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WO2015098783A1 - Composition durcissable par voie radicalaire, feuille plastique, rouleau de feuille plastique, et produit moulé - Google Patents

Composition durcissable par voie radicalaire, feuille plastique, rouleau de feuille plastique, et produit moulé Download PDF

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Publication number
WO2015098783A1
WO2015098783A1 PCT/JP2014/083808 JP2014083808W WO2015098783A1 WO 2015098783 A1 WO2015098783 A1 WO 2015098783A1 JP 2014083808 W JP2014083808 W JP 2014083808W WO 2015098783 A1 WO2015098783 A1 WO 2015098783A1
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Prior art keywords
plastic sheet
meth
acrylate
curable composition
alicyclic structure
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English (en)
Japanese (ja)
Inventor
佐藤　弘章
由佳 堤
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Mitsubishi Chemical Corp
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Nippon Synthetic Chemical Industry Co Ltd
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Priority to CN201480071335.0A priority Critical patent/CN105849143A/zh
Priority to KR1020167018316A priority patent/KR20160104633A/ko
Publication of WO2015098783A1 publication Critical patent/WO2015098783A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • 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
    • C08F120/00—Homopolymers 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/14—Methyl esters, e.g. methyl (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
    • 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
    • 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
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(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
    • 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
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • 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
    • 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
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/02—Homopolymers or copolymers of 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
    • 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
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • 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
    • C08J2333/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2333/04—Characterised by the use 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; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use 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; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical

Definitions

  • the present invention relates to a radically curable composition for forming a plastic sheet, and more specifically, a sheet roll formed by winding up a plastic sheet can be easily formed.
  • the present invention relates to a radical curable composition for forming a plastic sheet having excellent hardness.
  • a glass substrate is often used as a display substrate.
  • a chemically strengthened glass substrate having a thickness of about 0.5 to 2 mm is widely used as a protective plate.
  • a glass substrate having a thickness of about 0.2 to 1.1 mm is widely used.
  • a glass substrate having a thickness of about 0.2 to 0.7 mm is widely used in liquid crystal displays and organic electroluminescence (organic EL) displays.
  • plastic substrates have begun to be used from the viewpoint of weight reduction and safety and for the purpose of manufacturing flexible displays.
  • PMMA polymethyl methacrylate
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • Such plastic substrates have not only optical performance such as light transmittance and birefringence, but also thermal properties such as heat resistance and linear expansion coefficient, mechanical properties such as surface hardness and bending elastic modulus, water absorption and specific gravity, and resistance to resistance. High processability such as chemicals and solvent resistance is required.
  • a molded product obtained by photocuring a specific photopolymerizable composition is also seen.
  • a photopolymerizable composition comprising a polyfunctional urethane (meth) acrylate having an alicyclic structure and a polyfunctional (meth) acrylate having an alicyclic structure gives a resin molded article having high pencil hardness.
  • Patent Document 1 monofunctional (meth) acrylate having an alicyclic structure, polyfunctional urethane (meth) acrylate having an alicyclic structure, and polyfunctional (meth) acrylate having an alicyclic structure It is disclosed that the photopolymerizable composition gives a resin molded article having excellent optical properties and thermomechanical properties (see, for example, Patent Document 2).
  • plastic sheets having a high surface hardness are obtained, these are produced by casting a photocurable composition between two glass plates by a batch method. A sheet is manufactured, and a flat plastic sheet is obtained. Therefore, further three-dimensional molding cannot be performed on the obtained plastic sheet.
  • the “three-dimensional molding process” means that the conventional plastic sheet can only obtain a flat molded product, but is molded in a direction other than the plane, for example, a substantially vertical direction. It means a molding method for obtaining a molded product.
  • Japanese Patent Application Laid-Open No. 2009-127019 discloses cracks when continuously manufacturing a plastic sheet, when it is wound around a roll, when it is transported between rolls, and even when a support sheet is peeled off.
  • a method is described in which the bending elastic modulus of the predetermined region at both ends is lower than the bending elastic modulus of the predetermined region at the center with respect to the width direction of the plastic sheet.
  • it is difficult to obtain a sheet that is optically and mechanically uniform because only the edges are cured.
  • the reaction rate of at least a part of the plastic sheet exceeds 80%, and it has been difficult to perform a subsequent three-dimensional molding process using such a plastic sheet.
  • An object of the present invention is to provide a radical curable composition for forming a sheet, and further, using such a radical curable composition, a plastic sheet, a plastic sheet roll, and a three-dimensional molded product are also obtained. It is intended to provide.
  • the present invention contains a polyfunctional urethane (meth) acrylate having an alicyclic structure, a polyfunctional (meth) acrylate having an alicyclic structure, and a polymerization initiator.
  • a (meth) acrylic resin having an alicyclic structure By adding a (meth) acrylic resin having an alicyclic structure to the radical curable composition, the viscosity of the radical curable composition can be increased, so that a plastic sheet obtained by curing can be wound up. It has been found that a plastic sheet roll can be formed easily, and a thicker film can be formed, and a plastic sheet excellent in optical properties and surface hardness of a three-dimensional molded product to be a final cured product can be obtained.
