WO2014061817A1 - Stratifié - Google Patents

Stratifié Download PDF

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Publication number
WO2014061817A1
WO2014061817A1 PCT/JP2013/078395 JP2013078395W WO2014061817A1 WO 2014061817 A1 WO2014061817 A1 WO 2014061817A1 JP 2013078395 W JP2013078395 W JP 2013078395W WO 2014061817 A1 WO2014061817 A1 WO 2014061817A1
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WIPO (PCT)
Prior art keywords
resin
laminate
resin layer
roll
thermoplastic resin
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PCT/JP2013/078395
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English (en)
Japanese (ja)
Inventor
雄太 豊嶋
智清 土井
常守　秀幸
Original Assignee
帝人株式会社
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Application filed by 帝人株式会社 filed Critical 帝人株式会社
Priority to KR1020157009005A priority Critical patent/KR102139840B1/ko
Priority to JP2014542207A priority patent/JP5872058B2/ja
Priority to CN201380053406.XA priority patent/CN104703796A/zh
Publication of WO2014061817A1 publication Critical patent/WO2014061817A1/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
    • B32B27/06—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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (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
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays

Definitions

  • the present invention relates to a laminate having high pencil hardness, excellent heat resistance, and hardly warping and deforming.
  • Polycarbonate resin sheets are excellent in transparency, heat resistance, impact resistance, and mechanical strength, and are used in displays for OA / electronic devices, touch panel front plates, and the like.
  • the polycarbonate resin has a drawback that the surface of the resin is easily scratched due to its low pencil hardness, and discoloration tends to occur during outdoor use due to its low weather resistance.
  • a layer made of a methacrylic resin excellent in weather resistance and pencil hardness hereinafter sometimes abbreviated as PMMA layer
  • PC layer polycarbonate resin
  • Patent Document 1 discloses a laminate in which a PMMA layer having excellent weather resistance is laminated on a PC layer. According to Patent Document 1, it is described that this laminate hardly causes warpage due to water absorption and is excellent in weather resistance.
  • Patent Document 1 does not discuss the suppression of warpage deformation of the laminate in a high temperature and high humidity environment.
  • Patent Document 2 discloses a laminate in which warpage fluctuations in a high-temperature and high-humidity environment are suppressed by curving the sheet with a constant radius of curvature when forming the sheet.
  • the thermoplastic resin used in the laminate is mainly composed of methyl methacrylate, and in a long-term high-temperature and high-humidity environment (temperature 85 ° C., humidity 85% for 120 hours), heat resistance and water absorption In terms of properties, it is insufficient to suppress warpage deformation.
  • Patent Document 3 when a laminate is formed with three rolls, the warp after heating to 80 ° C.
  • Patent Document 4 discloses a laminate in which a modified polycarbonate resin layer excellent in heat resistance and pencil hardness is laminated on a PC layer. However, Patent Document 4 does not discuss the suppression of warpage deformation of the laminate in a high temperature and high humidity environment.
  • An object of the present invention is a laminate having excellent pencil hardness, scratch resistance, heat resistance, and low water absorption, small warpage deformation in a normal temperature and normal humidity environment, and low warpage deformation in a long-term high temperature and high humidity environment. Is to provide. Moreover, the objective of this invention is providing the laminated body with few peeling by curvature deformation, when it uses for display cover panels, such as a smart phone, and a touchscreen front plate.
  • the inventors melt-extruded a laminate including a resin layer (A) and a resin layer (B) made of two different thermoplastic resins having a specific glass transition point and water absorption, and three cooling rolls.
  • the present invention has been completed by finding that the rate can be 0.2% or less.
  • the present invention is based on the finding that the warpage rate under a high-temperature and high-humidity environment is reduced by finely stretching a laminate composed of two specific types of thermoplastic resins. That is, the present invention is a laminate comprising a resin layer (A) comprising a thermoplastic resin (A) and a resin layer (B) comprising a thermoplastic resin (B) laminated on at least one surface thereof.
  • the thickness of the resin layer (B) is 40 to 150 ⁇ m, and the total thickness of the resin layer (A) and the resin layer (B) is 0.8 mm to 3.0 mm,
  • the glass transition points TgA and TgB of the thermoplastic resin (A) and the thermoplastic resin (B) are both 115 ° C. or higher, and the difference between TgA and TgB is 30 ° C. or lower.
  • thermoplastic resin (A) and the thermoplastic resin (B) are both 0.7% or less and the difference in water absorption is 0.5% or less
  • thermoplastic resin (B) are both 0.7% or less and the difference in water absorption is 0.5% or less
  • the warpage rate after leaving the laminate for 120 hours in a high-temperature and high-humidity environment at a temperature of 85 ° C. and a humidity of 85% RH is 0.2% or less. It is the laminate.
