WO2008047940A1 - Stratifié comprenant une résine de polycarbonate - Google Patents

Stratifié comprenant une résine de polycarbonate Download PDF

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Publication number
WO2008047940A1
WO2008047940A1 PCT/JP2007/070672 JP2007070672W WO2008047940A1 WO 2008047940 A1 WO2008047940 A1 WO 2008047940A1 JP 2007070672 W JP2007070672 W JP 2007070672W WO 2008047940 A1 WO2008047940 A1 WO 2008047940A1
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WO
WIPO (PCT)
Prior art keywords
resin
polycarbonate resin
acrylic resin
laminate
acrylic
Prior art date
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PCT/JP2007/070672
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English (en)
Japanese (ja)
Inventor
Tomofuyu Marumo
Fumiaki Kakeya
Takeshi Onishi
Original Assignee
Mgc Filsheet Co., Ltd.
Mitsubishi Gas Chemical Company, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mgc Filsheet Co., Ltd., Mitsubishi Gas Chemical Company, Inc. filed Critical Mgc Filsheet Co., Ltd.
Priority to JP2008539898A priority Critical patent/JPWO2008047940A1/ja
Priority to KR1020097009932A priority patent/KR101113472B1/ko
Publication of WO2008047940A1 publication Critical patent/WO2008047940A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters

