Classifications

• • 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
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • G—PHYSICS
  • G06—COMPUTING OR CALCULATING; COUNTING
  • G06F—ELECTRIC DIGITAL DATA PROCESSING
  • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
  • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
  • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
  • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

Definitions

• the present invention relates to a resin laminate used as a transparent substrate material or a protective material. More specifically, the present invention relates to a resin laminate having excellent thermoformability at a low temperature and having a good appearance that suppresses the generation of interference fringes.
• Acrylic resin has excellent surface hardness, transparency, scratch resistance and weather resistance.
• the polycarbonate resin has excellent impact resistance and the like.
• the laminate having the acrylic resin layer and the polycarbonate resin layer is excellent in surface hardness, transparency, scratch resistance, weather resistance, impact resistance, etc., and is excellent in automobile parts, home appliances, electronic devices, and portable information terminals. It is used for the display window of.
• thermoforming such as vacuum forming and compressed air forming on the front plate of display devices.
• a laminate having an acrylic resin layer and a polycarbonate resin layer has been attempted to be applied to a front plate from the above-mentioned excellent performance aspects.
• the laminate having the acrylic resin layer and the polycarbonate resin layer is heat-molded, it is necessary to heat the sheet to a temperature at which the polycarbonate resin is sufficiently stretched, which causes excessive heat to be applied to the acrylic resin. Peeling may occur at the interface between the acrylic resin layer and the polycarbonate resin layer, and the surface may be whitened or cracks may occur.
• the molding temperature is lowered in order to suppress the occurrence of whitening and cracks, "springback" that does not reproduce the shape of the mold may occur.
• Patent Document 1 discloses a molding resin sheet of a polycarbonate resin having a specific terminal group and an acrylic resin as a molding resin sheet suitable for thermoforming such as vacuum forming and pneumatic molding. Such a resin sheet is suppressed from whitening and cracking during bending by thermoforming. However, when the surface of the acrylic resin layer of the resin sheet is hard coated, there is a problem that cracks occur during bending in thermoforming.
• Patent Document 2 discloses a laminate of a styrene-maleic anhydride copolymer, an alloy layer of a methacrylic resin, and a polycarbonate resin layer for thermoforming at a temperature of 160 ° C. Such a laminate does not cause any problems when thermoformed at a temperature of 160 ° C. However, when the resin laminate having the styrene-maleic anhydride copolymer and the hard coat layer on the surface of the alloy layer of the methacrylic resin is thermoformed at a temperature of 160 ° C., cracks are formed in the bent portion of the resin laminate. There was a problem that it occurred.
• An object of the present invention is to provide a resin laminate having excellent thermoformability at low temperature and having a good appearance to suppress the generation of interference fringes.
• the present inventors have completed the present invention as a result of repeated diligent studies to solve the above problems. Specifically, the present invention is as follows.
• a layer containing a thermoplastic resin (B) is provided on at least one surface of a layer containing a polycarbonate resin (A), and a hard coat layer is provided on at least one surface of the layer containing the thermoplastic resin (B). It is a resin laminate having The polycarbonate resin (A) has a glass transition temperature of 115 ° C to 140 ° C, and has a glass transition temperature of 115 ° C to 140 ° C.
• the thermoplastic resin (B) contains a methacrylic resin (C) and a styrene copolymer (D), and the total content of the methacrylic resin (C) and the styrene copolymer (D) is based on 100 parts by mass.
• the content of the methacrylic resin (C) is 15 to 70 parts by mass, and the content of the styrene copolymer (D) is 85 to 30 parts by mass.
• the styrene copolymer (D) is a copolymer containing 68 to 84% by mass of a vinyl aromatic monomer unit (d1) and 16 to 32% by mass of a cyclic acid anhydride monomer unit (d2).
• the weight average molecular weight is 50,000 to 130,000.
• This resin laminate does not cause cracks or springback in the bent portion after thermoforming at a mold temperature of 120 ° C. with a heat press machine of 50 mmR.
• thermoplastic resin (B) is a polymer alloy of the methacrylic resin (C) and the styrene copolymer (D). .. [4] The resin laminate according to any one of the above [1] to [3], wherein the vinyl aromatic monomer unit (d1) contained in the styrene copolymer (D) is styrene.
• the polycarbonate-based resin (A) has a terminal structure derived from a monovalent phenol represented by the following general formula (1) and a structural unit derived from a divalent phenol, and has the above-mentioned [1] to [1] to [ 5] The resin laminate according to any one of.
• R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms
• R 2 to R 5 are carbons which may have a hydrogen, a halogen or a substituent, respectively.
• the thickness of the layer containing the thermoplastic resin (B) is 10 to 250 ⁇ m, and the total thickness of the resin laminate is in the range of 0.4 to 4.0 mm.
• the resin laminate according to any one of the above [1] to [10] is a thermoformed body obtained by thermoforming.
• a front plate for a car navigation system, an OA device, or a portable electronic device which comprises the resin laminate according to any one of the above [1] to [12] or the thermoformed body according to the above [11].
• a method for producing a thermoformed body which comprises a step of hot bending a resin laminate at a mold temperature of 100 ° C. to 135 ° C.
• the resin laminate has a layer containing a thermoplastic resin (B) on at least one surface of a layer containing a polycarbonate resin (A), and is on at least one side surface of the layer containing the thermoplastic resin (B).
• the polycarbonate resin (A) has a glass transition temperature of 115 ° C to 140 ° C, and has a glass transition temperature of 115 ° C to 140 ° C.
• the thermoplastic resin (B) contains a methacrylic resin (C) and a styrene copolymer (D), and the total content of the methacrylic resin (C) and the styrene copolymer (D) is based on 100 parts by mass.
• the content of the methacrylic resin (C) is 15 to 70 parts by mass, and the content of the styrene copolymer (D) is 85 to 30 parts by mass.
• the styrene copolymer (D) is a copolymer containing 68 to 84% by mass of a vinyl aromatic monomer unit (d1) and 16 to 32% by mass of a cyclic acid anhydride monomer unit (d2). This is the production method, wherein the weight average molecular weight is 50,000 to 130,000.
• the resin laminate of the present invention can be obtained as a molded product having a good appearance by suppressing the occurrence of whitening and cracks during thermoforming.
• the resin laminate can be used as a transparent substrate material or a transparent protective material.
• portable display devices such as mobile phone terminals, portable electronic play equipment, mobile information terminals, and mobile PCs
• stationary display devices such as notebook PCs, desktop PC LCD monitors, car navigation LCD monitors, and LCD TVs. In, for example, it can be suitably used as a front plate for protecting these devices.
• the polycarbonate-based resin (A) used in the present invention is a polycarbonate-based resin (A) containing a polycarbonate resin as a main component.
• “having a polycarbonate resin as a main component” means that the content of the polycarbonate resin exceeds 50% by mass.
• the polycarbonate resin (A) preferably contains 75% by mass or more of the polycarbonate resin, more preferably 90% by mass or more of the polycarbonate resin, and further preferably substantially composed of the polycarbonate resin. ..
• the polycarbonate resin (A) contains a carbonic acid ester bond in the molecular main chain.
• R contains an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and further has a linear structure or a branched structure. Is not particularly limited as long as it contains), but it is particularly preferable to use a polycarbonate containing the structural unit of the following formula (2). By using such polycarbonate, a resin laminate having excellent impact resistance can be obtained.
• the polycarbonate resin (A) is preferably synthesized by using a monohydric phenol represented by the following general formula (1) as a terminal terminator.
• R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms.
• R 2 to R 5 represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, which may have hydrogen, halogen, or a substituent, respectively, and the substituents are halogen and 1 carbon dioxide group. It is an alkyl group of up to 20 or an aryl group having 6 to 12 carbon atoms.
• the monohydric phenol of the general formula (1) is more preferably a monohydric phenol represented by the following general formula (3).
• R 1 represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms.
• the carbon number of R 1 in the general formula (1) or the general formula (3) is within a specific numerical range. Specifically, as the upper limit of the number of carbon atoms of R 1 , 36 is preferable, 22 is more preferable, and 18 is particularly preferable. Further, as the lower limit of the number of carbon atoms of R 1 , 8 is preferable, and 12 is more preferable.
• one or both of the parahydroxybenzoic acid hexadecyl ester and the parahydroxybenzoic acid 2-hexyldecyl ester are terminated. It is particularly preferable to use it as an agent.
• a monohydric phenol (terminal terminator) having an alkyl group having 16 carbon atoms is used as R 1 in the general formula (1) or the general formula (3), the glass transition temperature, melt fluidity, moldability, and the like. It has excellent draw-down resistance and solvent solubility of monohydric phenol during production of a polycarbonate resin, and is particularly preferable as a terminal terminator used in the polycarbonate resin used in the present invention.