  • the present invention also includes (i) extruding a laminate including a resin layer (A) and a resin layer (B) laminated on at least one surface thereof from a die in a molten state, (Ii) cooling the extruded laminate with the first to third cooling rolls while taking it with the take-up roll; Including each process,
  • the first to third cooling rolls have parallel rotation center axes, are on the same plane, are arranged close to each other, and the peripheral speed of the take-up roll with respect to the second roll peripheral speed is 0.996 to 1..
  • FIG. 1 is a diagram showing the apparatus used in the example.
  • the resin layer (A) is made of a thermoplastic resin (A).
  • the thermoplastic resin (A) has a glass transition point TgA of 115 ° C. or higher and a water absorption of 0.7% or lower.
  • the glass transition point TgA is preferably 115 to 180 ° C, more preferably 130 to 160 ° C, and still more preferably 140 to 150 ° C.
  • the glass transition point in the present invention is obtained by using a differential scanning calorimeter (DSC) and measuring at a heating rate of 20 ° C./min in accordance with JIS K7121.
  • the water absorption is preferably 0.5% or less, and more preferably 0.4% or less.
  • a polycarbonate resin is preferably a main component.
  • the content of the polycarbonate resin in the thermoplastic resin (A) is preferably 50% by weight or more, more preferably 70% by weight or more, still more preferably 80% by weight or more, and particularly preferably 90% by weight. Most preferably, it consists essentially of a polycarbonate resin.
  • the polycarbonate resin is an aromatic polycarbonate resin produced by reacting a dihydric phenol and a carbonate precursor by a known method such as an interfacial polycondensation method or a melt transesterification method.
  • dihydric phenols include 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4-hydroxyphenyl).
  • bisphenol A 2,2-bis (4-hydroxyphenyl) propane
  • 1,1-bis (4-hydroxyphenyl) ethane 1,1-bis (4-hydroxyphenyl
  • Cyclohexane 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) sulfide, Bis (4-hydroxyphenyl) sulfone etc.
  • Preferred dihydric phenols are bis (4-hydroxyphenyl) alkanes, and bisphenol A is particularly preferred.
  • Examples of the carbonate precursor include carbonyl halide, carbonate ester, haloformate, and the like, and specifically include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.
  • the above dihydric phenols can be used alone or in combination of two or more thereof, and a molecular weight regulator, a branching agent, a catalyst and the like can be used as necessary.
  • the viscosity average molecular weight of the polycarbonate resin used for the resin layer (A) is preferably 1.0 ⁇ 10 4 to 10.0 ⁇ 10 4 , more preferably 1.5 ⁇ 10 4 to 4.5 ⁇ 10 4 , It is preferably 1.8 ⁇ 10 4 to 3.0 ⁇ 10 4 .
  • the viscosity average molecular weight is obtained by inserting the specific viscosity ( ⁇ sp ) obtained from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride at 20 ° C. into the following equation.
  • polycarbonate resins may contain additives such as heat stabilizers (0.001 to 0.2% by weight) such as phosphites, phosphates and phosphonates, and esters of alcohol and fatty acids. Molding agents (0.005 to 2.0% by weight), tetrabromobisphenol A, low molecular weight polycarbonate of tetrabromobisphenol A, flame retardants (3 to 15% by weight) such as decabromodiphenyl ether, colorants, fluorescent whitening agents Etc. may be blended.
  • the thickness of the resin layer (A) is in the range of 0.65 mm to 2.96 mm. Preferably, it is in the range of 0.8 mm to 2.5 mm.
  • the resin layer (B) is made of a thermoplastic resin (B).
  • the thermoplastic resin (B) has a glass transition point TgB of 115 ° C. or higher and a water absorption of 0.7% or lower.
  • the glass transition point TgB is preferably 115 to 150 ° C., more preferably 117 to 140 ° C., and still more preferably 120 to 130 ° C.
  • the water absorption is preferably 0.6% or less, more preferably 0.5% or less. When TgB is less than 115 ° C.
  • the laminate is warped by heat and moisture absorption in a high-temperature and high-humidity environment at a temperature of 85 ° C. and a humidity of 85% RH. It is easy to generate.
  • the difference (TgA-TgB) of the glass transition point TgA and the glass transition point TgB is 30 degrees C or less.
  • the difference between the glass transition point TgA and the glass transition point TgB is preferably 28 ° C. or lower, more preferably 25 ° C. or lower. Further, the difference in water absorption between the thermoplastic resin (A) and the thermoplastic resin (B) (water absorption of the thermoplastic resin (B) ⁇ water absorption of the thermoplastic resin (A)) is 0.5% or less. . When the difference in water absorption exceeds 0.5%, a dimensional change occurs due to hygroscopic expansion in a high-temperature and high-humidity environment at a temperature of 85 ° C. and a humidity of 85% RH, and warpage is likely to occur.