  • the present invention has been completed.
  • the gist of the present invention is the following (1) to (10).
  • a radical curable composition containing the following components (A), (B), (C) and (D).
  • (D) Polymerization initiator (2) The content of (meth) acrylic resin (C) having alicyclic structure has the alicyclic structure.
  • the radical curability according to (1) wherein the amount is 1 to 50 parts by weight with respect to 100 parts by weight of the total of the functional urethane (meth) acrylate (A) and the polyfunctional (meth) acrylate (B) having the alicyclic structure.
  • Composition. (3) The radical curable composition according to the above (1) or (2), wherein the (meth) acrylic resin (C) having an alicyclic structure has a weight average molecular weight of 50,000 to 3,000,000. (4) Any one of (1) to (3) above, wherein the (meth) acrylic resin (C) having an alicyclic structure is a homopolymer of a mono (meth) acrylate (c1) having an alicyclic structure.
  • the reaction rate becomes 75% or more. Molded product [II] obtained by curing as described above.
  • the radically curable composition of the present invention can form a plastic sheet having a desired film thickness, and can form a rolled plastic sheet roll. It is easy to obtain a plastic sheet that is excellent in optical properties and surface hardness of the molded product that is the final cured product. Moreover, the viscosity of a radically curable composition can be made high by adjusting content of a component (C). Therefore, the plastic sheet formed from the radically curable composition of the present invention is useful for applications such as a protective plate for a display, a three-dimensional component around a display unit in a copying machine, an automobile, a home appliance, and the like.
  • (meth) acrylate is a generic term for acrylate and methacrylate
  • (meth) acryl is a generic term for acrylic and methacrylic
  • polyfunctional here means having two or more (meth) acryloyl groups in a molecule
  • the radically curable composition of the present invention contains the following components (A), (B), (C) and (D).
  • Component (A) is a urethane (meth) acrylate containing two or more (meth) acryloyl groups in the molecule. Since it is polyfunctional, the curing rate is improved and a plastic sheet can be obtained with high productivity. Moreover, a crosslinked resin can be formed by radical polymerization reaction by heat or light, and a plastic sheet with high surface hardness can be obtained. In addition, component (A) has a urethane group in the molecule, and a flexible plastic sheet excellent in mechanical strength such as flexural modulus and impact resistance can be obtained by hydrogen bonding. The improvement of the surface hardness is manifested particularly with a tetrafunctional or higher urethane (meth) acrylate. Moreover, polyfunctional urethane (meth) acrylate (A) has an alicyclic structure in a molecule
  • the number average molecular weight of component (A) is preferably 200 to 5,000. More preferably, it is 400 to 3,000, and still more preferably 500 to 1,000. When the number average molecular weight is too small, curing shrinkage increases and birefringence tends to occur. On the other hand, if it is too large, the crosslinkability tends to decrease and the heat resistance tends to decrease.
  • the polyfunctional urethane (meth) acrylate having an alicyclic structure as the component (A) is prepared by using a polyisocyanate compound having an alicyclic structure and a hydroxyl group-containing (meth) acrylate, if necessary, using a catalyst such as dibutyltin dilaurate. Can be obtained by reaction.
  • polyisocyanate compound having an alicyclic structure examples include, for example, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, hydrogenated xyly
  • examples include a diisocyanate, a hydrogenated diphenylmethane diisocyanate, and a trimer compound of isophorone diisocyanate. Of these, isophorone diisocyanate is preferred because of its good light resistance.
  • 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.
  • pentaerythritol tri (meth) acrylate dipentaerythritol penta (meth) acrylate, and dipentaerythritol tri (meth) acrylate are preferable in terms of surface hardness. Particularly preferred is pentaerythritol tri (meth) acrylate.
  • the polyfunctional urethane (meth) acrylate (A) having an alicyclic structure obtained by a reaction between a polyisocyanate compound having an alicyclic structure and a hydroxyl group-containing (meth) acrylate includes two or more kinds in the radical curable composition. You may mix and use. Among these reactants, acrylate is preferable from the viewpoint of curing rate, tetrafunctional or higher is more preferable from the viewpoint of heat resistance, and alicyclic rings represented by the following formulas (1) to (4) from the viewpoint of surface hardness. A tetrafunctional or higher functional urethane acrylate having a structure is particularly preferred.
  • R 1 is hydrogen or a methyl group.
  • component (B) is also a polyfunctional (meth) acrylate, it gives a highly heat-resistant plastic sheet. Although the effect of improving heat resistance is greater than that of the component (A) urethane (meth) acrylate, this monomer alone is too brittle because it becomes a glass-like crosslinked resin. Therefore, it is preferable to mix and copolymerize the urethane (meth) acrylate of component (A) and the polyfunctional (meth) acrylate of component (B) at a specific ratio. Thereby, a plastic sheet having good surface hardness, heat resistance and flexibility can be obtained.