• the carbon number of R1 in the general formula (1) or the general formula (3) is increased too much, the organic solvent solubility of the monohydric phenol (terminal terminator) tends to decrease, and the polycarbonate resin is manufactured. Productivity may decrease.
• the carbon number of R 1 is 36 or less, the productivity is high and the economy is good in producing the polycarbonate resin.
• the monohydric phenol is particularly excellent in organic solvent solubility, and can greatly increase the productivity in producing the polycarbonate resin and also improve the economic efficiency. If the carbon number of R 1 in the general formula (1) or the general formula (3) is too small, the glass transition temperature of the polycarbonate resin does not become a sufficiently low value, and the thermoformability may deteriorate.
• the polyester resin may contain terephthalic acid as a main component as the dicarboxylic acid component, and may contain a dicarboxylic acid component other than terephthalic acid.
• a glycol component containing 20 to 40 (molar ratio, 100 in total) of 1,4-cyclohexanedimethanol with ethylene glycol 80 to 60 (molar ratio) as the main component and a dicarboxylic acid component are polycondensed.
• a polyester resin, so-called "PETG” is preferable.
• the polycarbonate-based resin (A) may contain a polyester carbonate-based resin having an ester bond and a carbonate bond in the polymer skeleton.
• the weight average molecular weight of the polycarbonate resin (A) affects the impact resistance and molding conditions of the resin laminate. That is, if the weight average molecular weight is too small, the impact resistance of the resin laminate is lowered, which is not preferable. If the weight average molecular weight is too high, an excessive heat source may be required when laminating the layer containing the polycarbonate resin (A), which is not preferable. Further, since a high temperature is required depending on the molding method, the polycarbonate resin (A) is exposed to a high temperature, which may adversely affect its thermal stability.
• the weight average molecular weight of the polycarbonate resin (A) is preferably 10,000 to 75,000, more preferably 15,000 to 60,000. More preferably, it is 20,000 to 50,000.
• the weight average molecular weight of the polycarbonate resin (A) can be measured based on the description in paragraphs 0061 to 0064 of JP-A-2007-179018. The details of the measurement method are shown below.
• the relationship between the elution time and the molecular weight of polycarbonate (PC) is obtained by a universal calibration method and used as a calibration curve. Then, the elution curve (chromatogram) of PC is measured under the same conditions as in the case of the calibration curve, and each average molecular weight is obtained from the elution time (molecular weight) and the peak area (molecular number) of the elution time. Assuming that the number of molecules of the molecular weight Mi is Ni, the weight average molecular weight is expressed as follows. The following formula was used as the conversion formula.
• MPC 0.47822MPS 1.01470 MPC indicates the molecular weight of PC, and MPS indicates the molecular weight of PS.
• the glass transition temperature of the polycarbonate resin (A) used in the present invention is preferably 115 to 140 ° C, more preferably 115 to 135 ° C, further preferably 115 ° C to 130 ° C, and particularly preferably 115 ° C or higher and lower than 130 ° C. preferable.
• the glass transition temperature of the polycarbonate resin (A) in the present specification is measured at a heating rate of 10 ° C./min using a differential scanning calorimeter and calculated at the intersection of the baseline and the tangent at the inflection. It is the temperature at the time of.
• the melt flow rate of the polycarbonate resin (A) is preferably in the range of 1 to 30 g / 10 minutes, more preferably in the range of 8 to 20 g / 10 minutes, and in the range of 11 to 15 g / 10 minutes. It is even more preferable to have it. When the melt flow rate is in the range of 1 to 30 g / 10 minutes, the stability of heat melt molding is good.
• the melt flow rate of the polycarbonate resin (A) in the present specification is measured using a melt indexer under the conditions of a temperature of 300 ° C. and a load of 1.2 kg.
• the method for producing the polycarbonate resin (A) used in the present invention can be appropriately selected depending on the monomer used, such as a known phosgene method (interfacial polymerization method) or transesterification method (melting method).
• thermoplastic resin (B) used in the present invention contains a methacrylic resin (C) and a styrene copolymer (D). Each component will be described below.
• thermoplastic resin (B) examples include a resin containing a structural unit derived from a methacrylic acid ester monomer.
• Examples of the methacrylic acid ester monomer of the methacrylic acid resin (C) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate.
• Alkyl methacrylate esters such as pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate; 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cyclomethacrylate.
• Cycloalkyl esters of methacrylic acid such as heptyl, cyclooctyl methacrylate, tricyclo methacrylate [5.2.1.02,6] deca-8-yl; aryl methacrylate esters such as phenyl methacrylate; methacrylics such as benzyl methacrylate.
• Examples thereof include acid aralkyl esters, and from the viewpoint of availability, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate are preferable. , Methyl methacrylate is most preferred.
• the methacrylic resin (C) preferably contains 80% by mass or more of structural units derived from the methacrylic acid ester monomer, more preferably 90% by mass or more, and 95% by mass. It is more preferable to contain% or more.
• the methacrylic resin (C) contains 80% by mass or more of structural units derived from the methacrylic acid ester monomer, the compatibility with the styrene copolymer (D) is good, which is preferable.
• the structural unit derived from the methacrylic acid ester monomer is less than 80% by mass, it may become cloudy without being compatible with the styrene copolymer (D).
• the methacrylic resin (C) may contain a structural unit derived from a monomer other than the methacrylic acid ester.
• examples of such other monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, and 2 acrylate.
• the lower limit of the syndiotacticity (rr) of the triplet display of the methacrylic resin (C) is preferably 50 mol% or more, more preferably 51% mol or more, and 52% mol or more. Is even more preferable. When the lower limit of the content of such a structure is 50 mol% or more, the heat resistance is excellent.
• syndiotacticity (rr) of the triplet display (hereinafter, may be simply referred to as “syngiotacticity (rr)”) is a chain of three consecutive structural units (triplet, triad). ) Has two chains (double element, diad), both of which are racemic (denoted as rr). In the chain of structural units (double element, diad) in the polymer molecule, those having the same configuration are referred to as meso, and the opposite ones are referred to as racemo, which are referred to as m and r, respectively.
• the weight average molecular weight of the methacrylic resin (C) is determined by the ease of mixing (dispersing) with the styrene copolymer (D) and the ease of producing these thermoplastic resins (B). That is, if the weight average molecular weight of the methacrylic resin (C) is too large, the difference in melt viscosity with the styrene copolymer (D) becomes too large, so that the mixture (dispersion) of the two becomes poor and the thermoplastic resin (B) ) May deteriorate in transparency, or stable melt-kneading cannot be continued.
• the weight average molecular weight of the methacrylic resin (C) is preferably in the range of 50,000 to 700,000, more preferably in the range of 60,000 to 500,000. More preferably, it is in the range of 70,000 to 200,000.
• the weight average molecular weight is a standard polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).
• the glass transition temperature of the methacrylic resin (C) is preferably 100 ° C. or higher, more preferably 105 ° C. or higher, and even more preferably 108 ° C. or higher. When the glass transition temperature is 100 ° C. or higher, the resin laminate provided in the present invention is less likely to be deformed or cracked in a thermal environment.
• the glass transition temperature of the methacrylic resin (C) in the present specification is measured at a heating rate of 10 ° C./min using a differential scanning calorimeter and calculated at the intersection of the baseline and the tangent at the inflection. The temperature of the time.
• the melt flow rate of the methacrylic resin (C) is preferably in the range of 1 to 10 g / 10 minutes.
• the lower limit of the melt flow rate is more preferably 1.2 g / 10 minutes or more, and further preferably 1.5 g / 10 minutes.
• the upper limit of the melt flow rate is more preferably 7.0 g / 10 minutes or less, and further preferably 4.0 g / 10 minutes or less.
• the melt flow rate of the methacrylic resin (C) in the present specification is a value measured using a melt indexer at a temperature of 230 ° C. under a load of 3.8 kg.
• the styrene copolymer (D) contained in the thermoplastic resin (B) according to the present invention contains a vinyl aromatic monomer unit (d1) and a cyclic acid anhydride monomer unit (d2), and has a vinyl fragrance.
• the total ratio of the group monomer unit (d1) and the cyclic acid anhydride monomer unit (d2) is 92 to 100% by mass with respect to the total of all the monomer units in the styrene copolymer (D). It is characterized by being.
• the vinyl aromatic monomer unit (d1) of the styrene copolymer (D) is not particularly limited, and any known aromatic vinyl monomer can be used, but it is easy to obtain. From the viewpoint, styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene and the like can be mentioned. Of these, styrene is particularly preferable from the viewpoint of compatibility. Two or more kinds of these aromatic vinyl monomers may be mixed.
• Examples of the cyclic acid anhydride monomer unit (d2) of the styrene copolymer (D) include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, which are compatible with acrylic resins.
• Maleic anhydride is preferable from the viewpoint of. Two or more kinds of these unsaturated dicarboxylic acid anhydride monomers may be mixed.