Definitions

  • the present invention relates to a laminate including a polycarbonate resin used as a mobile terminal display member such as a liquid crystal display cover and a sub display.
  • a preferred embodiment of the present invention can be achieved by a polycarbonate resin laminate for a portable terminal display member such as a liquid crystal display cover or a sub-display having excellent surface hardness, impact resistance and weather resistance, particularly a general polycarbonate resin.
  • the present invention relates to a laminate containing a polycarbonate resin for a portable terminal display member such as a liquid crystal display cover or a sub display having a high pencil hardness. Background art
  • Polycarbonate resin is widely used as a structural material to replace glass because of its excellent transparency, impact resistance, heat resistance, freedom of processing, lightness, etc.
  • Meter covers for electrical, electronic and OA equipment, etc. It is widely used in automobile applications such as LCD display covers, window glass, sunroofs, and instrument covers, and building materials such as daylighting roofing materials.
  • polycarbonate resin has a low surface hardness, and its application is limited due to insufficient surface properties such as low reflectivity.
  • various devices, devices have become smaller, lighter, higher performance, lower in price, and the conditions for using resin molded products such as liquid crystal display covers have become more stringent. High productivity and resin materials are strongly demanded in order to cope with low volume / multi-product production.
  • a transparent resin plate having a UV coating film on the surface of a transparent resin plate and a retardation film on the back surface is proposed as a liquid crystal display cover (Japanese Patent Laid-Open No. 2000-03-3). 2 1 9 9 3)
  • the material of the transparent resin plate was not described at all in terms of impact resistance, and was not practical.
  • polycarbonate resin with excellent impact resistance and visibility is also a proposal to use polycarbonate resin with excellent impact resistance and visibility as a protective cover for liquid crystal display devices (see Japanese Laid-Open Patent Publication No. 2 0 1 1 1 3 4 1 96) It was not practical at all.
  • the problem to be solved by the present invention is a laminate comprising a polycarbonate resin having excellent surface hardness, impact resistance and weather resistance, in particular, a high level and pencil hardness that cannot be achieved with a general polycarbonate resin board.
  • An object of the present invention is to provide a laminate containing a polycarbonate resin suitable for a liquid crystal display cover or a mobile terminal display member.
  • the present inventor has controlled the thickness of the layer including the acrylic resin constituting the laminate including the polycarbonate resin and the total thickness of the laminate within a specific range. Furthermore, by applying a hard coat treatment on a layer containing an acrylic resin or a layer containing an acrylic resin and a substrate containing a polycarbonate resin, a liquid crystal display with a good balance of surface hardness, especially pencil hardness and impact resistance. The inventors have found that a laminate containing a polycarbonate resin suitable for a bar can be obtained, and have completed the present invention.
  • One embodiment of the present invention is a laminate having a base material containing a polycarbonate resin and a layer containing an acryl resin, wherein the layer containing the acrylic resin is formed on the surface of the base material containing the polycarbonate resin by coextrusion.
  • the thickness of the layer containing the acrylic resin is 20 to 120 ⁇
  • the total thickness of the laminate is 0.3 to 1.5 mm
  • the surface of the layer containing the acrylic resin is The acrylic resin is a copolymer of methyl methacrylate and acrylic acid ester
  • the copolymerization ratio (methyl methacrylate / acrylic acid ester) is 8 0 20 to 9 9.5 / 0. 5 is the laminate.
  • Another embodiment of the present invention is a liquid crystal display cover having any one of the above laminates, and is used with a layer containing an acrylic resin laminated on the surface of a substrate containing the polycarbonate resin as an outside.
  • the liquid crystal display cover is a layer containing an acrylic resin laminated on the surface of a substrate containing the polycarbonate resin as an outside.
  • another embodiment of the present invention is a portable terminal display member having any one of the above laminates, and a layer containing an acrylic resin laminated on the surface of a base material containing the polycarbonate resin is arranged outside.
  • the mobile terminal display member used.
  • the thickness of the layer containing the acrylic resin constituting the laminate containing the polycarbonate resin and the total thickness of the laminate are controlled within a specific range, and further on the layer containing the acrylic resin or including the acrylic resin. It is possible to produce a laminate containing a polycarbonate resin suitable for a liquid crystal display cover or a portable terminal member having a balanced surface hardness and impact resistance by performing a hard coat treatment on a substrate containing a layer and a polycarbonate resin. it can.
  • Figure 1 shows the relationship between L (arbitrary chord length) and ⁇ (vertical length drawn from the center of the chord to the arc) used to calculate the stress ⁇ .
  • the polycarbonate resin according to the present invention is an aromatic dihydroxy compound or this. Or a small amount of a polyhydroxy compound and phosgene obtained by an interfacial polymerization method, or an optionally branched thermoplastic produced by an ester exchange reaction between the above aromatic dihydroxy compound and a diester of carbonic acid.
  • Polycarbonate polymer for example, carbonate ester polymer made mainly of bisphenol A is used.
  • the molecular weight of the polycarbonate resin used is from the viewpoint that it is preferable that a sheet can be produced by ordinary extrusion molding, and the viscosity average molecular weight is 15, 000 0 to 4 0, 0 0 0, preferably 2 0, 0 0 0 ⁇ 35, 0 0 0, more preferably 2 2, 5 0 0-2 5, 0 0.
  • Various commonly used additives may be added to the polycarbonate resin. Examples of the additives include an antioxidant, an anti-coloring agent, an ultraviolet absorber, a light diffusing agent, a flame retardant, a release agent, Examples include lubricants, antistatic agents, dyes and pigments.
  • methyl metatalylate is 90 to 99% and acrylic acid ester is 1 to 10%.
  • an acrylic resin containing a crosslinking component can be used as long as it can be extruded and does not impair the transparency.
  • the molecular weight is 3 to 300,000 in terms of weight average molecular weight, but is not limited thereto.
  • the load deflection temperature of the acrylic resin is preferably 90 ° C. or higher, preferably 95 ° C. or higher, more preferably 100 ° C. or higher. In order to ensure high pencil hardness, it is preferable that the acrylic resin does not substantially contain a rubber component.