  • component (B) is preferably bifunctional and more preferably methacrylate.
  • component (B) also has an alicyclic structure, which also reduces the saturated water absorption rate of the plastic sheet.
  • pentadecane di (meth) acrylate, bis (hydroxymethyl) pentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13 ]
  • pentadecane di (meth) acrylate, bis (hydroxy) pentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13 ]
  • pentadecane acrylate methacrylate, bis (hydroxymethyl) pentacyclo [6.5.1.1 3,6 . 0 2,7 .
  • pentadecane acrylate methacrylate, 2,2-bis [4- ( ⁇ -methacryloyloxyethoxy) cyclohexyl] propane, 1,3-bis (methacryloyloxymethyl) cyclohexane, 1,3-bis (methacryloyloxyethyl) Bifunctional (meth) acrylates such as oxymethyl) cyclohexane, 1,4-bis (methacryloyloxymethyl) cyclohexane, 1,4-bis (methacryloyloxyethyloxymethyl) cyclohexane, 1,3,5-tris (methacryloyloxymethyl) ) Trifunctional (meth) acrylates such as cyclohexane and 1,3,5-tris (methacryloyloxyethyloxymethyl) cyclohexane, among which bifunctional (meth) acrylates from the viewpoint of flexibility
  • the bifunctional methacrylate is more preferable
  • R 2 is an alkylene group which may contain an ether bond having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, R 3 is hydrogen or a methyl group, a is 1 or 2, and b is 0 or 1.
  • R 4 is an alkylene group which may contain an ether bond having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and R 5 is hydrogen or a methyl group.
  • R 6 is hydrogen or a methyl group
  • R 7 is an alkylene group which may contain an ether bond having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms
  • R 8 is hydrogen or a methyl group.
  • a preferable range of the blending ratio is 15:85 to 45:55 (weight ratio), and more preferably 20:80 to 40:60 (weight ratio).
  • the (meth) acrylic resin having an alicyclic structure as the component (C) is effective for increasing the viscosity of the radical curable composition.
  • a homopolymer of mono (meth) acrylate (c1) having an alicyclic structure is preferable in terms of compatibility, and in particular, poly (dicyclopentanyl) (Meth) acrylate), poly (adamantyl (meth) acrylate) and the like are preferable.
  • the weight average molecular weight of the acrylic resin (C) having an alicyclic structure is preferably 50,000 to 3,000,000, particularly 100,000 to 2,000,000, more preferably 300,000 to 1,500,000. If the weight average molecular weight is too small, a large amount of the acrylic resin (C) is required, so that the surface hardness tends to decrease, and if it is too large, the solubility becomes poor and the productivity tends to decrease.
  • said weight average molecular weight means the weight average molecular weight (Mw) of standard polystyrene conversion using GPC (gel permeation chromatography).
  • Such an acrylic resin (C) can be produced by a polymerization method by irradiation with active energy rays in addition to a solution polymerization method, and a polymerization method by ultraviolet irradiation is particularly preferable in terms of control of molecular weight.
  • the content of the acrylic resin (C) having an alicyclic structure is 1 to 50 parts by weight with respect to a total of 100 parts by weight of the components (A) and (B), from the viewpoint of thick film formation by increasing the viscosity. It is preferably 1 to 30 parts by weight, more preferably 1 to 15 parts by weight. When the content is too small, the increase in viscosity is insufficient and the film thickness tends to be difficult, and when the content is too large, the viscosity becomes too high and the productivity tends to decrease.
  • the radically curable composition of the present invention contains a polymerization initiator (D).
  • a polymerization initiator examples include a photopolymerization initiator (Dl) and a thermal polymerization initiator (Dh).
  • Dl photopolymerization initiator
  • Dh thermal polymerization initiator
  • Examples of the photopolymerization initiator (Dl) include benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethyl. Examples include benzoyldiphenylphosphine oxide. Among these, radical cleavage type photopolymerization initiators such as 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are preferable. These photopolymerization initiators (Dl) may be used alone or in combination of two or more.
  • thermal polymerization initiator (Dh) A known compound can be used as the thermal polymerization initiator (Dh).
  • hydroperoxide such as hydroperoxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide
  • Dialkyl peroxides such as t-butyl peroxybenzoate, peroxyesters such as t-butylperoxy (2-ethylhexanoate), diacyl peroxides such as benzoyl peroxide, and peroxycarbonates such as diisopropyl peroxycarbonate And peroxides such as peroxyketal and ketone peroxide.
  • photopolymerization initiators (Dl) and thermal polymerization initiators (Dh) can be used in combination.
  • the content of the polymerization initiator (D) is usually from 0.1 to 5 parts by weight, more preferably from 0.2 to 4 parts by weight, particularly preferably 0 to 100 parts by weight in total of the components (A) and (B) It is preferably 3 to 3 parts by weight. If the content is too large, the retardation of the plastic sheet increases and the light transmittance at 400 nm tends to decrease. On the other hand, when the amount is too small, the polymerization rate is decreased, and the polymerization may not proceed sufficiently.