• the total ratio of the vinyl aromatic monomer unit (d1) and the cyclic acid anhydride monomer unit (d2) is the styrene copolymer (d). It is 92 to 100% by mass, preferably 95 to 100% by mass, and more preferably 98 to 100% by mass with respect to the total of all the monomer units in D). That is, the styrene copolymer (D) contains the vinyl aromatic monomer unit (d1) and the cyclic acid anhydride monomer in a range of 8% by mass or less with respect to the total of all the monomer units. It may contain a monomer unit other than the unit (d2).
• Examples of the monomer unit other than the vinyl aromatic monomer unit (d1) and the cyclic acid anhydride monomer unit (d2) include a methacrylic acid ester monomer unit and an N-substituted maleimide unit.
• the body etc. can be mentioned.
• Examples of the methacrylic acid ester monomer unit in the styrene copolymer (D) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert methacrylate.
• -Alkyl methacrylate esters such as butyl, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate; 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, Cycloalkyl methacrylate esters such as cycloheptyl methacrylate, cyclooctyl methacrylate, tricyclo methacrylate [5.2.1.02,6] deca-8-yl; aryl methacrylate esters such as phenyl methacrylate; benzyl methacrylate Examples thereof include methacrylic acid aralkyl esters such as, and methyl methacrylate is preferable from the viewpoint of compatibility with methacrylic acid.
• N-substituted maleimide monomer in the styrene copolymer (D) examples include N-phenylmaleimide, N-chlorophenylmaleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, and N-methoxy.
• N-arylmaleimide such as phenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, and N-tribromophenylmaleimide, and N-phenylmaleimide is preferable from the viewpoint of compatibility with methacrylic resin. Two or more kinds of these N-substituted maleimide monomers may be mixed.
• the ratio of the vinyl aromatic monomer unit (d1) is 68 to 84% by mass, preferably 70 to 82% by mass, based on the total of all the monomer units in the styrene copolymer (D). It is more preferably 74 to 80% by mass, and further preferably 76 to 79% by mass.
• the ratio of the cyclic acid anhydride monomer unit (d2) is 16 to 32% by mass, preferably 18 to 30% by mass, based on the total of all the monomer units in the styrene copolymer (D). %, More preferably 20 to 26% by mass, still more preferably 21 to 24% by mass.
• the ratio of the vinyl aromatic monomer unit (d1) to the total of all the monomer units in the styrene copolymer (D) is other than 68 to 84% by mass, the phase with the methacrylic resin (C). Poor solubility. Further, when the ratio of the cyclic acid anhydride monomer unit (d2) to the total of all the monomer units in the styrene copolymer (D) is other than 16 to 32% by mass, the methacrylic resin (C) and the methacrylic resin (C) are used. The compatibility of the product becomes worse.
• the weight average molecular weight of the styrene copolymer (D) is preferably 50,000 to 130,000, more preferably 55,000 to 100,000 from the viewpoint of thermoformability at low temperature. , 60,000 to 90,000 is particularly preferable.
• the weight average molecular weight is a standard polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).
• the glass transition temperature of the styrene copolymer (D) is preferably in the range of 120 to 190 ° C, more preferably in the range of 130 to 170 ° C.
• the resin laminate provided in the present invention is less likely to be deformed or cracked in a thermal environment.
• the temperature is 190 ° C. or lower, the workability is excellent such as continuous heat shaping by a mirror surface roll or a shaping roll, or batch type heat shaping by a mirror surface mold or a shaping die.
• the glass transition temperature of the styrene copolymer (D) in the present specification is measured at a heating rate of 10 ° C./min using a differential scanning calorimeter, and is at the intersection of the baseline and the tangent at the inflection. It is the temperature at the time of calculation.
• the melt flow rate of the styrene copolymer (D) is preferably in the range of 1 to 10 g / 10 minutes, more preferably in the range of 3 to 8 g / 10 minutes, and 4 to 7 g / 10 minutes. Is even more preferable. When the melt flow rate is in the range of 1 to 10 g / 10 minutes, the stability of heat melt molding is good.
• the melt flow rate of the styrene copolymer (D) in the present specification is a value measured using a melt indexer at a temperature of 230 ° C. under a load of 3.8 kg.
• the method for producing the styrene copolymer (D) is not particularly limited, but a known solution polymerization method, bulk polymerization method, suspension polymerization method, or the like can be appropriately selected.
• the styrene copolymer (D) is a binary copolymer containing a vinyl aromatic monomer unit (d1) and a cyclic acid anhydride monomer unit (d2), or a multiple copolymer.
• the methacrylic resin (C) in combination, the hardness is higher than when only the styrene copolymer (D) is used, and the resin is superior in thermoformability as compared with the case where only the methacrylic resin (C) is used. A laminate is obtained.
• the mass ratio of the methacrylic resin (C) to the styrene copolymer (D) is based on 100 parts by mass of the total content of the methacrylic resin (C) and the styrene copolymer (D).
• the amount of the styrene copolymer (D) is preferably 85 to 30 parts by mass with respect to 15 to 70 parts by mass of the methacrylic resin (C). More preferably, the styrene copolymer (D) is 80 to 35 parts by mass with respect to 20 to 65 parts by mass of the methacrylic resin (C), and more preferably 20 to 55 parts by mass of the methacrylic resin (C).
• the amount of the styrene copolymer (D) is 80 to 45 parts by mass with respect to parts by mass.
• the thermoplastic resin (B) has excellent heat resistance, high refractive index, excellent thermoformability at low temperature, and good appearance while maintaining transparency.
• the glass transition temperature of the thermoplastic resin (B) is preferably in the range of 120 to 165 ° C, more preferably in the range of 120 to 155 ° C.
• the resin laminate provided in the present invention is less likely to be deformed or cracked in a thermal environment.
• the temperature is 165 ° C. or lower, the workability is excellent such as continuous heat shaping by a mirror surface roll or a shaping roll, or batch type heat shaping by a mirror surface mold or a shaping die.
• the glass transition temperature of the thermoplastic resin (B) in the present specification is measured at a heating rate of 10 ° C./min using a differential scanning calorimeter and calculated at the intersection of the baseline and the tangent at the inflection. It is the temperature at the time of.
• the melt flow rate of the thermoplastic resin (B) is preferably in the range of 1 to 10 g / 10 minutes, more preferably in the range of 1.5 to 7 g / 10 minutes, and in the range of 2 to 5 g / 10 minutes. It is more preferable to have. When the melt flow rate is in the range of 1 to 10 g / 10 minutes, the stability of heat melt molding is good.
• the melt flow rate of the thermoplastic resin (B) in the present specification is a value measured using a melt indexer at a temperature of 230 ° C. under a load of 3.8 kg.
• the method for producing the thermoplastic resin (B) is not particularly limited, and necessary components are mixed in advance using a mixer such as a tumbler, a Henschel mixer, or a super mixer, and then a Banbury mixer.
• a mixer such as a tumbler, a Henschel mixer, or a super mixer, and then a Banbury mixer.
• a known method such as melt-kneading with a machine such as a roll, a brabender, a single-screw extruder, a twin-screw extruder, or a pressure kneader can be applied.
• the glass transition temperature of the thermoplastic resin (B) used in the present invention is relatively high and the difference from the glass transition temperature of the polycarbonate resin (A) is small, the polycarbonate resin is used during hot press molding or hot bending. Even when the temperature approaches the glass transition temperature of (A), there is an advantage that there is little problem that the layer containing the thermoplastic resin (B) has an appearance defect.
• the difference between the glass transition temperature of the polycarbonate resin (A) and the glass transition temperature of the thermoplastic resin (B) is preferably in the range of 0 to 15 ° C, more preferably in the range of 0 to 10 ° C. ..
• a further layer may be present between the hardcourt layer according to the present invention and the layer containing the thermoplastic resin (B), but preferably the hardcoat layer is the surface of the layer containing the thermoplastic resin (B) or the surface of the layer containing the thermoplastic resin (B). It is laminated on both sides.
• the hard coat layer is preferably an acrylic hard coat.
• acrylic hardcoat means a coating film formed by polymerizing a monomer or oligomer or prepolymer containing a (meth) acryloyl group as a polymerization group to form a crosslinked structure.
• the composition of the acrylic hard coat preferably contains 2 to 98% by mass of the (meth) acrylic monomer, 2 to 98% by mass of the (meth) acrylic oligomer, and 0 to 15% by mass of the surface modifier. It is preferable to contain 0.001 to 7 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the total of the (meth) acrylic monomer, the (meth) acrylic oligomer and the surface modifier.
• the hard coat layer more preferably contains 5 to 50% by mass of the (meth) acrylic monomer, 50 to 95% by mass of the (meth) acrylic oligomer, and 1 to 10% by mass of the surface modifier, and is particularly preferable. , 20-40% by mass of (meth) acrylic monomer, 60-80% by mass of (meth) acrylic oligomer and 2-5% by mass of surface modifier.
