WO2015115154A1 - 樹脂成形体、及びその用途 - Google Patents

樹脂成形体、及びその用途 Download PDF

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Publication number
WO2015115154A1
WO2015115154A1 PCT/JP2015/050503 JP2015050503W WO2015115154A1 WO 2015115154 A1 WO2015115154 A1 WO 2015115154A1 JP 2015050503 W JP2015050503 W JP 2015050503W WO 2015115154 A1 WO2015115154 A1 WO 2015115154A1
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WIPO (PCT)
Prior art keywords
resin molded
meth
molded body
acrylate
resin
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PCT/JP2015/050503
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English (en)
French (fr)
Japanese (ja)
Inventor
渡邉　朗
早川　誠一郎
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日本合成化学工業株式会社
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Application filed by 日本合成化学工業株式会社 filed Critical 日本合成化学工業株式会社
Priority to KR1020167017200A priority Critical patent/KR20160113588A/ko
Priority to CN201580003415.7A priority patent/CN105849161A/zh
Publication of WO2015115154A1 publication Critical patent/WO2015115154A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/22—Component parts, details or accessories; Auxiliary operations
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/111—Anti-reflection coatings using layers comprising organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/003—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor characterised by the choice of material
    • B29C39/006—Monomers or prepolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/22—Component parts, details or accessories; Auxiliary operations
    • B29C39/24—Feeding the material into the mould
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F20/18—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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Definitions

  • the present invention relates to a transparent resin molded product obtained by photocuring a photocurable composition. More specifically, the present invention relates to a display substrate that is excellent in optical properties and thermomechanical properties, and is particularly safe and reliable. In addition, the present invention relates to a resin molded body useful for a protective plate, a touch panel substrate, an antireflection plate and the like.
  • a glass plate has been often used as a substrate for a display.
  • a flat glass substrate is used for a protective plate (cover), an antireflection plate, a touch panel, a liquid crystal display, an organic EL display, and the like that are the forefront of the display.
  • the UL94HB test horizontal flammability test
  • a resin having a thickness of 3 mm or more passes a UL standard if a burning rate is less than 40 mm / min using a 125 mm ⁇ 13 mm test piece.
  • display substrates require not only optical performance such as high light transmittance and low optical distortion (low birefringence), but also thermomechanical properties such as heat resistance and high hardness, and processing suitability such as solvent resistance. Is done. In order to satisfy these performances, resin molded bodies obtained by photocuring have been proposed (see, for example, Patent Documents 1 to 3).
  • the 1 mm thick resin molded body of Patent Document 1 may break at a height of about 1 m in a ball drop impact test of at most 8 g (impact energy 0.08 J).
  • the resin molded body having a thickness of 0.7 mm disclosed in Patent Document 2 may break at about 30 cm (impact energy 0.4 J) in a 130 g falling ball test.
  • the 0.2 mm resin molded body of Patent Document 3 may break at about 50 cm in a ball drop test of at most 16 g (impact energy 0.08 J).
  • As a protective plate for the display it is necessary to have an impact resistance that does not break even if the mobile phone is dropped from the pocket. (Impact energy 1.3J).
  • the flexural modulus of the resin molding is about 4 GPa in any of the disclosed technologies, which is only a few tenths of glass. If the thickness is 0.1 to 1 mm, it will bend greatly when pressed. For example, if the center part of a 10 cm square sheet is pushed with a finger at a load of about 1 kg, it will bend by 1 mm or more. Thus, the role of the protective plate for protecting the device is difficult to fulfill, and further improvement is desired. In order to reduce the amount of deflection, it is effective to increase the flexural modulus and increase the thickness.
  • the amount of deflection at the time of pressing depends on the flexural modulus of the resin molded body (inversely proportional to the flexural modulus), but more largely depends on the thickness (inversely proportional to the cube of the thickness).
  • a resin molded body having a thickness of 1 mm or more, preferably 1.5 mm or more, particularly preferably 2 mm or more is required.
  • Such a substrate has a haze value increased by roughening the surface or light scattering inside the resin, but coloring and bleeding out due to the addition of a flame retardant must be avoided.
  • the present invention is a transparent resin molded body obtained by curing a photocurable composition under such a background, and has a resin substrate that is excellent in optical performance and thermomechanical properties and excellent in safety and reliability. It is intended to provide.
  • the present inventors have obtained a resin molded body obtained by curing the photocurable composition (A), which is thicker than the conventional resin and has a slow burning rate.
  • the present inventors have found that the molded article has excellent optical performance and thermomechanical properties and is excellent in safety and reliability, thereby completing the present invention.
  • the gist of the present invention is a resin molded body obtained by curing the photocurable composition (A), has a thickness of 1 to 10 mm, and has a UL94HB flammability test (horizontal flammability test).
  • the combustion rate (S) measured in is about 40 mm / min or less.
  • a touch panel substrate using the resin molded body and an antireflection plate are also provided.
  • the present invention provides a resin base material having impact resistance, low flexibility, and low flammability, but also provides a method capable of photocuring even at a thickness that is unthinkable by common sense. is there.
