A-DCP Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) represented by the following formula (e).
  • Thermal polymerization initiator 1,1-di (t-hexylperoxy) cyclohexane (manufactured by NOF Corporation) represented by the following formula (f1).
  • Antioxidant (TP-D) a thioether-based antioxidant represented by the following formula (f2) (manufactured by Sumitomo Chemical Co., Ltd., pentaerythrityltetrakis (3-laurylthiopropionate), number average molecular weight : 1162). (H 25 C 12 SCH 2 CH 2 COOCH 2) 4 C (f2)
  • Antioxidant (ADK STAB A-80) a hindered phenol-based antioxidant represented by the following formula (f3) (manufactured by ADEKA Corporation, number average molecular weight: 741).
  • compositions of Examples 1a to 8a all have high viscosities at 25 ° C. of 1000 mPa ⁇ s or more, and are excellent in workability. Further, the various optical performances of the molded products obtained from the compositions of Examples 1a to 8a were all good. On the other hand, the compositions of Comparative Examples 1a and 2a both had low viscosities at 25 ° C., resulting in problems in workability.
  • compositions of Examples 1b to 8b all have a high viscosity at 25 ° C. of 500 mPa ⁇ s or more, and are excellent in workability. Further, the various optical performances of the molded products obtained from the compositions of Examples 1b to 8b were all good. On the other hand, the compositions of Comparative Examples 1b and 2b both had low viscosities at 25 ° C., resulting in problems with workability.
  • the molded products obtained from the compositions of Examples 1c to 5c all have a high refractive index of 1.55 or more at d-line (wavelength: 589.3 nm) at 20 ° C. Moreover, it can be seen that the light transmittance at 440 nm is high and the transparency is excellent. It can also be seen that the transparency does not decrease even after a heat history of 260 ° C., has very high heat resistance that can withstand the solder reflow process, and is excellent in shape stability.
  • the (meth) acrylate composition of the present invention has excellent processability due to its high viscosity, and also has excellent heat resistance while maintaining optical performance such as excellent transparency and shape stability due to thermal history. In addition, a molded article having a high refractive index can be obtained. Therefore, the (meth) acrylate composition of the present invention is suitable as a material for forming optical parts such as lenses used in various devices and lenses for optical communication.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Composition à base de (méth)acrylate comprenant un composé (méth)acrylate (A) qui possède un groupe adamantyle représenté par la formule générale (A-1) et un composé (méth)acrylate (B) qui a une structure spécifique dans une molécule unique. Ladite composition présente une excellente aptitude au façonnage en raison de sa viscosité élevée et affiche de bonnes propriétés en termes de résistance à la chaleur, de stabilité de forme et de performance optique (indice de réfraction et transparence). [Dans la formule (A-1), chaque R1 représente indépendamment un atome d'hydrogène ou un groupe méthyle ; chaque X représente indépendamment une liaison simple, un groupe alkylène C1-4 ou un groupe oxyalkylène C1-4 ; U représente un groupe alkyle C1-4, un groupe halogéné, un groupe hydroxyle ou =O formé par liaison de deux U ; k représente un nombre entier de 0 à 15 ; et m représente un nombre entier de 1 à 4]
PCT/JP2013/054832 2012-02-29 2013-02-25 Composition à base de (méth)acrylate, résine, et article moulé WO2013129345A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018030339A1 (fr) * 2016-08-10 2018-02-15 東亞合成株式会社 Composition thermodurcissable
US10456965B2 (en) 2015-02-20 2019-10-29 Enplas Corporation Method of manufacturing a composite

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3438142B1 (fr) * 2016-03-29 2021-08-04 Asahi Kasei Kabushiki Kaisha Composition de résine méthacrylique et corps moulé
WO2019235465A1 (fr) * 2018-06-05 2019-12-12 出光興産株式会社 Composition thermodurcissable, procédé de production d'un article moulé l'utilisant, et produit durci
FR3085682B1 (fr) * 2018-09-11 2020-10-16 Arkema France Compositions reticulables ayant une faible viscosite pour revetements et materiaux a haut indice de refraction et a temperature de deflexion thermique elevee
JP7078134B2 (ja) * 2018-11-09 2022-05-31 株式会社ニコン 化合物、樹脂前駆体、硬化物、光学素子、光学系、カメラ用交換レンズ、光学装置、接合レンズ、及び接合レンズの製造方法