  • a mercapto group containing compound (E) at the point which raises a crosslinking density.
  • the mercapto group-containing compound (E) include pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-sulfanylbutanoate), 1,3,5 -Tris (2- (3-sulfanylbutanoyloxy) ethyl) and the like.
  • mercapto group-containing compounds are preferably used in a proportion of usually 10 parts by weight or less, more preferably 5 parts by weight or less, in particular, with respect to 100 parts by weight of the total of component (A) and component (B). 4 parts by weight or less is preferable. When there is too much this usage-amount, there exists a tendency for the heat resistance and rigidity of the plastic sheet obtained to fall.
  • the curable composition may contain a small amount of auxiliary components as long as the physical properties of the plastic sheet of the present invention are not impaired.
  • auxiliary components for example, monomers having an ethylenically unsaturated bond other than components (A) and (B), polymerization inhibitors, antioxidants, ultraviolet absorbers, antifoaming agents, leveling agents, bluing agents, dyes and pigments And fillers.
  • a photoinitiator (Dl) and a thermal-polymerization initiator (Dh) a photoinitiator (Dl) and a thermal-polymerization initiator (Dh).
  • Monomers having an ethylenically unsaturated bond other than components (A) and (B) include methyl methacrylate, 2-hydroxyethyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meta ) Acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, norbornene (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl methanol and (meth) acrylate condensation composition, etc.
  • Monofunctional (meth) acrylates such as mono (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol Poly (ethylene glycol) di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-hydroxy 1 , 3-di (meth) acryloxypropane, 2,2-bis [4- (meth) acryloyloxyphenyl] propane, polyfunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate, acrylamide, methacrylamide, Examples thereof include (meth) acrylic acid derivatives such as acrylonitrile and methacrylonitrile, and styrene compounds such as styren
  • the compounding amount of the monomer having an ethylenically unsaturated bond other than the components (A) and (B) is 30 parts by weight or less with respect to a total of 100 parts by weight of the component (A) and the component (B). It is preferably 20 parts by weight or less, particularly 10 parts by weight or less. If the amount is too large, the heat resistance of the plastic sheet tends to decrease.
  • 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 blending ratio of the antioxidant is usually preferably 0.001 to 1 part by weight, particularly preferably 0.01 to 0.5 part by weight based on 100 parts by weight of the total of component (A) and component (B). Parts by weight.
  • the amount of the antioxidant is too small, the light resistance of the plastic sheet tends to be lowered, and when the amount is too large, the light transmittance tends to be lowered.
  • the radical curable composition of this invention can be manufactured by the method similar to well-known. For example, by mixing the components (A), (B), (C) and (D) with the component (E) and auxiliary components as necessary, and stirring and mixing until uniform at a temperature of 20 to 50 ° C. Can be manufactured. Thus, the radical curable composition of the present invention is obtained.
  • the radical curable composition of the present invention preferably has a viscosity at 23 ° C. of 100 to 20,000 mPa ⁇ s, more preferably 400 to 10,000 mPa ⁇ s, still more preferably 800 to 6,000 mPa ⁇ s. is there. If the viscosity is too low, the thick film formability tends to decrease, and conversely if it is too high, the productivity tends to decrease. Examples of the method for adjusting the viscosity include appropriately controlling the types and blending amounts of the components (A), (B) and (C).
  • composition viscosity at this time is a value measured using a cone / plate viscometer (TPE-100, manufactured by Toki Sangyo) at a Peltier plate temperature of 23 ° C. and a cone rotor of use: 3 ° ⁇ R14. is there.
  • the plastic sheet [I] of the present invention is obtained by curing a radically curable composition by heating or irradiation with active energy rays so that the reaction rate is usually 50% or more and less than 75%.
  • Such a plastic sheet [I] is produced by a batch-type optical molding method, that is, a mold in which two transparent glasses are opposed to each other through a spacer for thickness control. It can be obtained by injecting a radical curable composition, curing by irradiation with heat or active energy rays, and demolding. However, from the viewpoint of productivity and long run property, it is preferably continuous by roll-to-roll. It can be obtained by the photoforming method of the formula. Such a continuous photoforming method can be performed as follows.
  • the radical curable composition layer is formed on the support film so as to have a desired film thickness, and the support film is in contact with the upper part.
  • the laminated body is prepared, and the laminated body is heated or irradiated with active energy rays to cure the radical curable composition, and then, as necessary, from both sides of the cured resin layer (plastic sheet).
  • the plastic film [I] can be obtained by peeling the support film.
  • the feeding direction of the support film in this step can be any of the horizontal direction, the vertical direction with respect to the horizontal, and the direction angled from the horizontal. From the viewpoint of production efficiency, a method of forming the film surface continuously and feeding it in the horizontal direction is preferable.