  • Acrylic resin production methods are generally roughly classified into emulsion polymerization methods, suspension polymerization methods, and continuous polymerization methods, but the acrylic resins used in the present invention can be used in any polymerization method. can do. It is preferably produced by suspension polymerization or continuous polymerization, and more preferably produced by continuous polymerization.
  • the continuous production method can be divided into a continuous bulk polymerization method and a continuous solution polymerization method. In the present invention, an acryl resin obtained by either production method can be used.
  • the laminate containing the polycarbonate resin of the present invention has a base material containing a polycarbonate resin, a layer containing an acrylic resin, and a hard coat layer.
  • a low reflection treatment layer may be formed if necessary, and the total thickness of the laminate (including polycarbonate resin)
  • the sum of the one or more layers containing the base material and the acrylore resin and the hard coat layer) is 0.3 to 1.5 mm, and preferably 0.4 to 1.5 mm.
  • the thickness of the layer containing the acrylic resin laminated on one side of the substrate containing the polycarbonate resin is 20 to 120 ⁇ m, preferably 40 to: lOO / m, more preferably 40 to 80 / xm. .
  • the total thickness of the laminate including the polycarbonate resin is less than 0.3 mm, the sag against the external load becomes large, and if it exceeds 1.5 mm, it is not preferable because the thickness and weight of the liquid crystal product are hindered. Further, if the thickness of the layer containing the acrylic resin is less than 20 / xm, the pencil hardness is low, and if it exceeds 120 ⁇ , the impact resistance of the laminate is lowered, which is not preferable.
  • a layer containing acryl resin having a thickness of 10 to 30 / m can be laminated on the back surface of the base material containing polycarbonate resin on which the layer containing acrylic resin is not laminated.
  • the presence of a layer containing acryl resin on both sides allows a wider range of molding conditions in extrusion molding. In addition, there is no need to use different paints on the front and back sides when hard-coating on both sides. If the thickness of the layer containing the acryl resin exceeds 30 ⁇ , the impact resistance decreases, and if it is less than 10 jum, it is difficult to make the thickness uniform.
  • the layer containing the acrylic resin has a thickness of 15 to 25 ⁇ .
  • an ultraviolet absorber in the acrylic resin for the purpose of maintaining the weather resistance for a long period of time.
  • an antioxidant and an anti-coloring agent may be added.
  • Antioxidants should be added in an amount of 0.01 to 3% by weight, based on acrylic resin.
  • the anti-coloring agent can be added in an amount of 0.01 to 3% by weight based on the acrylic resin. If the total amount of UV absorber, antioxidant and anti-coloring agent is less than 0.1% by weight, sufficient weather resistance may not be exhibited. In addition, even if added in excess of 5% by weight, it is not possible to expect further improvement in weather resistance, but these additives cause bleed-out and cause whitening, resulting in decreased adhesion and impact strength. Sometimes.
  • UV absorbers added to the layer containing these acryl resins include benzotriazolone-based, benzophenone-based, salicinoleic acid phenolinoesterol-based, and triazine-based ultraviolet absorbers.
  • Benzotriazole UV absorbers include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-1,3-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2 ⁇ —Benzotriazole, 2_ (2′—Hydroxyl 5 ′ _ t—Octylphenol) Benzotriazole, 2,2-Methylenebis [4— (1, 1, 3, 3-Tetramethylenebutyl) 6- (2 H-benzotriazolone 2-yl) phenol] and the like.
  • benzophenone-based UV absorbers examples include 2-hydroxyoxy-4-octoxybenzophenone, 2, 4-dihydroxybenzo Phenone, 2-Hydroxy 4-methoxy 4'—Chronolebenzophenone, 2, 2-Dihydroxy 4-methoxybenzophenone, 2, 2-Dihydroxy 4,
  • UV absorbers examples include p-tert-butylphenyl salicylate, and triazine UV absorbers include 2, 4-diphenyl mono 6- (2 —Hydroxy 4-methoxyphenyl) 1, 1, 5, 5-triazine, 2, 4-diphenyl 6- (2-hydroxy _4-ethoxyphenyl) 1, 3, 5-triazine, 2, 4— Diphenyl mono (2-hydroxy-4 monopropoxyphenyl) 1, 1, 3, 5-triazine, 2, 4-diphenyl mono (2-hydroxy 4-butoxyphenyl) 1, 3, 3, 5-triazine 2, 4—Diphenyl 1-6— (2—Hydroxy 1 4-Butoxyphenyl) 1 1, 3, 5-Triazine, 2, 4-Diphenyl 1 6— (2-Hydroxy 4 1-Hexyloxyphenyl) 1 1, 3, 5 — Triazine, 2, 4-D
  • Antioxidants and anti-coloring agents added to these acrylic resin-containing layers include various types described in catalogs such as Ciba Specialty Chemicals Co., Ltd., Sumitomo Chemical Co., Ltd., Asahi Denka Kogyo Co., Ltd. Antioxidants and colorants can be used.
  • antioxidants include 2,6-di-tert-butyl-4-methylphenol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2, -methylenebis (4-ethylethyl).
  • 6-t-phenol 3, 3 ', 3 ", 5, 5', 5" — hexer t-butyl-a, a ', a "-(mesitylene, 2, 4, 6_tril) Tri-p-cresol, ethylene bis (oxyethylene) bis [3- (5 1-t-butyl-4-hydroxy_m-tolyl) propionate], hexamethylenbis [3- (3,5-5-t butyl 4- (Hydroxyphene-Nole) propionate], 2, 6-di-t-butyl-1-41 [4,6-bis (octylthio) -l 1,3,5-triazine _ 2-ylamino] phenol, pentaerythritol tetarakis [3 — (3,5—Di-t-Butinole 4-Hydroxyphenyl) Propi Sulfonate], N, N '- hexane one 1 to 6- Jiirubisu [3- (3, 5-
  • anti-coloring agents examples include tris (noyulphenyl) phosphite, tris (dinourylphenyl) phosphite, 4, 4'-thiobis (3-6-t-butylphenol), thiojetylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], trisolinolephenyl phosphite, triphenyl / phosphite, tris (2,4-di-tert-butylphenyl) phosphite .
  • HALS highly sterically hindered amine compound
  • a laminate in which a layer containing an acrylic resin is laminated on the surface of a substrate containing a polycarbonate resin is manufactured by the following coextrusion.
  • it is composed of one main extruder for extruding polycarbonate resin and a sub-extruder for extruding acryl resin constituting the coating layer, and the sub-extruder is usually smaller than the main extruder.
  • the temperature condition of the main extruder is usually 230 to 290 ° (preferably 240 to 280 ° C, and the temperature condition of the sub-extruder is usually 220 to 270 ° C, preferably 230 to 260 ° C.
  • a known method such as a multi-hold method or a feed block method can be used.
  • the molten resin laminated in the die is formed into a sheet inside the die, and then flows into a molding roll (poly Tsushinda roll) whose surface is mirror-finished. Form. This sheet-like molded product is mirror-finished and cooled while passing through the molding roll, and a laminate is formed.
  • the molten resin laminated in the feed block is guided to a sheet forming die such as a T die, and after being formed into a sheet shape, surface finishing and cooling are performed with a forming roll to form a laminated body.
  • the die temperature is usually 250 to 320 ° C, preferably 270 to 300.
  • the molding roll temperature is usually 100 to 190 ° C, preferably 110 to 80 ° C.
  • a vertical roll or a horizontal roll can be used as appropriate.