  • the thickness of an object obtained by photocuring is several microns to several hundreds of microns, as represented by UV coating, and is the thickest in the resin molded products of Patent Documents 1, 2, and 3 described above. It is 1 mm. There are two reasons why thick photocuring is difficult.
  • a photocurable composition particularly a photocurable composition containing a (meth) acryloyl group
  • a photocurable composition containing a (meth) acryloyl group is a liquid and causes volume shrinkage of several percent to several tens of percent when cured (curing shrinkage). Called). For this reason, the resin is cracked by the internal stress generated by the curing shrinkage, and the molded body cannot form a desired surface shape.
  • a method of reducing the curing shrinkage by intentionally making the curing reaction inadequate can be considered, the obtained resin molding becomes unstable to light and heat, and expresses the original physical properties such as impact resistance and hardness. It will not do.
  • the resin molded body of the present invention has a flat and smooth surface without cracking even with a sufficient curing reaction using a photocurable composition having a large curing shrinkage, and has a small optical distortion (birefringence). It becomes a thick resin molding.
  • the resin molded body of the present invention is a thick resin molded body excellent in optical characteristics, thermomechanical characteristics, safety and reliability, and is a display substrate or protective plate such as an antireflection plate, a touch panel substrate, or a liquid crystal display. It is suitable as a substrate, an organic EL display substrate, a screen, a projector component and the like.
  • (meth) acrylate is a generic term for acrylate and methacrylate
  • (meth) acryl is a generic term for acrylic and methacrylic.
  • polyfunctional as used herein means having two or more (meth) acryloyl groups in the molecule.
  • the resin molded body of the present invention is obtained by curing the photocurable composition (A), and the thickness of the resin molded body is 1 to 10 mm.
  • the thickness is preferably 1.5 to 8 mm from the viewpoint of low flexibility, more preferably 2 to 6 mm from the viewpoint of impact resistance, and further preferably 3 to 5 mm from the viewpoint of low flammability. If the thickness of the resin molded body is too thin, all of the low flexibility, impact resistance and low flammability will be reduced. If it is too thick, it will be difficult to reduce the weight of the display.
  • the resin molded body of the present invention has a burning rate of 40 mm / min or less as measured by the UL94HB flammability test (horizontal flammability test).
  • the burning rate is preferably 30 mm / min or less from the viewpoint of improving safety, and more preferably 20 mm / min or less from the viewpoint of further improving safety. If the burning rate is too fast, the safety of the display will be reduced. In general, the lower limit of the burning rate in transparent resin is 1 mm / min.
  • the flame retardant reduces the transparency of the resin and causes bleed out.
  • the oxygen content in the resin structure is reduced, and a thermal decomposition temperature is improved by incorporating a crosslinked structure into the resin.
  • the total atoms constituting the photocurable composition (A) are controlled by controlling the chemical structure and the mixing ratio of each component in the photocurable composition (A).
  • a method of reducing the proportion of oxygen atoms (oxygen fraction) is preferable.
  • the method of selecting the monomer and oligomer which have an alicyclic structure, or raising the compounding ratio of this monomer and oligomer is mentioned.
  • the oxygen fraction is preferably 30% or less, more preferably 25% or less, and particularly preferably 23% or less in terms of reducing the combustion rate.
  • the oxygen fraction in the present invention is a value calculated from the chemical structure, and is the weight percent of oxygen with respect to the total weight of the photocurable composition (A).
  • a photocurable composition (A) consists of three components of component A, B, and C, it can calculate according to following formula (1).
  • the compounding quantity in following formula (1) may be a weight part or weight%.
  • Oxygen fraction (%) 100 ⁇ [ ⁇ (number of oxygen in chemical structure of component A ⁇ oxygen atomic weight / molecular weight of component A) ⁇ mixing amount of component A ⁇ + ⁇ (number of oxygen in chemical structure of component B ⁇ Oxygen atomic weight / molecular weight of component B) ⁇ mixing amount of component B ⁇ + ⁇ (number of oxygen in chemical structure of component C ⁇ oxygen atomic weight / molecular weight of component C) ⁇ mixing amount of component C ⁇ ] (1)
  • the oxygen fraction of PMMA (chemical formula: (C 5 H 8 O 2 ) n) is 32% as calculated by the following formula.
  • the thermal decomposition temperature is preferably 300 ° C. or higher, more preferably 350 ° C. or higher, and particularly preferably 370 ° C. or higher in terms of reducing the combustion rate.
  • the upper limit of the thermal decomposition temperature is usually 500 ° C.
  • the thermal decomposition temperature in this invention is a thermal decomposition start temperature measured based on JISK7120.
  • the photocurable composition (A) used in the present invention is not particularly limited as long as it can be cured by light irradiation, but in particular, it is a composition containing a (meth) acryloyl group in terms of the productivity of the resin molded product. Preferably there is.
  • the photocurable composition (A) contains the following components (A1) and (A2), preferably further contains a photopolymerization initiator (A3). It is preferable from the viewpoint of the heat resistance of the resin molded body.
  • A1 Urethane (meth) acrylate compound
  • A2) Multifunctional (meth) acrylate compound
  • A3) Photopolymerization initiator
  • the urethane (meth) acrylate compound (A1) used in the present invention is obtained, for example, by reacting a polyisocyanate and a hydroxyl group-containing (meth) acrylate using a catalyst such as dibutyltin dilaurate as necessary. It is preferable.