  • the layer structure of the laminate is, for example, a three-layer structure of support film / curable composition [I] / support film, or support film / curable composition [I] / support film / curable composition [I]. / A five-layer structure of the support film is also possible.
  • a three-layer structure of supporting film / curable composition [I] / supporting film is preferable in that the curing process described later proceeds efficiently.
  • a plastic sheet roll which is a roll body of the plastic sheet [I] can be obtained by winding the obtained plastic sheet [I] around a branch pipe.
  • the support film may be any film as long as it does not inhibit curing due to radical polymerization, and among them, a gas barrier resin film is preferable from the viewpoint of not inhibiting curing due to oxygen.
  • the oxygen permeability is 200 cc / m 2 ⁇ day ⁇ atm or less in an environment of 20 ° C. and dry conditions when the thickness of the gas barrier resin film is 20 ⁇ m. It is preferable in that it can be cured well (that is, radical polymerization) and can be cured efficiently, and is particularly preferably 100 cc / m 2 ⁇ day ⁇ at or less, more preferably 20 cc / m 2 ⁇ day ⁇ It is preferably at or below. If this value is too high, good curing cannot be achieved due to oxygen inhibition, and the degree of polymerization and conversion tend to decrease. The lower limit is usually 0.01 cc / m 2 ⁇ day ⁇ atm.
  • Such measurement of oxygen permeability is obtained by measurement using an oxygen permeability meter according to the measurement method shown in JIS K 716-2: 2006.
  • the glass transition temperature of the resin constituting the support film is usually 0 ° C. or higher, particularly It is preferably 30 ° C or higher, more preferably 50 ° C or higher. If the glass transition temperature is too low, the glass transition temperature may melt and break when subjected to heat. In addition, the upper limit of this glass transition temperature is 400 degreeC normally.
  • the thickness of the support film used in the present invention is usually 100 ⁇ m or less, particularly 10 to 75 ⁇ m, more preferably 15 to 50 ⁇ m from the viewpoint of light transmittance. If the thickness is too thick, the light transmittance tends to be lowered, and if it is too thin, there is a tendency that breakage occurs during the operation or the safety is impaired.
  • the support film examples include polyester resin films such as polyethylene terephthalate film, nylon resin films such as nylon 6, biaxially stretched nylon, acrylonitrile resin films such as modified polyacrylonitrile, and polyvinyl alcohols.
  • polyester resin films such as polyethylene terephthalate film
  • nylon resin films such as nylon 6, biaxially stretched nylon
  • acrylonitrile resin films such as modified polyacrylonitrile
  • polyvinyl alcohols examples include resin films, vinyl alcohol resin films such as ethylene-vinyl alcohol resin films, and such uniaxially stretched and biaxially stretched vinyl alcohol resin films.
  • vinyl alcohol A resin film and further a biaxially stretched vinyl alcohol resin film is preferred.
  • Such a vinyl alcohol-based resin film is formed from a vinyl alcohol-based resin, and the vinyl alcohol-based resin only needs to have a vinyl alcohol unit formed by saponifying a vinyl ester unit.
  • the average saponification degree is 90 mol% or more, particularly preferably 95 mol% or more, and more preferably 97 mol% or more.
  • Examples of the vinyl alcohol resin of the vinyl alcohol resin film include a polyvinyl alcohol resin (hereinafter sometimes abbreviated as PVA resin) and an ethylene-vinyl alcohol copolymer (hereinafter abbreviated as EVOH). May be included).
  • PVA resin polyvinyl alcohol resin
  • EVOH ethylene-vinyl alcohol copolymer
  • examples of the PVA resin include PVA obtained by homopolymerizing vinyl acetate and saponification thereof, and modified PVA.
  • Examples of such modified PVA include copolymer modified products and post-modified products. it can.
  • a biaxially stretched PVA resin film is particularly preferable from the viewpoint of heat resistance.
  • the film thickness of the support film is usually 10 to 200 ⁇ m, preferably 15 to 100 ⁇ m, more preferably 15 to 50 ⁇ m. If the film thickness is too thin, the yield due to breakage tends to decrease, and if it is too thick, the weight of the roll-shaped material tends to be too large.
  • the external haze of the support film is a value obtained by subtracting the internal haze from the total haze of the object measured using a Nippon Denshoku Industries Co., Ltd. haze meter “NDH-4000” in accordance with JIS K 7361-1: 1997.
  • This internal haze measures haze (Hz1) by sandwiching only liquid paraffin between two glass plates in advance, and then measures haze (Hz2) by sandwiching a film wetted with liquid paraffin.
  • the value calculated by taking the difference of (1) is usually 0.4 or less, preferably 0.4 to 0.01, particularly preferably 0.2 to 0.01.
  • the resulting plastic sheet [I] has a tendency to increase the haze value of a molded product [II] obtained by three-dimensionally molding the plastic sheet [I].
  • the radical curable composition is usually cured by irradiation with active energy rays or heat (that is, radical polymerization).