• the amount of the photopolymerization initiator is more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total of the (meth) acrylic monomer, the (meth) acrylic oligomer and the surface modifier. It is particularly preferably 0.1 to 3 parts by mass.
• the (meth) acrylic monomer can be used as long as the (meth) acryloyl group is present as a functional group in the molecule, and may be a monofunctional monomer, a bifunctional monomer, or a trifunctional or higher functional monomer.
• the monofunctional monomer include (meth) acrylic acid and (meth) acrylic acid ester, and specific examples of bifunctional and / or trifunctional or higher (meth) acrylic monomers include diethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate.
• the (meth) acrylic oligomer a bifunctional or higher polyfunctional urethane (meth) acrylate oligomer [hereinafter, also referred to as a polyfunctional urethane (meth) acrylate oligomer], a bifunctional or higher polyfunctional polyester (meth) acrylate oligomer [hereinafter, , Also referred to as polyfunctional polyester (meth) acrylate oligomer], bifunctional or higher functional epoxy (meth) acrylate oligomer [hereinafter, also referred to as polyfunctional epoxy (meth) acrylate oligomer] and the like.
• the hardcoat layer may contain one or more (meth) acrylic oligomers.
• polyfunctional urethane (meth) acrylate oligomer a urethanization reaction product of a (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule and a polyisocyanate; polyols are polyisocyanates. Examples thereof include a urethanization reaction product of an isocyanate compound obtained by reacting with and a (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule.
• Examples of the (meth) acrylate monomer having at least one (meth) acryloyloxy group and a hydroxyl group in one molecule used in the urethanization reaction include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
• 2-Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerindi (meth) acrylate, trimerol propandi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta Examples include (meth) acrylate.
• the polyisocyanate used in the urethanization reaction includes hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and diisocyanate obtained by hydrogenating aromatic isocyanates among these diisocyanates.
• diisocyanate such as hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate
• di or tri polyisocyanate such as triphenylmethane triisocyanate, dimethylene triphenyl triisocyanate, or polyisocyanate obtained by increasing the amount of diisocyanate.
• polyols used in the urethanization reaction in addition to aromatic, aliphatic and alicyclic polyols, polyester polyols, polyether polyols and the like are generally used.
• aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, ethylene glycol, propylene glycol, trimethylolethane, trimethylolpropane, dimethylolheptan, and di. Examples thereof include trimethylolpropionic acid, dimethylolbutylionic acid, glycerin, hydrogenated bisphenol A and the like.
• polyester polyol examples include those obtained by the dehydration condensation reaction between the above-mentioned polyols and the polycarboxylic acid.
• specific examples of the polycarboxylic acid include succinic acid, adipic acid, maleic acid, trimellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may be anhydrous.
• examples of the polyether polyols include the above-mentioned polyols or polyoxyalkylene-modified polyols obtained by reacting phenols with alkylene oxides.
• the polyfunctional polyester (meth) acrylate oligomer is obtained by a dehydration condensation reaction using (meth) acrylic acid, a polycarboxylic acid and a polyol.
• the polycarboxylic acid used in the dehydration condensation reaction include succinic acid, adipic acid, maleic acid, itaconic acid, trimellitic acid, pyromellitic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, and terephthalic acid. These polycarboxylic acids may be anhydrous.
• the polyols used in the dehydration condensation reaction include 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, propylene glycol, neopentyl glycol, dimethylolheptan, dimethylolpropionic acid, and dimethylol.
• Examples thereof include butyionic acid, trimethylolpropane, trimethylolpropane, pentaerythritol, and dipentaerythritol.
• the polyfunctional epoxy (meth) acrylate oligomer is obtained by an addition reaction between polyglycidyl ether and (meth) acrylic acid.
• the polyglycidyl ether include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and bisphenol A diglycidyl ether.
• the surface modifier used in the present invention changes the surface performance of a hard coat layer such as a leveling agent, an antistatic agent, a surfactant, a water-repellent oil-repellent agent, inorganic particles, and organic particles.
• a leveling agent include polyether-modified polyalkylsiloxane, polyether-modified siloxane, polyester-modified hydroxyl group-containing polyalkylsiloxane, polyether-modified polydimethylsiloxane having an alkyl group, modified polyether, silicon-modified acrylic and the like.
• antistatic agent examples include glycerin fatty acid ester monoglyceride, glycerin fatty acid ester organic acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, cationic surfactant, anionic surfactant and the like.
• examples of the inorganic particles include silica particles, alumina particles, zirconia particles, silicon particles, silver particles, and glass particles.
• organic particles include acrylic particles and silicon particles.
• surfactant and the water- and oil-repellent agent examples include a fluorine-containing surfactant such as a fluorine-containing group / lipophilic group-containing oligomer and a fluorine-containing group / hydrophilic group / lipophilic group / UV-reactive group-containing oligomer. And water and oil repellents.
• the hard coat layer may contain a photopolymerization initiator.
• the photopolymerization initiator refers to a photoradical generator.
• Examples of the monofunctional photopolymerization initiator that can be used in the present invention include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone [Darocure 2959: manufactured by Merck]; ⁇ -hydroxy. - ⁇ , ⁇ '-Dimethylacetophenone [Darocure 1173: manufactured by Merck]; Acetphenone-based initiators such as methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone [Irgacure-651], 1-hydroxy-cyclohexylphenylketone.
• Benzoin ether-based initiators such as benzoin ethyl ether and benzoin isopropyl ether; other examples include halogenated ketones, acylphosphinoxides, and acylphosphonates.
• the method for forming the hard coat layer is not particularly limited, but for example, it can be formed by applying a hard coat liquid on a layer located below the hard coat layer and then photopolymerizing it.
• the method of applying the hard coat liquid (polymerizable composition) is not particularly limited, and a known method can be used. For example, spin coating method, dip method, spray method, slide coating method, bar coating method, roll coating method, gravure coating method, meniscus coating method, flexographic printing method, screen printing method, beat coating method, handling method and the like can be mentioned. ..
• a lamp having a light emission distribution with a light wavelength of 420 nm or less is used, and examples thereof include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, and a black light lamp. , Microwave-excited mercury lamp, metal halide lamp, etc.
• high-pressure mercury lamps or metal halide lamps efficiently emit light in the active wavelength region of the initiator, and heat short-wavelength light or reaction compositions that reduce the viscoelastic properties of the obtained polymer by cross-linking. It is preferable because it does not emit a large amount of long-wavelength light that causes evaporation.
• the irradiation intensity of the lamp is a factor that influences the degree of polymerization of the obtained polymer, and is appropriately controlled for each performance of the target product.
• the illuminance is preferably in the range of 0.1 to 300 mW / cm 2 .
• the photopolymerization reaction is inhibited by oxygen in the air or oxygen dissolved in the reactive composition. Therefore, it is desirable to carry out light irradiation using a method that can eliminate the reaction inhibition due to oxygen.
• One such method is to cover the reactive composition with a film made of polyethylene terephthalate or Teflon to cut off contact with oxygen and irradiate the reactive composition with light through the film. Further, the composition may be irradiated with light through a light-transmitting window in an inert atmosphere in which oxygen is replaced with an inert gas such as nitrogen gas or carbon dioxide gas.
• the air velocity of the inert gas is preferably 1 m / sec or less as a relative velocity with respect to the laminate coated with the hard coat liquid moving under the atmosphere of the inert gas. It is more preferably 0.1 m / sec or less.
• the coated surface may be pretreated for the purpose of improving the adhesion of the hard coat layer.
• Known treatment examples include sandblasting, solvent treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone treatment, ultraviolet treatment, and primer treatment with a resin composition. Can be mentioned.
• the hard coat layer preferably has a pencil hardness of 2H or more when irradiated with ultraviolet rays using a metal halide lamp having an irradiation output of UV light (254 nm) of 20 mW / cm 2 .
• the film thickness of the hard coat layer is preferably 1 ⁇ m or more and 40 ⁇ m or less, and more preferably 2 ⁇ m or more and 10 ⁇ m or less. Sufficient hardness can be obtained when the film thickness is 1 ⁇ m or more. Further, when the film thickness is 40 ⁇ m or less, it is possible to suppress the occurrence of cracks during bending.
• the film thickness of the hard coat layer can be measured by observing the cross section with a microscope or the like and actually measuring the film thickness from the coating film interface to the surface.
• the resin laminate of the present invention is not particularly limited, but is preferably Haze ⁇ 1.0%, more preferably Haze ⁇ 0.8%, and particularly preferably Haze ⁇ 0.7%. If Haze exceeds 1.0%, the resin laminate may appear whitish visually.