  • paints include organic solvents, UV absorbers, light stabilizers, antioxidants and other stabilizers, leveling agents, antifoaming agents, thickeners, antistatic agents, A surfactant such as an antifogging agent may be added as appropriate.
  • paints include organic solvents, UV absorbers, light stabilizers, antioxidants and other stabilizers, leveling agents, antifoaming agents, thickeners, antistatic agents, A surfactant such as an antifogging agent may be added as appropriate.
  • a bifunctional (meth) acrylate compound having a weight average molecular weight of 300 or less is 2 to 80 weight 0 /.
  • a photopolymerization initiator (B) is added in an amount of 1 to 1 with respect to 100 parts by weight of the photopolymerizable composition (A) consisting of 20 to 98% by weight of a hexafunctional urethane acrylate oligomer copolymerizable with Examples include those with 0 parts by weight.
  • bifunctional (meth) acrylate compound having a molecular weight of 300 or less examples include diethylene glycol di (meth) acrylate, dipropylene dalcol di (meth) acrylate, tripropylene dalcol diatalate, 1 , 6-hexanediol di (meth) acrylate, (meth) acrylic acid 2- (2'-vinyloxyethoxy) ethyl, 1,4 monobutanediol oligoacrylate, and the like.
  • photopolymerization initiator (B) those generally known can be used. Specifically, benzoin, benzophenone, benzoin ethinore ether, benzoin isopropyl etherol, 2, 2-dimethoxy-2-phenenoreacetophenone, 1-hydroxycyclohexenolephenol ketone, 2-hydroxy 2- Methyl 1-phenylprono ⁇ . 11-one, azobisisobutyronitrile, benzoyl peroxide and the like.
  • R 1 represents a substituted or unsubstituted monovalent hydrocarbon group, and R 2 represents an alkyl group
  • R 1 in the organotrialkoxysilane (C) represented by the formula (2) is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, n —Propyl group, n-butynole group, i-butyl group, sec-butynole group, n-hexyl group, n-heptyl group and other alkyl groups, other ⁇ -black propyl group, vinyl group, 3, 3 , 3-trifluoropropyl group, ⁇ -glycidoxypropyl group, ⁇ -methacryloxypropyl group, ⁇ -mercaptopropyl group, phenyl group, 3,4-epoxycyclohexylethyl group, and the like.
  • R 2 in organo trialkoxysilane (C) is an alkyl group having 1 to 5 carbon atoms, for example, methyl group, ethyl group, ⁇ -propyl group, ⁇ -butyl group, i-butyl group, sec- Examples thereof include a butyl group and a tert-butyl group.
  • colloidal Siri force As a product in which colloidal Siri force is dispersed in a basic aqueous solution, the products of Nissan Chemical Industries, Ltd. Snowtex 30, Snowtex 40, Catalytic Chemical Industry Co., Ltd. Taloyd S 30, Cataloid S 40, in acidic aqueous solution Snowtex 0 from Nissan Chemical Industries, Ltd. as a dispersed product, MA—ST, I PA—ST, NBA-ST, IBA—ST from Nissan Chemical Industries, Ltd. as products dispersed in an organic solvent, EG-ST, XBA-ST, NPC-ST, DMAC-ST, etc.
  • paints Akuriru resin cured with active energy ray to the back surface of the substrate comprising a polycarbonate resin which has not been coextruded, 1, 9 Nonanji ol di Atari rate (bl) 2 0 ⁇ 6 0 wt 0 / Photopolymerizable initiator (F) with a photopolymerization initiator (F) in an amount of 0 and other compounds (b 2) 40 to 80% by weight copolymerizable with (bl)
  • Examples thereof include an ultraviolet curable resin coating composition characterized by adding 1 to 10 parts by weight of G).
  • 1,9-Nonanediol diacrylate (bl) is an essential component, and the other compound (b 2) copolymerizable with (bl) is a polyfunctional (meth) acrylate monomer having two or more functions and 2 More than functional polyfunctional urethane (meth) acrylate oligomer [hereinafter referred to as polyfunctional urethane (meth) acrylate oligomer. ], Bifunctional or higher polyfunctional polyester (meth) acrylate oligomer [hereinafter referred to as polyfunctional polyester (meth) acrylate oligomer].
  • Bifunctional or higher polyfunctional epoxy (meth) acrylate oligomer [hereinafter referred to as polyfunctional epoxy (meth) acrylate oligomer]. ] And so on.
  • One or more (meth) acrylate monomers and oligomers can be used.
  • polyfunctional (meth) acrylate monomer examples include monomers having two or more (meth) acryloyloxy groups in the molecule.
  • Bifunctional (meth) acrylate monomers include alkylene dallicol di (meth) acrylates, polyoxyalkylene glycol di (meth) acrylates, halogen-substituted alkylene glycol di (meth) acrylates, fatty acid polyols Di (meth) acrylate, bisphenol A or bisphenol F alkylene oxide adduct di (meth) acrylate, bisphenol A or bisphenol F epoxy di (meth) acrylate
  • alkylene dallicol di (meth) acrylates include polyoxyalkylene glycol di (meth) acrylates, halogen-substituted alkylene glycol di (meth) acrylates, fatty acid polyols Di (meth) acrylate, bisphenol A or bisphenol F alkylene oxide adduct di (meth) acrylate, bisphenol A or bisphenol F epoxy di (meth) acrylate
  • bifunctional (meth) acrylate monomers include 2 — n — butyl — 2-ethyl -1,3 propanediol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene Examples include glycol diacrylate (meth) acrylate, polypropylene glycol diacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, and the like.
  • Trifunctional or higher (meth) acrylate monomers include trimethylol propan trimethacrylate, trimethylol propane ethylene oxide adduct triacrylate, glycerin propylene oxide adduct triatalylate, And entaerythritol tetraacrylate.
  • Polyfunctional urethane (meth) acrylate oligomers are urethanes of (meth) acrylate monomers having at least one (meth) acryloyloxy group and hydroxyl group in one molecule and a polyisocyanate. And the like.
  • the polyfunctional urethane (meth) acrylate oligomer includes a isocyanate compound obtained by reacting a polyol with a polyisocyanate, and at least one (meth) allyloyloxy group and hydroxyl group in one molecule. And urethanation reaction products with (meth) acrylate monomers.
  • the (meth) acrylate monomer having at least one (meth) atyloxy group and hydroxyl group in one molecule used in the urethanization reaction 2-hydroxyxetyl (meth) acrylate, 2-hydroxypropyl (Meth) Atarylate, 2-Hydroxybutyl (Meth) Atarylate, 2-Hydroxy -3-Hyphenoxypropyl (Meth) Atarylate, Glycerin di (meth) acrylate, Trimethylolpropanedi (Meth) Atallate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate.
  • the polyisocyanates used in the urethanization reaction include hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate.
  • diisocyanates obtained by hydrogenation of aromatic isocyanates eg, small diisocyanates such as hydrogenated tolylene diisocyanate and hydrogenated xylylene diisocyanate
  • triphenylmethane triisocyanate diisocyanate
  • diisocyanate examples thereof include di- or tri-polyisocyanates such as methylene triphenyl triisocyanate, or polyisocyanates obtained by multiplying diisocyanates.
  • polyols used for the urethanization reaction generally, aromatic polyols, aliphatic polyols and alicyclic polyols, polyester polyols, polyether polyols, and the like are used.
  • aliphatic and cycloaliphatic polyols include 1,4-monobutanediol, 1,6-hexanediol, neopentinoleglicol, ethylene glycol, propylene glycol, trimethylololeethane, trimethylolpropane.