  • polyisocyanate examples include aliphatic polyisocyanates such as ethylene diisocyanate and hexamethylene diisocyanate, isophorone diisocyanate, bis (isocyanatomethyl) tricyclo [5.2.1.0 2,6 ] decane, and norbornene diisocyanate.
  • Polyisocyanate having an alicyclic structure such as a trimer compound of added xylylene diisocyanate and isophorone diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, Polyisocyanate and the like having an aromatic ring of lid diisocyanate and the like.
  • polyisocyanates having an alicyclic structure specifically isophorone diisocyanate and norbornene diisocyanate are preferred from the viewpoint of low curing shrinkage.
  • hydroxyl group-containing (meth) acrylate examples include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3- (meth) Examples include acryloyloxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol tri (meth) acrylate.
  • polyfunctional (meth) acrylates such as pentaerythritol tri (meth) acrylate and dipentaerythritol tri (meth) acrylate are preferred from the viewpoint of pencil hardness of the resin molding.
  • urethane (meth) acrylate obtained by reaction of polyisocyanate and hydroxyl group-containing (meth) acrylate may be used.
  • reactants acrylate compounds are preferable from the viewpoint of curing speed, and 2-9 functions, particularly 2-6 functions, are particularly preferable from the viewpoint of surface hardness and flexural modulus.
  • polyfunctional (meth) acrylate type compound (A2) what is necessary is just to have two or more (meth) acryloyl groups, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetra Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, Phosphorus di (meth) acrylate, pentaerythritol di (meth) acrylate,
  • trimethylolpropane tri (meth) acrylate pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra ( (Meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene oxide Modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol Aliphatic compounds such as rutri
  • the content (weight ratio) of the urethane (meth) acrylate compound (A1) and the polyfunctional (meth) acrylate compound (A2) is the point of thermomechanical properties of the resin molded product.
  • the urethane (meth) acrylate compound (A1) / polyfunctional (meth) acrylate compound (A2) (weight ratio) is preferably 10/90 to 70/30, and more preferably 20/80 to 60 / It is preferably 40, particularly 30/70 to 50/50. If the content ratio of the urethane (meth) acrylate compound (A1) is too small, the pencil hardness tends to decrease, and if it is too large, the water absorption rate tends to increase.
  • the photocurable composition (A) used in the present invention may contain a monofunctional (meth) acrylate compound
  • examples of the monofunctional (meth) acrylate compound include methyl (meta) ) Acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, tricyclodecyl (meth) acrylate , Tricyclodecyloxy
  • cyclohexyl (meth) acrylate, tricyclodecyl (meth) acrylate, tricyclodecyloxymethyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, adamantyl (meth) acrylate, and the like can be mentioned.
  • (meth) acrylates having an alicyclic structure are preferable in terms of low curing shrinkage.
  • the content is 100% by weight with respect to 100 parts by weight of the polyfunctional (meth) acrylate compound. 50 parts by weight or less, more preferably 30 parts by weight or less, and particularly preferably 10 parts by weight or less. If the content is too large, the heat resistance tends to decrease.
  • the photopolymerization initiator (A3) used in the present invention is not particularly limited as long as it can generate radicals upon irradiation with active energy rays.
  • benzophenone benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone 1-hydroxycyclohexyl phenyl ketone, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2 -(O-benzoyloxime) and the like.
  • 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime) and 2,4 are preferable in terms of producing a thick resin molding. It is preferably at least one selected from 1,6-trimethylbenzoyldiphenylphosphine oxide.
  • photopolymerization initiators (A3) may be used alone or in combination of two or more.
  • the content of the photopolymerization initiator (A3) is 0.01 to 5 parts by weight with respect to 100 parts by weight as a total of the urethane (meth) acrylate compound (A1) and the polyfunctional (meth) acrylate compound (A2). It is preferably 0.05 to 3 parts by weight, more preferably 0.1 to 1 part by weight, particularly preferably 0.1 to 0.5 part by weight. If the content is too small, the polymerization rate tends to decrease, and the polymerization tends not to proceed sufficiently. If the content is too large, the light absorption of the photopolymerization initiator increases excessively and the interior of the resin molded product tends to be uncured. It is in.
  • 0.05 to 3 parts by weight is preferable from the viewpoint of manufacturing a thick resin molded body having a thickness of 1 mm or more.
  • 0.1 to 1 part by weight is preferable, and 0.1 to 0.5 part by weight is preferable from the viewpoint of manufacturing a thick resin molded body of 3 mm or more.
  • thermal curing also proceeds in addition to photocuring, which is advantageous in terms of improving the degree of curing.
  • thermal polymerization initiator (A4) known compounds can be used.
  • hydroperoxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl Hydroperoxide such as hydroperoxide, dialkyl peroxide such as di-t-butyl peroxide and dicumyl peroxide, t-amylperoxybenzoate, t-butylperoxybenzoate, t-butylperoxy (2-ethyl) Peroxyesters such as hexanoate), diacyl peroxides such as benzoyl peroxide, peroxycarbonates such as diisopropylperoxycarbonate, peroxides such as peroxyketal and ketone peroxide.