• the thickness of the layer containing the thermoplastic resin (B) affects the surface hardness and impact resistance of the resin laminate. That is, if the thickness of the layer containing the thermoplastic resin (B) is too thin, the surface hardness becomes low, which is not preferable. If the thickness of the layer containing the thermoplastic resin (B) is too large, the impact resistance deteriorates, which is not preferable.
• the thickness of the layer containing the thermoplastic resin (B) is preferably 10 to 250 ⁇ m, more preferably 20 to 200 ⁇ m. More preferably, it is 30 to 150 ⁇ m.
• the total thickness of the layer containing the polycarbonate resin (A), the layer containing the thermoplastic resin (B), and the hard coat layer is too thin or too thick, molding is difficult.
• the total thickness of the resin laminate is preferably 0.4 to 4.0 mm, more preferably 0.5 to 3.5 mm, and even more preferably 0.5 to 3.0 mm.
• the difference in refractive index between the polycarbonate resin (A) and the thermoplastic resin (B) is preferably in the range of 0 to 0.07, more preferably in the range of 0 to 0.06. It is more preferably in the range of 0 to 0.05.
• the difference in refractive index between the polycarbonate resin (A) and the thermoplastic resin (B) is larger than 0.07, the reflected light intensity at the interface between the layer containing the polycarbonate resin (A) and the layer containing the thermoplastic resin (B). Is large, and problems such as interference fringes may occur.
• the resin laminate of the present invention may be subjected to any one or more of anti-fingerprint treatment, anti-reflection treatment, anti-fouling treatment, anti-static treatment, weather resistance treatment and anti-glare treatment on one or both sides thereof.
• the methods of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment are not particularly limited, and known methods can be used. For example, a method of applying a reflection-reducing paint, a method of depositing a dielectric thin film, a method of applying an antistatic paint, and the like can be mentioned.
• the layer containing the polycarbonate resin (A) forming the base material layer and / or the layer containing the thermoplastic resin (B) forming the surface layer may contain components other than the above-mentioned main components. ..
• an ultraviolet absorber can be mixed and used in the layer containing the polycarbonate resin (A), the layer containing the thermoplastic resin (B), and / or the hard coat layer.
• the hard coat layer may contain an ultraviolet absorber. If the content of the UV absorber is too high, depending on the molding method, the excess UV absorber may be scattered due to the high temperature, which may contaminate the molding environment and cause a problem. From this, the content ratio of the ultraviolet absorber is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, still more preferably 0 to 1% by mass.
• Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, and 2-hydroxy.
• -4-octadecyloxybenzophenone 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, etc.
• Benzophenone UV absorber 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- (2-hydroxy-3) -T-butyl-5-Methylphenyl) benzotriazole, (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol and other benzotriazole-based ultraviolet absorbers, salicylic acid Phenyl, benzoate-based UV absorbers such as 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, bis (2,2,6,6-tetramethylpiperidine-4) -Il) Hinderdamine-based ultraviolet absorbers such as sebacate, 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6
• various additives other than the above-mentioned ultraviolet absorber are added to the layer containing the polycarbonate resin (A) forming the base material layer and / or the layer containing the thermoplastic resin (B) forming the surface layer.
• Such additives include, for example, antioxidants, anticolorants, antistatic agents, mold release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, organic fillers and the like. Reinforcing materials such as inorganic fillers can be mentioned.
• the mixing method is not particularly limited, and a method of total compounding, a method of dry blending the masterbatch, a method of total dry blending, and the like can be used.
• the materials of the layer containing the polycarbonate resin (A), the layer containing the thermoplastic resin (B), and the hard coat layer in the present invention are filtered. It is preferable that the plastic is filtered and purified by. By purifying or laminating through a filter, it is possible to obtain a resin laminate having few appearance defects such as foreign substances and defects.
• the filtration method is not particularly limited, and melt filtration, solution filtration, or a combination thereof can be used.
• the filter medium of the filter is not particularly limited, but is a non-woven fabric of polypropylene, cotton, polyester, viscose rayon or glass fiber or roving yarn roll, phenol resin impregnated cellulose, metal fiber non-woven fabric sintered body, metal powder sintered body, breaker plate, etc. Alternatively, any combination of these can be used. In particular, considering heat resistance, durability, and pressure resistance, a type obtained by sintering a metal fiber non-woven fabric is preferable.
• the filtration accuracy is 50 ⁇ m or less, preferably 30 ⁇ m or less, and more preferably 10 ⁇ m or less for the polycarbonate resin (A) and the thermoplastic resin (B). Further, the filtration accuracy of the hard coat agent is 20 ⁇ m or less, preferably 10 ⁇ m or less, and more preferably 2 ⁇ m or less because it is applied to the outermost surface layer of the resin laminate.
• the polymer filter used for the thermoplastic resin melt filtration is classified into a leaf disc filter, a candle filter, a pack disc filter, a cylindrical filter and the like according to its structure, and a leaf disc filter having a large effective filtration area is particularly suitable.
• the thermal bending process of the resin laminate of the present invention is not particularly limited.
• "heat press molding” in which convex (male) and concave (female) molds are attached to a press machine and the heat-softened laminated sheet is sandwiched between the two molds, and the heat-softened laminated sheet and convex type “Vacuum forming” that makes the laminated sheet adhere to the mold by putting the (male type) mold in a vacuum state and finishes it in the desired shape.
• vacuum forming in which a laminated sheet is brought into close contact with a mold by applying a large pressure to finish it in a desired shape.
• thermoformed body> When a laminated sheet using a conventional polycarbonate resin (for example, Iupiron S-2000, Iupiron S-1000, Iupiron E-2000, which is commercially available from Mitsubishi Engineering Plastics Co., Ltd.) is heat-press molded, the temperature is 135 to 145 ° C. It is necessary to heat the sheet until the polycarbonate resin is sufficiently stretched underneath, and as a result, excessive heat is applied to the thermoplastic resin, resulting in peeling at the interface between the thermoplastic resin layer and the polycarbonate resin layer. , The surface may be whitened or cracks may occur. Further, when the sheet is heated to 160 ° C., the surface may be mellow or scratches on the mold may be transferred. On the other hand, in order to suppress thermoforming defects, when hot press molding is performed at a low temperature of 100 ° C to 135 ° C, the shape of the mold is not reproduced and the shape of the mold returns to a flat shape. May occur.
• a conventional polycarbonate resin for example, I
• the resin laminate of the embodiment of the present invention uses a specific polycarbonate-based resin (A), it springs back even when it is thermoformed at a low temperature of 100 ° C to 135 ° C. Can be obtained, and a thermoformed body having excellent designability at a low temperature can be obtained.
• a resin laminate having a layer containing a thermoplastic resin on a layer containing a polycarbonate resin and having a hard coat layer on the surface of the layer containing the thermoplastic resin is heat-pressed at a low temperature of 100 ° C to 135 ° C. When molding is performed, cracks may occur in the bent portion of the resin laminate.
• the resin laminate of the embodiment of the present invention uses a specific thermoplastic resin (B), it is a resin laminate having a hard coat layer on the surface of the layer containing the thermoplastic resin (B). Even when hot press molding is performed at a low temperature of 100 ° C. to 135 ° C., cracks do not occur in the bent portion of the resin laminate, and a thermoformed body having excellent designability at a low temperature can be obtained.
• the molded product of the embodiment (for example, a thermoformed product) is a molded product containing the resin laminate of the present invention containing various preferable forms and configurations described above. There are no restrictions on the shape, pattern, color, dimensions, etc. of the molded product, and it may be set arbitrarily according to the intended use.
• the resin laminate and the thermoformed body of the embodiment are excellent in thermoforming property at a low temperature (for example, 100 to 135 ° C.), and can suppress the generation of interference fringes. Therefore, it is suitably used as a transparent substrate material, a transparent protective material, and the like.
• portable display devices such as mobile phone terminals, portable electronic play equipment, mobile information terminals, and mobile PCs
• stationary display devices such as notebook PCs, desktop PC LCD monitors, car navigation LCD monitors, and LCD TVs.
• a transparent substrate material such as, and a transparent protective material (for example, a front plate).
• a touch panel front protective plate that requires high design, a front for a car navigation system, an OA device, or a portable electronic device. It is suitably used as a face plate.
• ⁇ Glass transition temperature> A differential scanning calorimetry device DSC6200 manufactured by Seiko Instruments Inc. was used. Nitrogen 30 ml / min. Under circulation, 10 ° C./min. The temperature was raised from 30 ° C to 200 ° C, and then 50 ° C / min. The temperature was lowered from 200 ° C to 30 ° C, and the temperature was changed to 10 ° C / min. The temperature was raised from 30 ° C to 200 ° C. The intersection of the baseline and the tangent at the inflection in the second temperature rise was used as the glass transition temperature.
• a test piece was prepared by an injection molding machine and cut into a length of 40 mm, a width of 10 mm, and a thickness of 3 mm.