  • the polyester polyol is obtained by a dehydration condensation reaction between the above polyols and a polybasic carboxylic acid (anhydride).
  • polybasic carboxylic acids are (anhydrous) succinic acid, adipic acid, (anhydrous) malein Acid, (anhydrous) trimellitic acid, hexahydro (anhydrous) phthalic acid, (anhydrous) phthalic acid, isophthalic acid, terephthalic acid and the like.
  • the polyether polyol include polyalkylene-modified polyols obtained by the reaction of the above polyols or phenols with alkylene oxides, in addition to polyalkylene dallicol.
  • the polyfunctional polyester (meth) acrylate oligomer is obtained by a dehydration condensation reaction of (meth) acrylic acid, polybasic carboxylic acid (anhydride) and polyol.
  • the polybasic carboxylic acid (anhydride) used in the dehydration condensation reaction is (anhydrous) succinic acid, adipic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, (no water) trimellitic acid, (anhydrous) pyro Mellitic acid, hexahydro (anhydrous) phthalic acid, (anhydrous) phthalic acid, isophthalic acid, terephthalic acid.
  • Polyols used in the dehydrocondensation reaction include 1,4-monobutanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentino glycol, dimethylolole heptane.
  • the polyfunctional epoxy (meth) acrylate oligomer is obtained by addition reaction of polyglycidyl ether and (meth) acrylic acid.
  • polyglycidyl ethers include ethylene glycolo-resin glycidinoate ethere, propylene glycol diglycidyl ether, tripropylene dallicol diglycidyl ether, 1,6-hexanedio diglycidinoreate ⁇ bisphenolore A diglycidyl ether, etc. Is mentioned.
  • the method of applying the paint to the surface of the layer containing the acrylic resin and the back surface of the substrate containing the polycarbonate resin not containing the acrylic resin according to the present invention includes brush, ronole, datebing, flow coating, spray, ronole.
  • the method proposed in Japanese Patent Application Laid-Open No. 2000-140-3040 can be applied.
  • the thickness of the hard coat layer cured by thermal curing or active energy rays is:! ⁇ 20 ⁇ m, preferably 2 ⁇ ! 5 / zm, more preferably 3 to 12 ⁇ m. If the thickness of the hard coat layer is less than 1 ⁇ , the effect of improving the surface hardness is insufficient. On the other hand, even if it exceeds 20 / m, the effect of improving the surface hardness is difficult to improve, which is disadvantageous in terms of cost and may cause a decrease in impact resistance.
  • the hard coat on the back side of the base material containing polycarbonate resin in which the acrylic resin is not laminated at 20 to 12 O xm, that is, the inner side when used as a product, is cracked under the stress expressed by the following formula (1). It is desirable not to occur.
  • cracks may occur below the above stress, cracks may occur on the inner surface when used as a product and may not be able to withstand use.
  • the above stress was calculated from the stress when no cracks occurred after the sheet was wound around a round bar of various diameters and left at room temperature for 48 hours.
  • the calculation formula was defined as the following formula (3).
  • Figure 1 shows the above and ⁇ .
  • the hard coat can be given a mat shape with a surface roughness Ra of 0.5 ⁇ or less.
  • Ra is the centerline average roughness.
  • the roughness curve is folded from the centerline, and the area obtained by dividing the roughness curve and centerline by the length L is ⁇ m. It is a manifestation. Further, the non-glare effect can be obtained by disposing the mat shape imparting surface on the side opposite to the liquid crystal.
  • An antireflection layer can be provided on the hard coat.
  • the antireflection layer is preferably one in which a high refractive index layer and a low refractive index layer are laminated in two or more layers so that the low refractive index layer is the outermost surface.
  • the material constituting the high refractive index layer is not particularly limited. For example, metal oxides such as T i 0 2 , Y 2 O 3 , La 2 O 3 , Z r 0 2 , A 1 2 0 3, etc. Can be mentioned.
  • the material for forming the low refractive index layer for example, S i 0 2, Mg F 2, L i F, 3Na F 'AIF 3, AIF 3, N a 3 AIF 6 , etc. of the metal oxide object Or a metal fluoride is mentioned.
  • the method for forming the antireflection layer on the hard coat layer is not particularly limited.
  • a known method such as sputtering, vapor deposition, plasma C V D, or coating can be used.
  • Polycarbonate resin manufactured by Mitsubishi Gas Chemical Company, Iupilon S—100, and viscosity average molecular weight 24, 500.
  • Acrylic resin Kuraray Co., Ltd., Parapet H R _ 1 0 0 0 L, deflection temperature under load: 10 1 ° C.
  • UV absorber Ciba 'Specialty' Chemicals, Tinuvin 1 5 7 7 (Product name) [Compound name: 2, 4-Diphenyl 6- (2-Hydroxy 1-Hexyloxyphenyl] ) 1,3,5-triazine].
  • the ultraviolet curable resin coating composition to be applied to the layer containing acrylic resin comprises the following raw materials.
  • E B-2 20 6-functional urethane acrylate oligomer (manufactured by Daicel Cytec Co., Ltd.)
  • thermosetting resin coating composition to be applied to the layer containing acryl resin is composed of the following raw materials.
  • Methyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.)
  • Snowtex 30 Colloidal silica (manufactured by Nissan Chemical Industries, Ltd.)
  • TAS Trimethylolethane succinate Z Acrylic acid molar ratio 1 2 4 condensate (Osaka Organic Chemical Co., Ltd.)
  • APO initiator Trimethylbenzoyldiphenylphosphine oxide (manufactured by BIAS, F. Japan Ltd.)
  • BNP initiator Benzophenone (Wako Pure Chemical Industries, Ltd.)
  • Pencil hardness Measured with a load of 1 kg according to JIS K 5400.
  • UV-curing resin coating on base material containing polycarbonate resin 2 In a mixing dissolution tank equipped with a stirring blade and temperature control jacket, Osaka Organic Chemical Co., Ltd. # 260: 1,9-nonanediol 40 parts of the rate, U6HA made by Shin-Nakamura Chemical Co., Ltd .: 4 parts of 6-functional urethane acrylate oligomer, TAS: 20 parts of condensate with a molar ratio of succinic acid trimethylolethanenoacrylic acid of 1 2 4 APO manufactured by BF Japan Co., Ltd .: 2.8 parts of trimethylbenzoyldiphenylphosphine oxide, BNP manufactured by Wako Pure Chemical Industries, Ltd.
  • the barrel diameter was 65 mm
  • the screw L, D was 35
  • the cylinder temperature was 270 ° C.
  • Two types of resin are melt-extruded at the same time, and a feed block is used for lamination.
  • Polycarbonate resin Mitsubishi Engineering Plastics Co., Ltd., product name: Iupilon S-1000
  • has an acrylic resin on one side Kuraray Co., Ltd. product name: Parapet HR—1000 L
  • the temperature inside the die head is 260 ° C, and the resin laminated and integrated in the die is guided to three mirror-finished polysinder rolls, and roll temperature 1 1 0 ° C
  • the second roll temperature was set to 140 ° C and the third roll temperature was set to 185 ° C.
  • Banks were formed at the first inflow roll interval, and then the No. 2 and No. 3 rolls were passed through to extrude a 0.4 mm thick coextruded sheet.
  • the average thickness of the layer containing acrylic resin in the coextruded sheet was 60 ⁇ .