  • thermal polymerization initiators (A4) may be used alone or in combination of two or more.
  • the content of the thermal polymerization initiator (A4) is 0.1 to 2 parts by weight with respect to a total of 100 parts by weight of the urethane (meth) acrylate compound (A1) and the polyfunctional (meth) acrylate compound (A2).
  • it is 0.2 to 1 part by weight, more preferably 0.3 to 1 part by weight, particularly preferably 0.4 to 1 part by weight.
  • 0.2 to 1 part by weight is preferable from the viewpoint of manufacturing a thick resin molded body of 1 mm or more, and a thick resin molded body of 2 mm or more is manufactured.
  • 0.3 to 1 part by weight is preferable, and 0.4 to 1 part by weight is preferable from the viewpoint of manufacturing a thick resin molded body of 3 mm or more.
  • the blending ratio (A3: A4 weight ratio) of the photopolymerization initiator (A3) and the thermal polymerization initiator (A4) is preferably 10:90 to 90:10, more preferably from the viewpoint of the curing rate. Is 20:80 to 70:30 in terms of deep curing. If the blending ratio of the photopolymerization initiator (A3) is too small, curing tends to be slow, and conversely if too large, internal curing tends to be difficult.
  • an ultraviolet absorber (A5) together with the photopolymerization initiator (A3).
  • the combination of UV absorbers seems to be a technology that seems to contradict thick film curing, but internal curing is possible with a small amount of blending, and it is possible to avoid defects such as cracks and sink marks due to the effect of curing shrinkage. it can.
  • the ultraviolet absorber (A5) is not particularly limited as long as it is soluble in the photocurable composition (A), and various ultraviolet absorbers can be used. Specifically, salicylic acid ester type, benzophenone type, triazole type, hydroxybenzoate type, hydroxyphenyl triazine type, cyanoacrylate type and the like can be mentioned. These ultraviolet absorbers may be used in combination. Of these, benzophenone-based, triazole-based, and hydroxyphenyltriazine-based compounds are preferable, and hydroxyphenyltriazine-based UV absorbers are particularly preferable from the viewpoint of compatibility with the photocurable composition (A).
  • the content of the ultraviolet absorber (A5) is usually preferably 0.001 to 0.1% by weight, particularly preferably 0.01 to 0.05% by weight, based on the photocurable composition (A). %. If the amount of the ultraviolet absorber is too small, the light resistance of the resin molded product tends to decrease, and if too large, the polymerization of the resin molded product tends to be insufficient.
  • the photocurable composition (A) used in the present invention appropriately includes a chain transfer agent, an antioxidant, a colorant, a thickener, an antistatic agent, a flame retardant, an antifoaming agent, various fillers, and the like.
  • the auxiliary component may be contained.
  • chain transfer agent examples include polyfunctional mercaptan compounds such as pentaerythritol tetrakisthioglycolate and pentaerythritol tetrakisthiopropionate. These polyfunctional mercaptan-based compounds are preferably used in a proportion of usually 10 parts by weight or less, more preferably 5 parts by weight or less, particularly 3 parts by weight, based on 100 parts by weight of the photocurable composition (A). Part or less is preferred. When there is too much this usage-amount, there exists a tendency for the heat resistance and rigidity of the resin molding obtained to fall.
  • polyfunctional mercaptan compounds such as pentaerythritol tetrakisthioglycolate and pentaerythritol tetrakisthiopropionate.
  • These polyfunctional mercaptan-based compounds are preferably used in a proportion of usually 10 parts by weight or less, more preferably 5 parts by weight or less, particularly 3 parts by
  • antioxidants examples include 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, 2,4,6-tri-t-butylphenol, and 2,6-di- t-butyl-4-s-butylphenol, 2,6-di-t-butyl-4-hydroxymethylphenol, n-octadecyl- ⁇ - (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) ) Propionate, 2,6-di-t-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 2,4 -Bis (n-octylthio) -6- (4-hydroxy-3 ', 5'-di-t-butylanilino) -1,3,5-triazine, 4,4-methylene-bis (2,6-di-)
  • the colorant is not particularly limited as long as it is soluble in the photocurable composition (A), and a known dye can be used, but a blueing agent is preferable in terms of the hue of the resin molded body.
  • the blending amount of the colorant is preferably 10 ppm or less. If the amount is too large, the light transmittance tends to decrease.
  • the manufacturing method of the resin molding of this invention is demonstrated.
  • the resin molded body of the present invention exceeds the thickness (usually about 0.01 to 0.2 mm) of a cured product obtained by photocuring that is generally performed.
  • the selection of a photopolymerization initiator and the combined use of a thermal polymerization initiator are effective for the production of a resin molded body having a thickness of 1 mm or more.
  • a light irradiation process is used for the production of a resin molded body having a thickness of 2 mm or more. It is also important.
  • the photocurable composition (A) is cast into a mold comprising two opposing glass plates and a spacer for controlling the thickness, and then the active energy rays are transferred while being conveyed in the horizontal direction. It is preferable to irradiate in order of one side, the other side, and both sides, and to photocure. By irradiating the active energy rays in three stages, the front and back and the inside of the thick resin molded product can be sufficiently cured.