  • the difference in water absorption between the thermoplastic resin (A) and the thermoplastic resin (B) is preferably 0.4% or less, more preferably 0.3% or less, and further preferably 0.2% or less. Yes, particularly preferably 0.1% or less.
  • the pencil hardness of the resin layer (B) is measured according to JIS K5600-5-4.
  • the pencil hardness of the resin layer (B) is preferably F or more, more preferably H or more, and further preferably 2H or more.
  • the thickness of the resin layer (B) is 40 to 150 ⁇ m, preferably 50 to 120 ⁇ m, more preferably 60 to 100 ⁇ m.
  • the thermoplastic resin (B) includes a unit [1] represented by the following formula and a unit [2] represented by the following formula, and the ratio of the unit [1] is 50 to 100 mol% based on all units. And a modified polycarbonate resin having a viscosity average molecular weight of 1.0 ⁇ 10 4 to 8.0 ⁇ 10 4 .
  • W represents a single bond, an alkanediyl group having 1 to 6 carbon atoms, an arylene group having 6 to 10 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms.
  • alkanediyl group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propanediyl group, a propane-2,2-diyl group, and a butanediyl group.
  • Examples of the arylene group having 6 to 10 carbon atoms include phenylene group, naphthalenediyl group, biphenoldiyl group, and toluenediyl group.
  • cycloalkylene having 3 to 8 carbon atoms examples include a cyclopentylene group, a cyclohexylene group, and a cyclooctylene group.
  • Unit [1] consists of 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-methylphenyl) propane and 2,2′-methyl-4,4. It is preferably a unit derived from at least one selected from the group consisting of '-biphenyldiol. In particular, a unit derived from 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane or 2,2-bis (4-hydroxy-3-methylphenyl) propane is preferable.
  • the proportion of the unit [1] in all units is preferably 60 mol% or more, more preferably 80 mol% or more, further preferably 90 mol% or more, and particularly preferably substantially 100%.
  • the modified polycarbonate resin may be a copolymer or a polymer blend resin as long as the ratio of the unit [1] is satisfied.
  • a method for producing the modified polycarbonate resin a method of reacting a dihydric phenol and a carbonate precursor by a known method such as an interfacial polycondensation method or a melt transesterification method is used in the same manner as the polycarbonate resin.
  • the viscosity average molecular weight of the modified polycarbonate resin is preferably 1.1 ⁇ 10 4 to 6.0 ⁇ 10 4 , more preferably 1.3 ⁇ 10 4 to 4.5 ⁇ 10 4 , and even more preferably 1 .5 ⁇ 10 4 to 3.0 ⁇ 10 4 .
  • the thermoplastic resin (B) contains 5 to 80% by weight of aromatic (meth) acrylate units and 20 to 95% by weight of methyl (meth) acrylate units, and has a weight average molecular weight of 5,000 to 30,000.
  • a blend resin of 20 to 60 parts by weight of a certain acrylic copolymer and 40 to 80 parts by weight of a polycarbonate resin (however, the total of the acrylic polymer and the polycarbonate resin is 100 parts by weight) can be mentioned.
  • a blend resin is preferable because it has high pencil hardness and good heat resistance.
  • the acrylic copolymer preferably contains 10 to 60% by weight of aromatic (meth) acrylate units and 40 to 90% by weight of methyl (meth) acrylate units, and 20 to 50% by weight of aromatic (meth) acrylate units and More preferably, it contains 50 to 80% by weight of methyl (meth) acrylate units.
  • the weight average molecular weight of the acrylic copolymer is preferably in the range of 8,000 to 28,000, and more preferably in the range of 10,000 to 25,000.
  • the blend resin is preferably a mixture of 25 to 55 parts by weight of an acrylic copolymer and 45 to 75 parts by weight of a polycarbonate resin, and a mixture of 30 to 50 parts by weight of an acrylic copolymer and 50 to 70 parts by weight of a polycarbonate resin. More preferred.
  • the polymer blending can be carried out by any method. For example, a method of mixing with a tumbler, V-type blender, nauter mixer, kneading roll, extruder or the like is appropriately used.
  • a thermoplastic resin (B) contains a ultraviolet absorber.
  • the resin layer (B) absorbs ultraviolet rays, thereby suppressing degradation of the resin layer (A) due to light energy. be able to.
  • the content of the ultraviolet absorber is preferably in the range of 0.5 to 5.0 parts by weight and more preferably in the range of 1.0 to 4.0 parts by weight with respect to 100 parts by weight of the thermoplastic resin (B).
  • Examples of the ultraviolet absorber include benzotriazole, benzophenone, benzoxazine, and triazine.
  • Examples of the benzotriazole ultraviolet absorber include 2,2′-methylenebis [6- (benzotriazol-2-yl) -4-tert-octylphenol], 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ ). -Dimethylbenzyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2H-benzotriazole, and the like.