  • the barrel diameter was 65 mm
  • the screw LZD was 35
  • the cylinder temperature was 270 ° C.
  • Two types of resin are melt-extruded at the same time, and a feed block is used for lamination.
  • Polycarbonate resin manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name: Iupilon S—1000
  • acrylic resin on one side Karl Fischer Co., Ltd. product name: Parapet HR—1000 L
  • the flow path of the feed block was made so that layers containing acrylic resin were laminated on both sides, and the choke bar opening in the feed block was adjusted so that the thickness of the layers containing acrylic resin on the front and back sides was 31.
  • the die head temperature is 260 ° C, and the resin laminated and integrated in the die is guided to three mirror-finished polisinda rolls, the first roll temperature is 1 10 ° C, The second roll temperature was set to 140 ° C and the third roll temperature was set to 1 85 ° C. After forming the bank with the first roll interval, the second and third rolls were passed through and 0.8 mm thick coextruded sheets were extruded.
  • the average thickness of the layer containing acrylic resin in the 0.8 mm thick coextruded sheet was 60 ⁇ on one side and 20 jum on the other side.
  • the paint described in Production Example 1 for thermosetting resin coating to be applied to a layer containing acrylic resin is flow-coated, air-dried for 15 minutes at room temperature, and then heated to 120 ° C. It was hardened with a hot air circulating dryer for 60 minutes.
  • the barrel diameter was 65 mm
  • the screw LZD was 35
  • the cylinder temperature was 270 ° C.
  • Two types of resin are melt extruded at the same time, and a feed block is used for lamination.
  • Polycarbonate resin (Made by Mitsubishi Engineering Plastics Co., Ltd., product name: Iupilon S-1000) on one side is acrylic resin (Kuraray) Co., Ltd., product name: Parapet HR-1000 L) was laminated.
  • the temperature inside the die head is 260 ° C, and the resin laminated and integrated in the die is guided to three mirror-finished polysinder rolls, and the first roll temperature is 1 10 ° C.
  • the second roll temperature was set to 140 ° C and the third roll temperature was set to 1 85 ° C.
  • the 2nd and 3rd rolls were passed through to extrude the 1.5 mm thick coextruded sheet.
  • the average thickness of the layer containing acrylic resin in the 5 mm thick coextruded sheet was 80 zm.
  • UV-curable resin production example 1 For coating described in UV-curable resin production example 1 between the acrylic resin surface of the co-extruded sheet adjusted to a surface temperature of 80 ° C with a hot air circulating dryer and a separately prepared 100 / xm thick PET film After curing the composition The film is sandwiched so that it becomes 38 ⁇ , and after pressure bonding, a high-pressure mercury lamp with an output density of 80 W / cm is used and irradiated with ultraviolet rays at a conveyor speed of 3 cm under the light source at a condition of 3. Om / min. After curing, the PET film was peeled off. Furthermore, the coating composition described in the UV curable resin production example 2 was applied and cured to the PC surface on which no acrylic resin was laminated by the same method to obtain a laminate containing a polycarbonate resin. The evaluation results of the manufactured laminate are shown in Table 1.
  • the barrel diameter was 65 mm
  • the screw LZD was 35
  • the cylinder temperature was 270 ° C.
  • the extruder for extruding acrylic resin forming the coating layer was set to a barrel diameter of 32 mm, a screw L / D 32, and a cylinder temperature of 250 ° C.
  • Two types of resin are melt extruded at the same time, and a feed block is used for lamination.
  • Polycarbonate resin (Made by Mitsubishi Engineering Plastics Co., Ltd., product name: Iupilon S-1000) on one side is acrylic resin (Kuraray) Co., Ltd., product name: Parapet HR_1000 L) was laminated.
  • the flow path of the feed block was made so that layers containing acrylic resin were laminated on both sides, and the choke bar opening in the feed block was adjusted so that the thickness of the layers containing acrylic resin on the front and back sides was 4Z1.
  • the temperature inside the die head is 260 ° C, and the resin laminated and integrated in the die is guided to three polisher rolls with a mirror-finished horizontal arrangement, and the first roll temperature 1 10 ° C 2 No. roll temperature 140 ° C No. 3 roll temperature was set to 185 ° C. After forming the bank at the first inflow roll interval, the second and third rolls were passed through to extrude the 1.5 mm thick coextruded sheet.
  • the average thickness of the layer containing acrylic resin in the 1.5 mm thick coextruded sheet was 80 ⁇ m on one side and 20 / Xm on the other side.
  • UV curable resin coating applied to acrylic resin between the acrylic resin surface of the co-extruded sheet adjusted to a surface temperature of 80 ° C with a hot air circulating dryer and a separately prepared 100 / xm PET film Product Preparation Example 1
  • the coating composition described in Example 1 is sandwiched so that the cured coating has a thickness of 38 ⁇ m.
  • Speed 3. Cured by UV irradiation under conditions of OmZ. After curing, the PET film was peeled off and both acrylic resin surfaces were hard-coated. Table 1 shows the evaluation results of the manufactured laminate.
  • the barrel diameter was 65 mm
  • the screw L, D was 35
  • the cylinder temperature was 270 ° C.
  • Two types of resin are melt extruded at the same time, and a feed block is used for lamination.
  • Polycarbonate resin (Made by Mitsubishi Engineering Plastics Co., Ltd., product name: Iupilon S-1000) on one side is acrylic resin (Kuraray) Co., Ltd., product name: Parapet HR_1000 L) was laminated.
  • UV-curable resin production example 1 Between the acrylic resin surface of the co-extruded sheet adjusted to a surface temperature of 80 ° C with a hot air circulating dryer and a separately prepared 100 ⁇ thick P ⁇ ⁇ film, as described in UV-curable resin production example 1 The coating composition is sandwiched so that the coating film after curing is 8 to 12 / m. After crimping, a high-pressure mercury lamp with an output density of 80 W / cm is used, and the conveyor speed is 12 cm below the light source. 3. OmZ Curing was performed by irradiating with ultraviolet rays under the conditions of minutes, and the PET film was peeled off after curing. Table 1 shows the evaluation results of the manufactured laminate.
  • the evaluation results are shown in Table 2.
  • the evaluation results are shown in Table 2.
  • the present invention is a laminate including a polycarbonate resin used as a mobile terminal display member such as a liquid crystal display cover and a sub display.
  • a preferred embodiment of the present invention is a polycarbonate resin laminate for a mobile terminal display member such as a liquid crystal display cover or a sub-display having excellent surface hardness, impact resistance and weather resistance, particularly a general polycarbonate resin.
  • Unachievable high A laminate comprising a polycarbonate resin for a mobile terminal display member such as a liquid crystal display cover or a sub-display having pencil hardness.