  • the glass plate preferably has a thickness of 1 to 10 mm from the viewpoint of strength, and more preferably, from the viewpoint of the surface smoothness of the resin molded body, at least one glass surface in contact with the photocurable composition (A) is optically polished. It is preferable. In particular, the surface smoothness (Ra) is preferably 50 nm or less. If the glass plate is too thin, it cannot withstand the shrinkage stress generated when the photocurable composition (A) is cured, and the glass plate is cracked or warped. The flatness tends to decrease.
  • the glass plate may be chemically strengthened from the viewpoint of such strength. If the glass plate is too thick, the weight of the glass increases and the load on the equipment increases. In order to improve the demoldability of the resin molded body, the glass plate may be treated with a release agent on the surface.
  • the spacer controls the thickness of the resin molded body, but the material is not particularly limited, and a known material such as a resin is used. Among the resins, a rubbery material such as a silicone resin is preferable. More preferably, a material having a Shore A hardness (JIS K 6253 Type A) of 40 to 60, particularly 43 to 57, more preferably 45 to 55, in terms of flatness of the resin molded body, alleviates curing shrinkage. This is preferable.
  • a Shore A hardness JIS K 6253 Type A
  • UV light is suitable as the active energy ray.
  • a general ultraviolet lamp can be used, and a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, an electrodeless lamp, an LED lamp, or the like is used.
  • a metal halide lamp and an electrodeless lamp are preferable from the viewpoint of high illuminance.
  • the irradiation light quantity is preferably 20 J / cm 2 or more, and the maximum illuminance is preferably 100 mW / cm 2 or more.
  • the amount of irradiation light is more preferably 30 to 50 J / cm 2 .
  • the maximum illuminance is more preferably 200 to 20000 mW / cm 2 . If the maximum illuminance is too small, the degree of polymerization inside the resin molded product tends to decrease.
  • the irradiation light quantity said here is the total light quantity from the upper surface side and the lower surface side.
  • the maximum illuminance is the maximum illuminance from the upper surface side or the lower surface side.
  • the photocurable composition (A) is photocured while being constantly pressed in the range of 1 to 10 g / cm 2 .
  • the weight of the upper glass may be adjusted to 1776 g to 17760 g.
  • a more preferable range of the pressure is 2 to 6 g / cm 2 from the viewpoint of preventing sink marks during curing.
  • a thick film can be cured even with a photocurable composition having a large curing shrinkage.
  • a photocurable composition having a small curing shrinkage rate is advantageous for producing a thick resin molding of the present invention, but satisfies various properties such as low haze, high bending elastic modulus, and high pencil hardness. Therefore, even a photocurable composition having a cure shrinkage of about 10% must be used. This is because the haze increases when a filler is added to the photocurable composition to reduce the curing shrinkage, and the flexural modulus and pencil hardness decrease when an oligomer or polymer is blended.
  • the polyfunctional (meth) acrylate compounds used in Patent Documents 1 to 3 have a cure shrinkage of 8%, and it is important that a photocurable composition having such a cure shrinkage can be cured with a thick film. become.
  • a thick resin molding of 1 to 10 mm can be obtained by pressure curing.
  • the degree of curing after photocuring is important.
  • the degree of cure in the present invention can be obtained by measuring the reaction rate of the (meth) acryloyl group in the resin molding by an analytical method such as solid NMR or IR.
  • the reaction rate of the (meth) acryloyl group after photocuring is preferably 70% or more from the viewpoint of stabilization of physical properties. More preferably, it is 80% or more, and particularly preferably 85% or more. When the reaction rate is too small, the burning rate is increased, and mechanical properties such as flexural modulus and surface hardness tend to decrease.
  • the upper limit of the reaction rate is usually 99%.
  • Examples of the method for controlling the reaction rate after photocuring include control of the type and amount of (meth) acrylate component and photopolymerization initiator, illuminance and light amount, and adjustment of curing temperature.
  • the difference in reaction rate between the upper surface, the inside and the lower surface after photocuring is also important.
  • the difference in reaction rate is preferably 5% or less, more preferably 3% or less, and particularly preferably 2% or less. If the difference is too large, the resin molded product tends to warp or swell.
  • the reaction rate said here cuts out resin from the upper surface layer part of a resin molding, an inside, and a lower surface layer part, and measured each reaction rate by solid state NMR. Further, the surface layer portion means about 0 to 0.2 mm from the surface toward the inside.
  • the resin molded body of the present invention can be obtained by removing the photo-cured resin molded body from the mold. It is also possible to heat-treat the resin molded body in order to improve the degree of cure and remove stress strain.
  • the heat treatment may be performed under atmospheric pressure, inert gas, or vacuum, and the temperature is 50 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 150 ° C. or higher. In addition, as an upper limit, it is 400 degreeC normally.
  • the resin molded product of the present invention preferably has a total light transmittance of 85% or more, more preferably 88% or more, and particularly preferably 90% or more. If the total light transmittance is too small, the brightness of the display tends to decrease.
  • the upper limit is usually 96%.
  • the resin molded body of the present invention preferably has a haze of 1% or less, more preferably 0.5% or less, and particularly preferably 0.3% or less. If the haze is too large, the fineness of the display tends to decrease.