  • active energy ray irradiation when curing by active energy ray irradiation, when irradiating the active energy ray to the curable composition, ultraviolet rays having a wavelength of 200 to 400 nm are usually used, and the irradiation light amount is usually 0.1 to 0.8 J / cm 2.
  • a more preferable range of the irradiation light amount is 0.1 to 0.7 J / cm 2 , and further preferably 0.15 to 0.5 J / cm 2 .
  • the illuminance of the active energy ray is usually 10 to 2,000 mW / cm 2 , particularly preferably 50 to 1,000 mW / cm 2 . If the illuminance is too small, the productivity tends to decrease. Conversely, if the illuminance is too large, the control of the degree of curing tends to be difficult.
  • the active energy ray source is not particularly limited as long as it is usually used in photocuring, and examples thereof include a metal halide lamp, a high-pressure mercury lamp lamp, an electrodeless mercury lamp, and LED-UV.
  • a metal halide lamp In order to prevent polymerization from running away due to infrared rays generated from a light source, it is also possible to use a filter that blocks infrared rays, a mirror that does not reflect infrared rays, or the like for the lamp.
  • the heat treatment temperature is usually 30 to 140 ° C.
  • the heat treatment time is usually 0.1 second to 30 minutes. If the heat treatment temperature is too low, the curing rate is slow, and if the temperature is too high, unintended side reactions and excessive curing can be considered. Further, if the heat treatment time is too long, curing tends to be excessive, and the three-dimensional molding process in the subsequent process tends to be difficult, and if it is too short, curing tends to be insufficient.
  • a support film can be peeled from both surfaces of the obtained plastic sheet [I], and only plastic sheet [I] can be taken out.
  • the obtained plastic sheet [I] can be used for a desired molding process as it is, but can also be wound around a branch pipe and stored as a plastic sheet roll. Without peeling off the support film, it can be wound into a branch pipe to form a plastic sheet roll.
  • polyolefin films such as polyethylene and polypropylene, polyethylene terephthalate, etc. It is also possible to wind together a polyester film, release paper, etc. as a separator.
  • the above-mentioned branch pipe has a diameter of usually 3 to 12 inches, preferably 3 to 6 inches.
  • the plastic sheet [I] of the present invention obtained above is obtained by curing a radically curable composition by heating or active energy ray irradiation so that the reaction rate is usually 50% or more and less than 75%. Yes, preferably 55 to 70%, particularly preferably 60 to 70%. If the reaction rate is too low, the film thickness tends to change during storage, and if it is too high, subsequent three-dimensional molding tends to be difficult.
  • the reaction rate can be measured as follows. That is, a test piece having a length of 50 mm and a width of 50 mm is freeze-pulverized and then measured with “AVANCE DPX-400” manufactured by BRUKER BIOSPIN using a solid NMR probe. The observation nucleus is measured at 13C, the rotation speed is 5,000 Hz, and 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 (%) is calculated from these peak area ratios.
  • the thickness of the plastic sheet [I] of the present invention is usually from 50 to 10,000 ⁇ m, particularly from 100 to 5,000 ⁇ m, more preferably from 400 to 3,000 ⁇ m, particularly preferably from 500 to 1,000 ⁇ m. It is preferable. If the thickness is too thin, the subsequent three-dimensional forming process tends to be difficult, and if it is too thick, roll formation tends to be difficult.
  • the plastic sheet [I] of the present invention preferably has a light transmittance of 80% or more, particularly 85% or more, more preferably 90% or more, from the viewpoint of increasing the brightness of the display.
  • the upper limit of the light transmittance is 99%.
  • the plastic sheet [I] of the present invention has a surface pencil hardness of usually 2B or more, particularly B or more, more preferably F or more, and preferably 2H or less, particularly H or less. If the pencil hardness is too low, the plastic sheet is likely to be damaged and the quality of the display tends to deteriorate. If the pencil hardness is too high, subsequent three-dimensional molding tends to be difficult.
  • the plastic sheet [I] of the present invention generally has a total haze of 3% or less, particularly 2% or less, more preferably 1.5% or less, from the viewpoint of high definition display. Further, the external haze is usually 0.5% or less, particularly 0.3% or less, and further preferably 0.15% or less.
  • the external haze is a value obtained by subtracting internal haze from the total haze of an object measured using a haze meter “NDH-4000” manufactured by Nippon Denshoku Industries Co., Ltd.
  • Such internal haze measures haze (Hz1) by sandwiching only liquid paraffin between two glass plates in advance, and then measures haze (Hz2) by sandwiching a film coated with liquid paraffin on the surface. Value calculated by taking the difference).
  • the reaction rate is usually 75% or more by normal heating or active energy ray irradiation. It can be set as the molded product [II] formed by curing.
  • the plastic sheet [I] of the present invention is not completely cured, it is a sheet that can be molded, and is subjected to a molding process corresponding to the design in order to have a desired design, and then usually By heating or irradiation with active energy rays, curing can be further advanced to obtain a molded product [II].