Landscapes

  • Laminated Bodies (AREA)
  • Telephone Set Structure (AREA)
  • Liquid Crystal (AREA)

Abstract

L'invention concerne un stratifié qui comprend un matériau de base comprenant une résine de polycarbonate et une couche comprenant une résine acrylique. La couche comprenant la résine acrylique est formée par co-extrusion sur la surface du matériau de base comprenant la résine de polycarbonate. La couche comprenant la résine acrylique présente une épaisseur de 20 à 120 μm et le stratifié présente une épaisseur de 0.3 à 1.5 mm. La surface de la couche comprenant la résine acrylique est traitée en couches dures, et la résine acrylique est un copolymère de méthacrylate de méthyle et d'un ester d'acide acrylique ayant un rapport de copolymérisation [par exemple, un rapport (méthacrylate de méthyle)/(ester d'acide acrylique)] de 80/20 à 99.5/0.5.
PCT/JP2007/070672 2006-10-20 2007-10-17 Stratifié comprenant une résine de polycarbonate WO2008047940A1 (fr)

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JP2008539898A JPWO2008047940A1 (ja) 2006-10-20 2007-10-17 ポリカーボネート樹脂を含む積層体
KR1020097009932A KR101113472B1 (ko) 2006-10-20 2007-10-17 폴리카보네이트 수지를 포함하는 적층체

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JP2010023444A (ja) * 2008-07-24 2010-02-04 Sumitomo Chemical Co Ltd 耐擦傷性樹脂板及びその用途
JP2010044163A (ja) * 2008-08-11 2010-02-25 Meihan Shinku Kogyo Kk ディスプレイ面板用透明多層シート
JP2010188719A (ja) * 2009-01-22 2010-09-02 Teijin Chem Ltd ポリカーボネート樹脂積層体
JP2011148168A (ja) * 2010-01-21 2011-08-04 Sumitomo Chemical Co Ltd 液晶ディスプレイ保護用積層板
JP2012076401A (ja) * 2010-10-05 2012-04-19 Kuraray Co Ltd 積層板
JP2012206378A (ja) * 2011-03-29 2012-10-25 Dainippon Printing Co Ltd ハードコート樹脂成型体
JP2014014986A (ja) * 2012-07-09 2014-01-30 Keiwa Inc インサートフィルム及びインサート成形品
KR20150024784A (ko) * 2013-08-27 2015-03-09 스미또모 가가꾸 가부시키가이샤 적층판
WO2015093516A1 (fr) * 2013-12-18 2015-06-25 三菱瓦斯化学株式会社 Stratifié à base de résine synthétique
JP2016124292A (ja) * 2014-12-26 2016-07-11 三菱化学株式会社 積層体及び表示体カバー
EP3107730A1 (fr) * 2014-02-19 2016-12-28 SABIC Global Technologies B.V. Feuille multicouche, procédés de fabrication et d'utilisation de celle-ci, et articles comprenant la feuille multicouche
CN106573454B (zh) * 2014-07-09 2018-09-18 三菱瓦斯化学株式会社 合成树脂叠层体
US10414133B2 (en) 2012-05-18 2019-09-17 Mitsubishi Gas Chemical Company, Inc. Synthetic resin laminate