  • the lower limit is usually 0.01%.
  • the resin molded body of the present invention preferably has a negative value of hue b *, more preferably ⁇ 0.1 or less, and particularly preferably ⁇ 0.2 or less. If b * is too large, the high-quality feeling of the resin molded product tends to decrease.
  • the lower limit is usually -10.
  • the resin molded body of the present invention preferably has a flexural modulus of 3 GPa or more. More preferably, it is 3.5 to 5 GPa. If the flexural modulus is too low, the rigidity of the display substrate tends to decrease.
  • a method of appropriately controlling the type of the photocurable composition (A) and the content of the components can be used. For example, it is possible to use a bifunctional to hexafunctional compound as the urethane (meth) acrylate compound (A1).
  • the resin molded body of the present invention has a deflection of 1 mm or less when a 100 mm ⁇ 100 mm test piece is fitted into a 10 mm wide square outer frame and the center of the test piece is pressed with a finger at 1 kg / cm 2.
  • the amount of deflection is 0.5 mm or less, and still more preferably the amount of deflection is 0.2 mm or less.
  • the amount of deflection is too large, the function as a protective plate becomes insufficient, and the reliability of the entire display tends to be reduced, such as damage to internal devices.
  • a method of appropriately controlling the type of the above-described photocurable composition (A) and the content of the components can be used.
  • a bifunctional to hexafunctional compound as the urethane (meth) acrylate compound (A1).
  • the resin molded body of the present invention preferably has a pencil hardness of 3H or more, more preferably 5H or more, and particularly preferably 7H or more. If the pencil hardness is too low, the surface hardness as the protective plate tends to decrease.
  • a method of appropriately controlling the type of the above-described photocurable composition (A) and the content of the components can be used. For example, a tri- to hexa-functional compound may be used as the urethane (meth) acrylate compound (A1).
  • the resin molded body of the present invention preferably has a glass transition temperature of 100 ° C. or higher from the viewpoint of heat resistance. If the glass transition temperature is too low, formation of a transparent conductive film tends to be difficult.
  • a preferable range of the glass transition temperature is 150 to 400 ° C, more preferably 190 to 300 ° C, and still more preferably 200 to 250 ° C.
  • the method of controlling suitably the kind of photocurable composition (A) mentioned above and content of a component is mentioned. For example, the technique of raising the functional group number of a polyfunctional (meth) acrylate type compound (A2) is mentioned.
  • the resin molded body of the present invention can be cut or cut to a desired size by known techniques such as laser processing, NC processing, and punching. Moreover, according to various uses, a transparent conductive film, an antireflection film, an adhesive layer, a hard coat layer, an antifouling coat layer, an anti-fingerprint coat layer, a slipping coat layer, a printing layer, and a gas barrier film are formed. Can do.
  • the transparent conductive film examples include inorganic films such as indium and tin oxide (ITO), and organic films such as poly (3,4-ethylenedioxythiophene) (PEDOT).
  • ITO indium and tin oxide
  • PEDOT poly (3,4-ethylenedioxythiophene)
  • an ITO film is preferable in terms of conductivity and transparency.
  • the film thickness of such a transparent conductive film is usually 100 to 5000 mm, preferably 200 to 3000 mm, more preferably 300 to 2000 mm. If the film thickness is too thin, the conductivity tends to be insufficient, and if it is too thick, a film crack tends to occur.
  • a known method such as vapor deposition or sputtering is used.
  • the film forming temperature is preferably 50 to 300 ° C., more preferably 100 to 250 ° C., and further preferably 130 to 200 ° C. is there. If the film forming temperature is too low, the conductivity tends to be insufficient. Conversely, if the film forming temperature is too high, the light transmittance of the resin molded product tends to decrease.
  • the conductivity of the obtained transparent conductive film is adjusted so that the surface resistance value thereof is preferably 500 ⁇ / ⁇ or less, more preferably 200 ⁇ / ⁇ or less, and further preferably 100 ⁇ / ⁇ or less. If the surface resistance value is too high (that is, the conductivity is too low), the display performance of the display tends to deteriorate.
  • the antireflection film examples include an inorganic multilayer film having a three-layer structure of SiO 2 / TiO 2 / SiO 2 and a low refractive index organic coat film made of a fluororesin.
  • an inorganic multilayer film is preferable from the viewpoint of low reflectance.
  • the film thickness of such an inorganic film is selected according to the application, but is usually preferably adjusted to ⁇ / 4 or ⁇ / 2.
  • the inorganic antireflection film In forming the inorganic antireflection film, known methods such as vapor deposition, sputtering, and CVD are used.
  • the film forming temperature is preferably 30 to 200 ° C., more preferably 50 to 150 ° C., and still more preferably 70 to 100 ° C. If the film forming temperature is too low, antireflection tends to be insufficient, and conversely if it is too high, warping tends to occur.
  • the reflectance of the obtained antireflection film is preferably 3% or less, more preferably 2% or less, and further preferably 1% or less. If it is too high, the visibility of the display tends to be lowered.