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01234406A (ja) * 1988-03-14 1989-09-19 Nippon Kayaku Co Ltd ジ（メタ）アクリル酸エステル、これを用いた樹脂組成物及びコーテイング剤
JPH0258511A (ja) * 1987-12-08 1990-02-27 Kureha Chem Ind Co Ltd 光学材料の製造方法
JPH0465406A (ja) * 1990-07-05 1992-03-02 Mitsubishi Rayon Co Ltd プラスチックレンズ用組成物
JPH04202309A (ja) * 1990-11-30 1992-07-23 Mitsubishi Rayon Co Ltd プラスチックレンズ用組成物
JP2000327950A (ja) * 1999-05-17 2000-11-28 Daicel Chem Ind Ltd コーティング組成物
JP2007186570A (ja) * 2006-01-12 2007-07-26 Hitachi Chem Co Ltd 光硬化性樹脂組成物及びパターン形成法
WO2009005036A1 (fr) * 2007-07-02 2009-01-08 Idemitsu Kosan Co., Ltd. Résine pour composant optique, composition de matière première utilisée pour la résine pour composant optique et composant optique
WO2009145061A1 (fr) * 2008-05-29 2009-12-03 旭硝子株式会社 Composition photodurcissable et procédé de fabrication pour un corps moulé ayant un motif fin sur la surface
WO2010116841A1 (fr) * 2009-03-30 2010-10-14 昭和電工株式会社 Composition durcissable et produit durci de celle-ci
JP2011090774A (ja) * 2010-12-08 2011-05-06 Toshiba Corp 紫外線硬化性樹脂材料
JP2011179009A (ja) * 2011-05-02 2011-09-15 Idemitsu Kosan Co Ltd 耐熱光学部品用材料

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU634338B2 (en) * 1990-02-08 1993-02-18 Mitsubishi Rayon Company Limited Composition for plastic lenses
US8829070B2 (en) * 2009-08-31 2014-09-09 Kabushiki Kaisha Toshiba Ultraviolet-curable resin material for pattern transfer and magnetic recording medium manufacturing method using the same

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0258511A (ja) * 1987-12-08 1990-02-27 Kureha Chem Ind Co Ltd 光学材料の製造方法
JPH01234406A (ja) * 1988-03-14 1989-09-19 Nippon Kayaku Co Ltd ジ（メタ）アクリル酸エステル、これを用いた樹脂組成物及びコーテイング剤
JPH0465406A (ja) * 1990-07-05 1992-03-02 Mitsubishi Rayon Co Ltd プラスチックレンズ用組成物
JPH04202309A (ja) * 1990-11-30 1992-07-23 Mitsubishi Rayon Co Ltd プラスチックレンズ用組成物
JP2000327950A (ja) * 1999-05-17 2000-11-28 Daicel Chem Ind Ltd コーティング組成物
JP2007186570A (ja) * 2006-01-12 2007-07-26 Hitachi Chem Co Ltd 光硬化性樹脂組成物及びパターン形成法
WO2009005036A1 (fr) * 2007-07-02 2009-01-08 Idemitsu Kosan Co., Ltd. Résine pour composant optique, composition de matière première utilisée pour la résine pour composant optique et composant optique
WO2009145061A1 (fr) * 2008-05-29 2009-12-03 旭硝子株式会社 Composition photodurcissable et procédé de fabrication pour un corps moulé ayant un motif fin sur la surface
WO2010116841A1 (fr) * 2009-03-30 2010-10-14 昭和電工株式会社 Composition durcissable et produit durci de celle-ci
JP2011090774A (ja) * 2010-12-08 2011-05-06 Toshiba Corp 紫外線硬化性樹脂材料
JP2011179009A (ja) * 2011-05-02 2011-09-15 Idemitsu Kosan Co Ltd 耐熱光学部品用材料

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10456965B2 (en) 2015-02-20 2019-10-29 Enplas Corporation Method of manufacturing a composite
WO2018030339A1 (fr) * 2016-08-10 2018-02-15 東亞合成株式会社 Composition thermodurcissable
CN109563212A (zh) * 2016-08-10 2019-04-02 东亚合成株式会社 热固化型组合物
JPWO2018030339A1 (ja) * 2016-08-10 2019-06-13 東亞合成株式会社 熱硬化型組成物
CN109563212B (zh) * 2016-08-10 2021-09-24 东亚合成株式会社 热固化型组合物
JP7028172B2 (ja) 2016-08-10 2022-03-02 東亞合成株式会社 熱硬化型組成物

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