• the refractive index of this sample was measured with a multi-wavelength Abbe refractometer DR-M2 manufactured by Atago Co., Ltd.
• the measurement temperature was 20 ° C.
• the measurement wavelength was 589 nm
• monobromonaphthalene was used as the intermediate solution.
• Total light transmittance> The total light transmittance of the resin laminate was measured according to JIS K7361-1 using a reflection / transmittance meter HR-100 (manufactured by Murakami Color Technology Laboratory Co., Ltd.).
• ⁇ Haze> The haze of the resin laminate was measured according to JIS K7136 using a reflection / transmittance meter HR-100 (manufactured by Murakami Color Technology Laboratory Co., Ltd.).
• ⁇ Pencil hardness> In accordance with JIS K 5600-5-4, the hardness of the surface of the hard coat layer on the layer containing the thermoplastic resin (B) near the center of the resin laminate is gradually increased at an angle of 45 degrees and a load of 750 g. The hardness of the hardest pencil that did not cause scars was evaluated as the pencil hardness.
• ⁇ Interference fringes> A black tape (black vinyl tape model number 117BLA manufactured by 3M Japan Co., Ltd.) is attached to the layer side containing the polycarbonate resin (A) or the layer side containing the thermoplastic resin (B) of the resin laminate, and the thermoplastic resin (B) is attached. ) was illuminated with a three-wavelength fluorescent lamp (Technica Inverter Light 60 AL-60231), and interference fringes were evaluated. The pass / fail judgment of the interference fringes was made according to the following criteria, and ⁇ was judged as a pass. ⁇ : Interference fringes are not visible or interference fringes appear weak ⁇ : Interference fringes appear strong
• ⁇ Hot press molding processability> A convex type (male type) and a concave type (female type) in which a 1 mmt resin laminate bends to 50 mmR were produced.
• the resin laminate is preheated at 90 ° C. for 1 minute before molding, placed on a mold so that the surface of the hard coat is convex, pressed at a mold temperature of 80 ° C., 120 ° C. or 160 ° C. for 3 minutes, and naturally. By cooling, a hot press molded product was produced.
• H-1 the materials shown below are used, but the material is not limited thereto.
• Synthesis Example 2 [Manufacturing of Polycarbonate Resin (A-1) Pellet] To 57.2 kg of 9 w / w% sodium hydroxide aqueous solution, 7.1 kg (31.14 mol) of bisphenol A (hereinafter referred to as BPA) manufactured by Nippon Steel Sumitomo Chemical Co., Ltd. and 30 g of hydrosulfite are added and dissolved. did. 40 kg of dichloromethane was added thereto, and 4.33 kg of phosgene was blown over 30 minutes while keeping the solution temperature in the range of 15 ° C. to 25 ° C. with stirring.
• BPA bisphenol A
• the polymerization solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing with pure water was repeated until the pH of the washing solution became neutral.
• a polycarbonate resin powder was obtained by evaporating and distilling off an organic solvent from this purified polycarbonate resin solution.
• the obtained polycarbonate resin powder was melt-kneaded at a cylinder temperature of 260 ° C. using a twin-screw extruder having a screw diameter of 35 mm, extruded into strands, and pelletized with a pelletizer.
• Weight average molecular weight of polycarbonate resin (A-1) 29,000, glass transition temperature: 127 ° C, temperature 300 ° C, melt flow rate under 1.2 kg load: 12.1 g / 10 minutes, refractive index 1.59 Met.
• thermoplastic resin (B-1) 25 parts by mass of methacrylic resin (C-1) and 75 parts by mass of styrene copolymer (D-1), for a total of 100 parts by mass, 500 ppm of phosphorus-based additive PEP-36 (manufactured by ADEKA Co., Ltd.), And stearate monoglyceride (product name: H-100, manufactured by Riken Vitamin Co., Ltd.) 0.2% by mass, mixed with a blender for 20 minutes, and then a twin-screw extruder with a screw diameter of 26 mm equipped with a polymer filter with a mesh opening of 10 ⁇ m.
• PEP-36 phosphorus-based additive
• stearate monoglyceride product name: H-100, manufactured by Riken Vitamin Co., Ltd.
• thermoplastic resin (B-1) (Made by Toshiba Machinery Co., Ltd., TEM-26SS, L / D ⁇ 40) was melt-kneaded at a cylinder temperature of 240 ° C., extruded into strands, and pelletized with a pelletizer.
• the pellets of the thermoplastic resin (B-1) could be stably produced.
• the pellets of the thermoplastic resin (B-1) had an appearance: ⁇ (transparent), a glass transition temperature: 134 ° C., and a refractive index of 1.56.
• thermoplastic resin (B-2) 50 parts by mass of methacrylic resin (C-1) and 50 parts by mass of styrene copolymer (D-1), for a total of 100 parts by mass, phosphorus-based additive PEP-36 500 ppm, and stearic acid monoglyceride 0. 2% by mass was added, and the mixture and pelletization were carried out in the same manner as in Production Example 1.
• the pellets of the thermoplastic resin (B-2) could be stably produced.
• the pellets of the thermoplastic resin (B-2) had an appearance: ⁇ (transparent), a glass transition temperature of 122 ° C., and a refractive index of 1.54.
• thermoplastic resin (G-7) Manufacturing of pellets of thermoplastic resin (G-7)
• E-1 100 parts by mass of the styrene copolymer (E-1)
• 500 ppm of the phosphorus-based additive PEP-36 and 0.2% by mass of stearic acid monoglyceride were added, and the mixture was mixed and pelletized in the same manner as in Production Example 1. rice field.
• the pellets of the thermoplastic resin (G-7) could be stably produced.
• the pellets of the thermoplastic resin (G-7) had an appearance: ⁇ (transparent), a glass transition temperature: 150 ° C., and a refractive index of 1.58.
• thermoplastic resin (G-8) 25 parts by mass of methacrylic resin (C-1) and 75 parts by mass of styrene copolymer (E-2), for a total of 100 parts by mass, phosphorus-based additive PEP-36 500 ppm, and stearic acid monoglyceride 0. 2% by mass was added, and the mixture and pelletization were carried out in the same manner as in Production Example 1.
• the pellets of the thermoplastic resin (G-8) could be stably produced.
• the pellets of the thermoplastic resin (G-8) had an appearance: ⁇ (semi-transparent).
• Example 1 Manufacturing of resin laminate (I-1)] Each is a multi-layer extruder having a single-screw extruder with a shaft diameter of 32 mm, a single-screw extruder with a shaft diameter of 65 mm, a feed block connected to all extruders, and a 650 mm wide T-die connected to the feed block.
• a resin laminate was molded using a multi-layer extruder with a multi-manifold die coupled to the extruder.
• the thermoplastic resin (B-1) obtained in Production Example 1 was continuously introduced into a single-screw extruder having a shaft diameter of 32 mm, and extruded under the conditions of a cylinder temperature of 240 ° C.
• the polycarbonate resin (A-1) obtained in Synthesis Example 2 was continuously introduced into a single-screw extruder having a shaft diameter of 65 mm, and extruded at a cylinder temperature of 280 ° C. and a discharge rate of 31.8 kg / h.
• the feed block connected to all extruders was equipped with two types and two layers of distribution pins, and a thermoplastic resin (B-1) and a polycarbonate resin (A-1) were introduced and laminated at a temperature of 270 ° C.
• a resin laminate of (B-1) and a polycarbonate resin (A-1) was obtained.
• the total thickness of the central portion of the obtained resin laminate was 1000 ⁇ m, and the thickness of the surface layer (layer containing the thermoplastic resin (B)) was 60 ⁇ m.
• thermoplastic resin (B-1) of the resin laminate obtained above 60 parts by mass of a hexafunctional urethane acrylate oligomer (product name: U6HA, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), PEG200 # diacrylate.
• the thickness of the hard coat layer (H-1) was 6 ⁇ m.
• This resin laminate (I-1) has a total light transmittance of 90.8%, Haze: 0.2%, pencil hardness: 3H, and interference fringes: ⁇ .
• hot press molding is performed at a mold temperature of 80 ° C.
• the appearance of the hot press molded body ⁇
• the crack in the bent portion of the hot press molded body ⁇
• the springback of the hot press molded body ⁇ .
• hot press molding is performed at a mold temperature of 120 ° C.
• the appearance of the hot press molded body is ⁇
• the crack in the bent portion of the hot press molded body is ⁇
• the springback of the hot press molded body is ⁇ .
• hot press molding was performed at a mold temperature of 160 ° C.
• the appearance of the hot press molded body was ⁇
• the crack in the bent portion of the hot press molded body was ⁇
• the springback of the hot press molded body was ⁇
• Example 2 [Manufacturing of resin laminate (I-2)] With the hard coat layer (H-1) in the same manner as the resin laminate (I-1) of Example 1 except that the thermoplastic resin (B-2) was used instead of the thermoplastic resin (B-1). A resin laminate (I-2) of a thermoplastic resin (B-2) and a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (I-2) was 1006 ⁇ m, the surface layer (B-2) thickness was 60 ⁇ m, and the hard coat layer (H-1) thickness was 6 ⁇ m.