  • a known molding method can be used for the molding process. Examples thereof include a mold forming method such as press forming, vacuum forming, and pressure forming, and a method of cutting out an arbitrary shape using a cutter, a knife, or the like.
  • a mold forming method such as press forming, vacuum forming, and pressure forming
  • a method of cutting out an arbitrary shape using a cutter, a knife, or the like in particular, in the present invention, in the conventional plastic sheet, only a flat molded product can be obtained, whereas a three-dimensional molded product molded in a direction other than the plane, for example, a substantially vertical direction, is used. Can be obtained. Therefore, it is preferable to use a molded product formed by giving an arbitrary design to a plane in a direction other than the plane, for example, a substantially vertical direction.
  • the plastic sheet [I] molded into a desired shape by molding is usually further cured by irradiation with active energy rays or heat to form the molded product [II] of the present invention.
  • active energy ray it is preferable that the active energy ray is irradiated with an ultraviolet ray having a wavelength of 200 to 400 nm and photocured with a normal irradiation light quantity of 0.5 to 40 J / cm 2 .
  • a more preferable range of the irradiation light amount is 5 to 35 J / cm 2 , and more preferably 10 to 30 J / cm 2 .
  • the illuminance of the active energy ray is usually 10 to 2,000 mW / cm 2 , particularly preferably 50 to 1,000 mW / cm 2 . If the illuminance is too small, the productivity tends to decrease. Conversely, if the illuminance is too large, yellowing tends to occur.
  • the active energy ray source is not particularly limited as long as it is usually used in photocuring, and examples thereof include a metal halide lamp, a high-pressure mercury lamp lamp, an electrodeless mercury lamp, LED-UV, and the like.
  • a filter that blocks infrared rays, a mirror that does not reflect infrared rays, or the like for the lamp.
  • heat treatment may be performed to improve the degree of polymerization or release stress strain. At this time, it is preferable to perform heat treatment usually at 50 to 250 ° C. in the air or in vacuum.
  • the heat treatment temperature is usually 30 to 140 ° C.
  • the heat treatment time is usually 0.1 seconds to 10 hours. If the heat treatment temperature is too low, curing tends to be insufficient. If the heat treatment time is too short, curing tends to be insufficient, and if it is too long, productivity is lowered and an unintended side reaction may proceed.
  • the obtained molded product [II] of the present invention is obtained by curing by irradiation with active energy rays so that the reaction rate is usually 75% or more, preferably 80% or more, particularly preferably 85% or more. is there. If the reaction rate is too low, the surface hardness of the molded product tends to be insufficient.
  • the reaction rate can be measured by the same method as described above.
  • the thickness of the molded product [II] of the present invention is usually 50 to 10,000 ⁇ m, particularly 100 to 5,000 ⁇ m, more preferably 400 to 3,000 ⁇ m, and particularly 500 to 1,000 ⁇ m. preferable. If the thickness is too thin, the mechanical properties tend to deteriorate, and if it is too thick, the optical properties tend to decrease.
  • the molded product [II] of the present invention preferably has a light transmittance of usually 80% or more, particularly 85% or more, and more preferably 90% or more from the viewpoint of increasing the brightness of the display.
  • the upper limit of the light transmittance is 99%.
  • the molded product [II] of the present invention preferably has a surface pencil hardness of usually 2H or more, particularly 3H or more, more preferably 4H or more. If the pencil hardness is too low, the plastic sheet tends to be damaged and the quality of the display tends to deteriorate.
  • the molded product [II] of the present invention preferably has a total haze of 3% or less, particularly 2% or less, and more preferably 1.5% or less from the viewpoint of high definition display. Further, the external haze is usually 0.5% or less, particularly 0.3% or less, and further preferably 0.15% or less. In addition, this external haze means the value by the same measuring method as the said plastic sheet [I].
  • a plastic sheet having a desired film thickness can be formed, and a rolled plastic sheet roll can be easily formed. Further, the optical properties and surface hardness of the molded product to be a final cured product can be obtained. An excellent plastic sheet can be obtained, and is useful for applications such as a protective plate for a display and a three-dimensional component around a display unit in a copying machine, an automobile, a home appliance, and the like.
  • Pencil hardness The pencil hardness of the plastic sheet was measured according to JIS K 5600-5-4: 1999. The load was measured at 50 g or 750 g.
  • Saturated water absorption (%) was calculated from the weight increase after immersion in water at 23 ° C. for 20 days using a 50 mm ⁇ 50 mm test piece.
  • the compounding component was prepared as follows.