  • the resin molded body of the present invention can be produced with high productivity, and the obtained resin molded body is excellent in optical properties and thermomechanical properties, and is a substrate and protective plate for display excellent in safety and reliability. Furthermore, it is suitable as a touch panel substrate and an antireflection plate.
  • Reaction rate of (meth) acryloyl group (%) After freeze-grinding a 50 mm ⁇ 50 mm resin molded body, about 0.3 g was packed in a solid NMR probe and measured with “AVANCE DPX-400” manufactured by BRUKER BIOSPIN (measuring condition: observation nucleus is 13C, rotation speed is 5000 Hz, room temperature). The carbonyl carbon in the unpolymerized (meth) acryloyl group is detected on the high magnetic field side (166 ppm), and the polymerized carbonyl carbon is detected on the low magnetic field side (176 ppm). The reaction rate (%) of the entire resin molded product (a) was calculated from the peak area ratio.
  • the upper surface layer portion (within a depth of 0.2 mm), the inside (the central portion 0 in the thickness direction). .2 mm) and the surface layer of the lower surface (within 0.2 mm depth), respectively, and after freeze-grinding, the measurement and the reaction rate (%) were calculated by the same method as described above.
  • Deflection (mm) A 100 mm ⁇ 100 mm test piece was fitted into a square outer frame with a width of 10 mm, and the amount of deflection when the center of the test piece was pressed with a finger at 1 kg / cm 2 was measured.
  • the evaluation criteria are as follows. ⁇ : When the deflection is 1 mm or less. ⁇ : When the deflection amount exceeds 1 mm and is 2 mm or less. X: When the amount of deflection exceeds 2 mm.
  • Pencil hardness Pencil hardness was measured in accordance with JIS K-5600 using a 50 mm ⁇ 50 mm molded resin.
  • Thermal decomposition temperature It measured based on JISK7120 and made thermal decomposition start temperature into thermal decomposition temperature. The heating rate was 5 ° C. per minute, and the maximum measurement temperature was 500 ° C. Further, nitrogen was used as the inflow gas, and was introduced at 50 ml per minute.
  • Example 1 Two optical polishing glass plates having a size of 390 mm ⁇ 500 mm are opposed to each other (upper glass weight 4680 g), and a silicone plate (Shore A hardness 50) having a thickness of 1.5 mm and a width of 10 mm is used as a spacer.
  • 30 parts of urethane acrylate having a functional alicyclic skeleton (A1) (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), bis (hydroxymethyl) tricyclo [5.2.1.0 2,6 ] decane dimethacrylate (A2) (new From 70 parts of Nakamura Chemical Co., Ltd.
  • Such mold placed horizontally, while conveying in the conveyor, by using a metal halide lamp, irradiance 120 mW / cm 2 from the top side, the light quantity 0.04 J / cm 2, then illuminance 120 mW / cm 2 from the lower surface side, the light quantity 0 .04 J / cm 2 , and finally cured by irradiating with ultraviolet rays having a single-sided illuminance of 200 mW / cm 2 and a light amount of 10 J / cm 2 (total of 20 J / cm 2 on both sides) from both the upper and lower surfaces.
  • the load on the photocurable composition is 2.6 g / cm 2 (4680 g / (37 cm ⁇ 48 cm)).
  • the cured product obtained by demolding was heated in a 200 ° C. vacuum oven for 2 hours to obtain a resin molded body of 370 mm ⁇ 480 mm ⁇ 1.5 mm.
  • Table 2 shows the reaction rate, cure shrinkage rate, and oxygen fraction of the obtained resin molding. The various properties were as shown in Table 3.
  • a transparent conductive film made of ITO having a thickness of 300 mm at 180 ° C. was formed on one side of the obtained resin molded body by a sputtering method, and a touch panel substrate was obtained.
  • the surface resistance was 100 ⁇ / ⁇ , which was good. there were.
  • an antireflection film having a three-layer structure of SiO 2 (300 nm) / TiO 2 (300 nm) / SiO 2 (300 nm) was formed on both surfaces of the obtained resin molded body by sputtering at 70 ° C. When the prevention plate was obtained, the total light transmittance was 98%, which was good.
  • Table 4 The evaluation results are shown in Table 4.
  • Examples 2 to 6 Except using the photocurable composition of Table 1 and the photocuring conditions of Table 2, resin molded bodies having various properties of Tables 2 and 3 and the touch panel substrate and reflection shown in Table 4 are the same as in Example 1. A prevention plate was obtained. Note that Luperox DC of the thermal polymerization initiator (A4) used has a one-hour half-life temperature of 135 ° C.
  • the resin molded body obtained by the present invention can be advantageously used for various optical materials and electronic materials.
  • various display members such as protective sheets, touch panels, antireflection plates, liquid crystal substrates, organic / inorganic EL substrates, PDP substrates, electronic paper substrates, light guide plates, retardation plates, optical filters, screens, projector parts, etc. It can be used for storage / recording applications including optical disk substrates, energy applications such as thin-film battery substrates and solar cell substrates, optical communication applications such as optical waveguides, functional films / sheets, and various optical films / sheets. In addition to optical materials and electronic materials, it can also be used for lighting materials, automotive materials, building materials, medical materials, stationery, and the like.