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CN102576112B (zh) * 2009-10-21 2014-12-31 三菱瓦斯化学株式会社 功能性片材和使用该功能性片材的透镜
JP2011232504A (ja) * 2010-04-27 2011-11-17 Sumitomo Chemical Co Ltd 液晶ディスプレイ保護用積層板
CN104520102B (zh) * 2012-08-06 2016-11-02 帝人株式会社 多层膜、装饰成型用膜及成型体
EP2979862B1 (fr) * 2013-03-26 2018-07-04 Shin-Etsu Chemical Co., Ltd. Stratifié en résine de polycarbonate
US10118988B2 (en) * 2014-10-15 2018-11-06 Mitsubishi Gas Chemical Company, Inc. Synthetic resin laminated sheet
EP3425448B1 (fr) * 2016-03-04 2020-07-08 Mitsubishi Gas Chemical Company, Inc. Plaque avant pour dispositif lcd embarqué
CN110254006A (zh) * 2019-05-21 2019-09-20 品诚塑胶科技（上海）有限公司 一种透明高表面硬度耐候pc板材及其制备方法
CN114502356B (zh) * 2019-10-09 2023-12-26 帝人株式会社 弯曲构件的制造方法和用于热弯的带硬涂层的聚碳酸酯树脂层叠体

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JP2006103169A (ja) * 2004-10-06 2006-04-20 Mitsubishi Gas Chem Co Inc 液晶ディスプレーカバー用ポリカーボネート樹脂積層体

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JP2005225018A (ja) * 2004-02-12 2005-08-25 Mitsubishi Gas Chem Co Inc ポリカーボネート樹脂積層体
JP2006103169A (ja) * 2004-10-06 2006-04-20 Mitsubishi Gas Chem Co Inc 液晶ディスプレーカバー用ポリカーボネート樹脂積層体

Cited By (21)

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JP2010023444A (ja) * 2008-07-24 2010-02-04 Sumitomo Chemical Co Ltd 耐擦傷性樹脂板及びその用途
JP2010044163A (ja) * 2008-08-11 2010-02-25 Meihan Shinku Kogyo Kk ディスプレイ面板用透明多層シート
JP2010188719A (ja) * 2009-01-22 2010-09-02 Teijin Chem Ltd ポリカーボネート樹脂積層体
JP2011148168A (ja) * 2010-01-21 2011-08-04 Sumitomo Chemical Co Ltd 液晶ディスプレイ保護用積層板
JP2012076401A (ja) * 2010-10-05 2012-04-19 Kuraray Co Ltd 積層板
JP2012206378A (ja) * 2011-03-29 2012-10-25 Dainippon Printing Co Ltd ハードコート樹脂成型体
US10414133B2 (en) 2012-05-18 2019-09-17 Mitsubishi Gas Chemical Company, Inc. Synthetic resin laminate
JP2014014986A (ja) * 2012-07-09 2014-01-30 Keiwa Inc インサートフィルム及びインサート成形品
CN104416999A (zh) * 2013-08-27 2015-03-18 住友化学株式会社 层叠板
JP2015063122A (ja) * 2013-08-27 2015-04-09 住友化学株式会社 積層板
KR20150024784A (ko) * 2013-08-27 2015-03-09 스미또모 가가꾸 가부시키가이샤 적층판
KR102241268B1 (ko) 2013-08-27 2021-04-15 스미또모 가가꾸 가부시키가이샤 적층판
CN104416999B (zh) * 2013-08-27 2019-03-29 住友化学株式会社 层叠板
WO2015093516A1 (fr) * 2013-12-18 2015-06-25 三菱瓦斯化学株式会社 Stratifié à base de résine synthétique
US9802395B2 (en) 2013-12-18 2017-10-31 Mitsubisshi Gas Chemical Company, Inc. Synthetic resin laminate
JP2017511759A (ja) * 2014-02-19 2017-04-27 サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ 多層シート、該多層シートの製造方法および使用方法、ならびに該多層シートを含む物品
EP3107730A1 (fr) * 2014-02-19 2016-12-28 SABIC Global Technologies B.V. Feuille multicouche, procédés de fabrication et d'utilisation de celle-ci, et articles comprenant la feuille multicouche
US10913247B2 (en) 2014-02-19 2021-02-09 Sabic Global Technologies B.V. Multilayer sheet, methods for making and using the same, and articles comprising the multilayer sheet
EP3107730B1 (fr) * 2014-02-19 2023-11-15 SABIC Global Technologies B.V. Feuille multicouche, procédés de fabrication de celle-ci, et articles comprenant la feuille multicouche
CN106573454B (zh) * 2014-07-09 2018-09-18 三菱瓦斯化学株式会社 合成树脂叠层体
JP2016124292A (ja) * 2014-12-26 2016-07-11 三菱化学株式会社 積層体及び表示体カバー

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KR101113472B1 (ko) 2012-03-14
CN101522415A (zh) 2009-09-02
KR20090080970A (ko) 2009-07-27
TW200833511A (en) 2008-08-16

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