  • a flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet 192.0 g (0.86 mol) of isophorone diisocyanate and pentaerythritol triacrylate [mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (hydroxyl value) 120 mg KOH / g)] 808.0 g (1.73 mol) was charged, 0.01 g of hydroquinone methyl ether as a polymerization inhibitor and 0.01 g of dibutyltin dilaurate as
  • C-2 After blending dicyclopentanyl methacrylate and dicyclopentanyl acrylate at a weight ratio of 1: 1, 1% 1-hydroxycyclohexyl phenyl ketone was further added as a photopolymerization initiator, and after defoaming treatment, Sealed in a tare of biaxially stretched polyvinyl alcohol film so as not to enter air bubbles, adjusted to a thickness of 0.7 mm, and then placed a 2.8 mm glass plate on the top of the tare. Then, irradiation was performed so that a wavelength of 360 nm was 20 J / cm 2 with an illuminance of 50 mW / cm 2 .
  • C-3 After adding 0.5% 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator to dicyclopentanyl acrylate and defoaming it, it is sealed in a tare of a biaxially stretched polyvinyl alcohol film to prevent bubbles from entering. After adjusting the thickness to be 1.0 mm, a 2.8 mm glass plate is placed on the upper part of the tare, and a metal halide lamp is placed on the glass plate, and the 360 nm wavelength is 20 J / cm 2 at an illuminance of 50 mW / cm 2.
  • C ′ The following were prepared as a (meth) acrylic resin (C ′) for comparison.
  • C′-1) Poly n-butyl methacrylate (weight average molecular weight (Mw): 760,000)
  • C′-2) Polymethyl methacrylate (weight average molecular weight (Mw): 990,000)
  • a coating film was continuously formed on a 25 ⁇ m-thick biaxially stretched polyvinyl alcohol film continuously conveyed in the horizontal direction using an applicator having a clearance of 880 ⁇ m.
  • a biaxially stretched polyvinyl alcohol film having a thickness of 25 ⁇ m was separately bonded onto the coating film, and a 50 mW / w was measured on the 25 ⁇ m thickness of the biaxially stretched polyvinyl alcohol film by a metal halide lamp with an ultraviolet ray measuring device at a wavelength of 360 nm. in the irradiation intensity of cm 2, the exposure amount is conveyed with ultraviolet irradiation so as to be 250 mJ / cm 2.
  • the biaxially stretched polyvinyl alcohol film having a thickness of 25 ⁇ m on both sides is peeled off, and only the cured plastic sheet (the thickness of the sheet is described in Table 1) is wound around a branch pipe to obtain a roll-shaped composition (plastic film roll). It was.
  • Various physical properties of the obtained plastic sheet were evaluated, and the results are shown in Table 2.
  • the plastic sheet obtained by the Example is denoted by [I]
  • the plastic sheet obtained by the comparative example is denoted by [I ′].
  • the molded product [II] model is not molded so as to impart designability in a direction perpendicular to the plastic sheet plane. However, when the designability is imparted, the surface of the plastic sheet [I] If impurities do not adhere, the presence or absence of the design does not affect various physical properties of the molded product [II], and therefore, the molded product is equivalent to the molded product formed by imparting the design property.
  • the molded product obtained in the example is denoted as [II]
  • the molded product obtained in the comparative example is denoted as [II ′].
  • Table 2 The evaluation results of Examples and Comparative Examples are shown in Table 2.
  • a radical curable composition comprising a polyfunctional urethane (meth) acrylate having an alicyclic structure, a polyfunctional (meth) acrylate having an alicyclic structure, and a polymerization initiator is further added to
  • a (meth) acrylic resin having a ring structure By containing a (meth) acrylic resin having a ring structure, the viscosity of the radically curable composition can be increased, so that a sheet roll formed by winding up the plastic sheet [I] obtained by curing is formed.
  • the plastic sheet using the radical curable composition of the present invention can be advantageously used for various optical materials and electronic materials.
  • liquid crystal substrates, organic / inorganic EL substrates, electronic paper substrates, light guide plates, phase difference plates, touch panels, etc. various display members, optical recording substrates and film / coating applications for optical disks, thin films, etc.
  • It can be used for energy applications such as battery substrates and solar cell substrates, optical communication applications such as optical waveguides, and various optical films, sheets and coatings such as functional films and sheets, antireflection films and optical multilayer films.
  • it is highly expected as a display protective plate or a capacitive touch panel substrate.

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Abstract

L'objet de la présente invention est de pourvoir à une composition durcissable par voie radicalaire, qui sert à former une feuille plastique tridimensionnelle qui est un produit durci final de celle-ci ayant d'excellentes propriétés optiques et dureté de surface, et qui sert à former une feuille plastique facile à enrouler. La composition durcissable par voie radicalaire selon l'invention comprend des composants (A), (B), (C), et (D) : (A) (méth)acrylate d'uréthanne polyfonctionnel à structure alicyclique, (B) (méth)acrylate polyfonctionnel à structure alicyclique (hors (A)), (C) résine (méth)acrylique à structure alicyclique, et (D) amorceur de polymérisation.
PCT/JP2014/083808 2013-12-27 2014-12-19 Composition durcissable par voie radicalaire, feuille plastique, rouleau de feuille plastique, et produit moulé Ceased WO2015098783A1 (fr)

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