• This resin laminate (I-2) has a total light transmittance of 90.8%, Haze: 0.2%, pencil hardness: 3H, and interference fringes: ⁇ .
• Comparative Example 1 Manufacturing of resin laminate (J-1)] With the hard coat layer (H-1) in the same manner as the resin laminate (I-1) of Example 1 except that the thermoplastic resin (G-1) was used instead of the thermoplastic resin (B-1). A resin laminate (J-1) of a thermoplastic resin (G-1) and a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (J-1) was 1006 ⁇ m, the surface layer (G-1) thickness was 60 ⁇ m, and the hard coat layer (H-1) thickness was 6 ⁇ m.
• This resin laminate (J-1) has a total light transmittance of 91.0%, Haze: 0.2%, pencil hardness: 3H, and interference fringes: ⁇ .
• Comparative Example 2 Manufacturing of resin laminate (J-2)] With the hard coat layer (H-1) in the same manner as the resin laminate (I-1) of Example 1 except that the thermoplastic resin (G-2) was used instead of the thermoplastic resin (B-1). A resin laminate (J-2) of a thermoplastic resin (G-2) and a polycarbonate resin (A-1) was obtained. The total thickness of the central portion of the obtained resin laminate (J-2) was 1006 ⁇ m, the surface layer (G-2) thickness was 60 ⁇ m, and the hard coat layer (H-1) thickness was 6 ⁇ m.
• This resin laminate (J-2) has a total light transmittance of 90.9%, Haze: 0.2%, pencil hardness: 3H, and interference fringes: ⁇ .
• Comparative Example 3 Manufacturing of resin laminate (J-3)
• the hard coat layer (H-1) in the same manner as the resin laminate (I-1) of Example 1 except that the thermoplastic resin (G-3) was used instead of the thermoplastic resin (B-1).
• a resin laminate (J-3) of a thermoplastic resin (G-3) and a polycarbonate resin (A-1) was obtained.
• the total thickness of the central portion of the obtained resin laminate (J-3) was 1006 ⁇ m
• the thickness of the surface layer (G-3) was 60 ⁇ m
• the thickness of the hard coat layer (H-1) was 6 ⁇ m.
• This resin laminate (J-3) has a total light transmittance of 91.2%, Haze: 0.2%, pencil hardness: 3H, and interference fringes: ⁇ .
• hot press molding is performed at a mold temperature of 80 ° C.
• the appearance of the hot press molded body ⁇
• the crack in the bent portion of the hot press molded body ⁇
• the springback of the hot press molded body ⁇ .
• hot press molding is performed at a mold temperature of 120 ° C.
• the appearance of the hot press molded body is ⁇
• the crack in the bent portion of the hot press molded body is ⁇
• the springback of the hot press molded body is ⁇ .
• hot press molding was performed at a mold temperature of 160 ° C.
• the appearance of the hot press molded body was ⁇
• the crack in the bent portion of the hot press molded body was ⁇
• the springback of the hot press molded body was ⁇ .
• Comparative Example 4 Manufacturing of resin laminate (J-4)
• the hard coat layer (H-1) in the same manner as the resin laminate (I-1) of Example 1 except that the thermoplastic resin (G-4) was used instead of the thermoplastic resin (B-1).
• a resin laminate (J-4) of a thermoplastic resin (G-4) and a polycarbonate resin (A-1) was obtained.
• the total thickness of the central portion of the obtained resin laminate (J-4) was 1006 ⁇ m
• the thickness of the surface layer (G-4) was 60 ⁇ m
• the thickness of the hard coat layer (H-1) was 6 ⁇ m.
• This resin laminate (J-4) has a total light transmittance of 91.2%, Haze: 0.2%, pencil hardness: 3H, and interference fringes: ⁇ .
• hot press molding is performed at a mold temperature of 80 ° C.
• the appearance of the hot press molded body ⁇
• the crack in the bent portion of the hot press molded body ⁇
• the springback of the hot press molded body ⁇ .
• hot press molding is performed at a mold temperature of 120 ° C.
• the appearance of the hot press molded body is ⁇
• the crack in the bent portion of the hot press molded body is ⁇
• the springback of the hot press molded body is ⁇ .
• hot press molding was performed at a mold temperature of 160 ° C.
• the appearance of the hot press molded body was ⁇
• the crack in the bent portion of the hot press molded body was ⁇
• the springback of the hot press molded body was ⁇ .
• Comparative Example 5 Manufacturing of resin laminate (J-5)
• the hard coat layer (H-1) heat is the same as that of the resin laminate (I-1) of Example 1 except that the thermoplastic resin (G-5) is used instead of the thermoplastic resin (B-1).
• a resin laminate (J-5) of a plastic resin (G-5) and a polycarbonate resin (A-1) were obtained.
• the total thickness of the central portion of the obtained resin laminate (J-5) was 1006 ⁇ m
• the surface layer (G-5) thickness was 60 ⁇ m
• the hard coat layer (H-1) thickness was 6 ⁇ m.
• This resin laminate (J-5) has a total light transmittance of 91.4%, a haze: 0.3%, a pencil hardness of 3H, and an interference fringe: ⁇ .
• hot press molding is performed at a mold temperature of 80 ° C.
• the appearance of the hot press molded body ⁇
• the crack in the bent portion of the hot press molded body ⁇
• the springback of the hot press molded body ⁇ .
• hot press molding is performed at a mold temperature of 120 ° C.
• the appearance of the hot press molded body is ⁇
• the crack in the bent portion of the hot press molded body is ⁇
• the springback of the hot press molded body is ⁇ .
• hot press molding was performed at a mold temperature of 160 ° C.
• the appearance of the hot press molded body was ⁇
• the crack in the bent portion of the hot press molded body was ⁇
• the springback of the hot press molded body was ⁇ .
• Comparative Example 7 Manufacturing of resin laminate (J-7)
• the hard coat layer (H-1) in the same manner as the resin laminate (I-1) of Example 1 except that the thermoplastic resin (G-7) was used instead of the thermoplastic resin (B-1).
• a resin laminate (J-7) of a thermoplastic resin (G-7) and a polycarbonate resin (A-1) was obtained.
• the total thickness of the central portion of the obtained resin laminate (J-7) was 1006 ⁇ m
• the surface layer (G-7) thickness was 60 ⁇ m
• the hard coat layer (H-1) thickness was 6 ⁇ m.
• This resin laminate (J-7) has a total light transmittance of 90.6%, Haze: 0.2%, pencil hardness: H, and interference fringes: ⁇ .
• Comparative Example 8 Manufacturing of resin laminate (J-8)
• Polycarbonate resin (F-1) is used instead of polycarbonate resin (A-1), and it is cooled while transferring the mirror surface with three mirror finishing rolls at temperatures of 130 ° C, 140 ° C, and 185 ° C from the upstream side.
• the hard coat layer (H-1), the thermoplastic resin (B-1), and the polycarbonate-based resin (F-1) are used in the same manner as in the resin laminate (I-1) of Example 1 except that the resin laminate (I-1) is changed to.
• a resin laminate (J-8) was obtained.
• the total thickness of the central portion of the obtained resin laminate (J-8) was 1006 ⁇ m, the surface layer (B-1) thickness was 60 ⁇ m, and the hard coat layer (H-1) thickness was 6 ⁇ m.
• This resin laminate (J-8) has a total light transmittance of 90.8%, Haze: 0.2%, pencil hardness: 3H, and interference fringes: ⁇ .
• Comparative Example 9 Manufacturing of resin laminate (J-9)
• the hard coat layer (H-1) in the same manner as the resin laminate (J-8) of Comparative Example 8 except that the thermoplastic resin (B-2) was used instead of the thermoplastic resin (B-1).
• a resin laminate (J-9) of a thermoplastic resin (B-2) and a polycarbonate resin (F-1) was obtained.
• the total thickness of the central portion of the obtained resin laminate (J-9) was 1006 ⁇ m
• the surface layer (B-2) thickness was 60 ⁇ m
• the hard coat layer (H-1) thickness was 6 ⁇ m.
• This resin laminate (J-9) has a total light transmittance of 90.8%, Haze: 0.2%, pencil hardness: 3H, and interference fringes: ⁇ .
• Comparative Example 10 Manufacturing of resin laminate (J-10)] With the hard coat layer (H-1) in the same manner as the resin laminate (J-8) of Comparative Example 8 except that the thermoplastic resin (G-1) was used instead of the thermoplastic resin (B-1). A resin laminate (J-10) of a thermoplastic resin (G-1) and a polycarbonate resin (F-1) was obtained. The total thickness of the central portion of the obtained resin laminate (J-10) was 1006 ⁇ m, the surface layer (G-1) thickness was 60 ⁇ m, and the hard coat layer (H-1) thickness was 6 ⁇ m.