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10921492B2 (en) 2018-01-09 2021-02-16 Corning Incorporated Coated articles with light-altering features and methods for the production thereof
CN112512433A (zh) * 2018-07-25 2021-03-16 富士胶片株式会社 超声波探针
US11940593B2 (en) 2020-07-09 2024-03-26 Corning Incorporated Display articles with diffractive, antiglare surfaces and methods of making the same

Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
JP7120240B2 (ja) * 2017-08-29 2022-08-17 東亞合成株式会社 樹脂シート及びこれを製造するための硬化型組成物

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5819371A (ja) * 1981-07-25 1983-02-04 Matsushita Electric Ind Co Ltd 光硬化型被覆用樹脂組成物
JPS5971313A (ja) * 1982-10-15 1984-04-23 Matsushita Electric Works Ltd 光硬化性材料
JPH01312750A (ja) * 1988-06-13 1989-12-18 Hitachi Ltd 透明硬質樹脂板およびその製造方法
JPH05170846A (ja) * 1991-12-25 1993-07-09 Three Bond Co Ltd 紫外線硬化型難燃性樹脂組成物
JP2004176031A (ja) * 2002-02-06 2004-06-24 Sekisui Chem Co Ltd 樹脂組成物
JP2006193596A (ja) * 2005-01-13 2006-07-27 Nippon Synthetic Chem Ind Co Ltd:The 樹脂成形体、その製造方法、及びその用途
JP2006265502A (ja) * 2005-03-25 2006-10-05 Fuji Xerox Co Ltd 光重合性組成物及び難燃性樹脂成形品
JP2007284650A (ja) * 2006-03-24 2007-11-01 Mitsubishi Chemicals Corp 硬化性組成物
JP2008074085A (ja) * 2006-08-21 2008-04-03 Nippon Synthetic Chem Ind Co Ltd:The 樹脂基板の製造方法、及び、樹脂基板
WO2008053931A1 (en) * 2006-10-31 2008-05-08 Hitachi Chemical Co., Ltd. Resin composition for optical use, resin material for optical use using the same, optical filter for image display device, and image display device
JP2012229405A (ja) * 2011-04-13 2012-11-22 Nippon Synthetic Chem Ind Co Ltd:The 樹脂成形体、及びそれを用いてなる積層体

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1058465A (ja) * 1996-08-23 1998-03-03 Mitsubishi Chem Corp 光硬化性樹脂を用いた樹脂シートの製造法
JP3449342B2 (ja) 2000-03-30 2003-09-22 三菱化学株式会社 光硬化性組成物、低複屈折光学部材及びその製造方法
JP4385573B2 (ja) * 2002-07-31 2009-12-16 Ｄｉｃ株式会社 熱伝導電気絶縁感圧接着剤用組成物、およびこれを用いた粘着シート

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5819371A (ja) * 1981-07-25 1983-02-04 Matsushita Electric Ind Co Ltd 光硬化型被覆用樹脂組成物
JPS5971313A (ja) * 1982-10-15 1984-04-23 Matsushita Electric Works Ltd 光硬化性材料
JPH01312750A (ja) * 1988-06-13 1989-12-18 Hitachi Ltd 透明硬質樹脂板およびその製造方法
JPH05170846A (ja) * 1991-12-25 1993-07-09 Three Bond Co Ltd 紫外線硬化型難燃性樹脂組成物
JP2004176031A (ja) * 2002-02-06 2004-06-24 Sekisui Chem Co Ltd 樹脂組成物
JP2006193596A (ja) * 2005-01-13 2006-07-27 Nippon Synthetic Chem Ind Co Ltd:The 樹脂成形体、その製造方法、及びその用途
JP2006265502A (ja) * 2005-03-25 2006-10-05 Fuji Xerox Co Ltd 光重合性組成物及び難燃性樹脂成形品
JP2007284650A (ja) * 2006-03-24 2007-11-01 Mitsubishi Chemicals Corp 硬化性組成物
JP2008074085A (ja) * 2006-08-21 2008-04-03 Nippon Synthetic Chem Ind Co Ltd:The 樹脂基板の製造方法、及び、樹脂基板
WO2008053931A1 (en) * 2006-10-31 2008-05-08 Hitachi Chemical Co., Ltd. Resin composition for optical use, resin material for optical use using the same, optical filter for image display device, and image display device
JP2012229405A (ja) * 2011-04-13 2012-11-22 Nippon Synthetic Chem Ind Co Ltd:The 樹脂成形体、及びそれを用いてなる積層体

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10921492B2 (en) 2018-01-09 2021-02-16 Corning Incorporated Coated articles with light-altering features and methods for the production thereof
CN112512433A (zh) * 2018-07-25 2021-03-16 富士胶片株式会社 超声波探针
US11940593B2 (en) 2020-07-09 2024-03-26 Corning Incorporated Display articles with diffractive, antiglare surfaces and methods of making the same
US11971519B2 (en) 2020-07-09 2024-04-30 Corning Incorporated Display articles with antiglare surfaces and thin, durable antireflection coatings
US11977206B2 (en) 2020-07-09 2024-05-07 Corning Incorporated Display articles with diffractive, antiglare surfaces and thin, durable antireflection coatings

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