• This resin laminate (J-10) has a total light transmittance of 91.0%, Haze: 0.2%, pencil hardness: 3H, and interference fringes: ⁇ .
• Comparative Example 11 Manufacturing of resin laminate (J-11)] With the hard coat layer (H-1) in the same manner as the resin laminate (J-8) of Comparative Example 8 except that the thermoplastic resin (G-2) was used instead of the thermoplastic resin (B-1). A resin laminate (J-11) of a thermoplastic resin (G-2) and a polycarbonate resin (F-1) was obtained. The total thickness of the central portion of the obtained resin laminate (J-11) was 1006 ⁇ m, the surface layer (G-2) thickness was 60 ⁇ m, and the hard coat layer (H-1) thickness was 6 ⁇ m.
• This resin laminate (J-11) has a total light transmittance of 90.9%, Haze: 0.2%, pencil hardness: 3H, and interference fringes: ⁇ .
• Comparative Example 12 Manufacturing of resin laminate (J-12)] With the hard coat layer (H-1) in the same manner as the resin laminate (J-8) of Comparative Example 8 except that the thermoplastic resin (G-3) was used instead of the thermoplastic resin (B-1). A resin laminate (J-12) of a thermoplastic resin (G-3) and a polycarbonate resin (F-1) was obtained. The total thickness of the central portion of the obtained resin laminate (J-12) was 1006 ⁇ m, the surface layer (G-3) thickness was 60 ⁇ m, and the hard coat layer (H-1) thickness was 6 ⁇ m.
• This resin laminate (J-12) has a total light transmittance of 91.2%, Haze: 0.2%, pencil hardness: 3H, and interference fringes: ⁇ .
• Comparative Example 13 Manufacturing of Resin Laminated Body (J-13)] With the hard coat layer (H-1) in the same manner as the resin laminate (J-8) of Comparative Example 8 except that the thermoplastic resin (G-4) was used instead of the thermoplastic resin (B-1). A resin laminate (J-13) of a thermoplastic resin (G-4) and a polycarbonate resin (F-1) was obtained. The total thickness of the central portion of the obtained resin laminate (J-13) was 1006 ⁇ m, the thickness of the surface layer (G-4) was 60 ⁇ m, and the thickness of the hard coat layer (H-1) was 6 ⁇ m.
• This resin laminate (J-13) has a total light transmittance of 91.2%, Haze: 0.2%, pencil hardness: 3H, and interference fringes: ⁇ .
• hot press molding is performed at a mold temperature of 80 ° C.
• the appearance of the hot press molded body ⁇
• the crack in the bent portion of the hot press molded body ⁇
• the springback of the hot press molded body ⁇ .
• hot press molding is performed at a mold temperature of 120 ° C.
• the appearance of the hot press molded body is ⁇
• the crack in the bent portion of the hot press molded body is ⁇
• the springback of the hot press molded body is ⁇ .
• hot press molding was performed at a mold temperature of 160 ° C.
• the appearance of the hot press molded body was ⁇
• the crack in the bent portion of the hot press molded body was ⁇
• the springback of the hot press molded body was ⁇ .
• Comparative Example 14 Manufacturing of resin laminate (J-14)] With the hard coat layer (H-1) in the same manner as the resin laminate (J-8) of Comparative Example 8 except that the thermoplastic resin (G-5) was used instead of the thermoplastic resin (B-1). A resin laminate (J-14) of a thermoplastic resin (G-5) and a polycarbonate resin (F-1) was obtained. The total thickness of the central portion of the obtained resin laminate (J-14) was 1006 ⁇ m, the surface layer (G-5) thickness was 60 ⁇ m, and the hard coat layer (H-1) thickness was 6 ⁇ m.
• This resin laminate (J-14) has a total light transmittance of 91.4%, a haze: 0.3%, a pencil hardness of 3H, and an interference fringe: ⁇ .
• hot press molding is performed at a mold temperature of 80 ° C.
• the appearance of the hot press molded body ⁇
• the crack in the bent portion of the hot press molded body ⁇
• the springback of the hot press molded body ⁇ .
• hot press molding is performed at a mold temperature of 120 ° C.
• the appearance of the hot press molded body is ⁇
• the crack in the bent portion of the hot press molded body is ⁇
• the springback of the hot press molded body is ⁇ .
• hot press molding was performed at a mold temperature of 160 ° C.
• the appearance of the hot press molded body was ⁇
• the crack in the bent portion of the hot press molded body was ⁇
• the springback of the hot press molded body was ⁇ .
• Comparative Example 15 Manufacturing of resin laminate (J-15)] With the hard coat layer (H-1) in the same manner as the resin laminate (J-8) of Comparative Example 8 except that the thermoplastic resin (G-6) was used instead of the thermoplastic resin (B-1). A resin laminate (J-15) of a thermoplastic resin (G-6) and a polycarbonate resin (F-1) was obtained. The total thickness of the central portion of the obtained resin laminate (J-15) was 1006 ⁇ m, the surface layer (G-6) thickness was 60 ⁇ m, and the hard coat layer (H-1) thickness was 6 ⁇ m.
• This resin laminate (J-15) has a total light transmittance of 90.5%, Haze: 0.2%, pencil hardness: H, and interference fringes: ⁇ .
• Comparative Example 16 Manufacturing of resin laminate (J-16)] With the hard coat layer (H-1) in the same manner as the resin laminate (J-8) of Comparative Example 8 except that the thermoplastic resin (G-7) was used instead of the thermoplastic resin (B-1). A resin laminate (J-16) of a thermoplastic resin (G-7) and a polycarbonate resin (F-1) was obtained. The total thickness of the central portion of the obtained resin laminate (J-16) was 1006 ⁇ m, the surface layer (G-7) thickness was 60 ⁇ m, and the hard coat layer (H-1) thickness was 6 ⁇ m.
• This resin laminate (J-7) has a total light transmittance of 90.6%, Haze: 0.2%, pencil hardness: H, and interference fringes: ⁇ .
• Production Examples 1 and 2 in which a specific methacrylic resin (C) and a specific styrene copolymer (D) are blended and specific production examples 1 and 2 are specified. Comparing with the production comparative example 5 of the methacrylic resin (C) alone, the refractive index was higher in the production examples 1 and 2. Further, Production Examples 1 and 2 were blended with a specific methacrylic resin (C) and a styrene copolymer (E-2, E-3) other than the specific styrene copolymer (D) in a specific mass ratio. Comparing with Production Comparative Examples 8 to 11, Production Examples 1 and 2 were more transparent and had a better appearance.
• the resin laminate after hard coat coating is blended with a specific methacrylic resin (C) and a specific styrene copolymer (D) at a specific ratio, and pelletized with a high refractive index.
• Examples 1 and 2 in which the thermoplastic resin (B) and the polycarbonate resin (A) are laminated and have a hard coat on one side surface of the thermoplastic resin (B), and a specific methacrylic resin (C) and a specific styrene.
• the copolymer (D) is blended at a ratio other than a specific ratio, the pelletized thermoplastic resin (G) and the polycarbonate resin (A) are laminated, and a hard coat is applied to one side surface of the thermoplastic resin (G).
• the resin laminates of Examples 1 and 2 suppressed cracks in the bent portion of the hot press molded body at a mold temperature of 120 ° C.
• the thermoplastic resin (G) obtained by blending Examples 1 and 2 with a specific methacrylic resin (C) and a styrene copolymer (E-1) having a specific weight average molecular weight in a specific ratio and pelletizing them.
• the polycarbonate resin (A) are laminated, and when compared with Comparative Examples 2 to 3 having a hard coat on one side surface of the thermoplastic resin (G), the resin laminates of Examples 1 and 2 are better. Cracks in the bent portion of the hot press molded product at a mold temperature of 120 ° C.
• thermoplastic resin (G) obtained by pelletizing a specific methacrylic resin (C) alone and a specific polycarbonate resin (A) are laminated, and a hard coat is provided on one side of the thermoplastic resin (G). Comparing with No. 5, the resin laminates of Examples 1 and 2 suppressed cracks in the bent portion of the hot press molded product at a mold temperature of 120 ° C.
• thermoplastic resin (G) obtained by pelletizing a specific styrene copolymer (D) alone and a specific polycarbonate resin (A) are laminated to form a thermoplastic resin (G).
• the resin laminates of Examples 1 and 2 had higher pencil hardness and suppressed cracks in the bent portion of the hot press molded body.
• Examples 1 and 2 are blended with a specific methacrylic resin (C) and a specific styrene copolymer (D) in a specific ratio, and pelletized into a thermoplastic resin (B) and a polycarbonate resin (F).

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