  • triazine ultraviolet absorbers examples include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2- [4,6-bis (2,4-dimethylphenyl). ) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol.
  • another additive can also be added to a thermoplastic resin (B).
  • a known antioxidant can be used as the antioxidant.
  • the content of the antioxidant is preferably in the range of 0.001 to 0.2 parts by weight with respect to 100 parts by weight of the thermoplastic resin (B).
  • Phenol antioxidants include n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, n-octadecyl-3- (3,5-di-t-butyl- 4-hydroxyphenyl) -acetate, n-octadecyl-3,5-di-t-butyl-4-hydroxybenzoate, n-hexyl-3,5-di-t-butyl-4-hydroxyphenylbenzoate, n-dodecyl -3,5-di-t-butyl-4-hydroxyphenylbenzoate, neo-dodecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate.
  • Examples of phosphorus antioxidants include tris (2,4-di-t-butylphenyl) phosphite, 2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f ] [1,3,2] dioxaphosphin-6-yl] oxy] -N, N-bis [2-[[2,4,8,10-tetrakis (1,1 dimethylethyl) dibenzo [d , F] [1,3,2] dioxaphosphin-6-yl] oxy] -ethyl] ethanamine, diphenyltridecyl phosphite.
  • a hard coat layer may be laminated on the resin (B).
  • the hard coat layer is not particularly limited in material, application method, and the like as long as it has sufficient adhesion without impairing transparency.
  • Examples of the method for forming the hard coat layer include a method of applying a curable coating that is cured by heat, ultraviolet rays, electron beams, and the like, a physical vapor deposition method, a chemical vapor deposition method, and the like. From the viewpoint of production, a method of applying an ultraviolet curable coating is preferred.
  • the ultraviolet curable coating is not particularly limited as long as it is a composition containing an ultraviolet curable resin and a photopolymerization initiator.
  • Examples of the ultraviolet curable resin include urethane acrylate, epoxy acrylate, polyether acrylate, polyester acrylate, glycidyl compound, alicyclic epoxy compound, and oxetane compound.
  • photopolymerization initiators 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, 2-methyl-1-[(4-methylthio) phenyl] -2-morpholinopropan-1-one, benzophenone, 4-benzoyl-4′-methylphenyl sulfide, 2,4-diethylthioxanthone and the like.
  • coating means for forming a hard coat layer using an ultraviolet curable coating include a micro gravure coating method, a spin coating method, a cast transfer method, a spray coating method, a flow coating method, a dipping method, a roll coating method, and a bar coating. Any method such as a method may be used. From the viewpoint of paint properties, a micro gravure coating method, a roll coating method, and a bar coating method are more preferable. Moreover, when coating on both surfaces, both surfaces may be coated by the same method, or by different methods.
  • the thickness of the hard coat layer is preferably in the range of 1 to 30 ⁇ m, more preferably in the range of 3 to 25 ⁇ m, and still more preferably in the range of 5 to 20 ⁇ m.
  • the thickness of the hard coat layer is less than 1 ⁇ m, sufficient scratch resistance cannot be obtained.
  • the thickness of the hard coat layer is more than 30 ⁇ m, cracks due to stress are likely to occur, which is not suitable for applications such as display cover panels and touch panels.
  • the pencil hardness of the hard coat layer is preferably 3H or more, more preferably 4H or more, and further preferably 5H or more.
  • the pencil hardness of the hard coat layer is measured according to JIS K5600-5-4.
  • ⁇ Laminated body> the resin layer (B) is laminated on at least one surface of the resin layer (A).
  • the total thickness of the resin layer (A) and the resin layer (B) is 0.8 mm to 3.0 mm.
  • the total thickness of the resin layer (A) and the resin layer (B) is preferably 0.9 mm to 2.5 mm, more preferably 1.0 to 2.0 mm.
  • the layered product of the present invention has a warp rate of preferably 0.2% or less, more preferably 0.15% or less after being left for 4 hours in an environment of temperature 23 ° C. and humidity 50% RH.
  • the laminate of the present invention has a warpage rate of 0.2% or less, preferably 0.15% or less after being left for 120 hours in a high-temperature and high-humidity environment at a temperature of 85 ° C.
  • the layered product on which the hard coat layer of the present invention is laminated has a warp rate of preferably 0.2% or less, more preferably 0.15 after standing for 4 hours in an environment of temperature 23 ° C. and humidity 50% RH. % Or less. Further, the laminate in which the hard coat layer of the present invention is laminated has a warpage rate of 0.2% or less after being left for 120 hours in a high-temperature and high-humidity environment at a temperature of 85 ° C. and a humidity of 85% RH, preferably It is 0.15% or less.
  • the laminate of the present invention is (i) extruding a laminate including a resin layer (A) and a resin layer (B) laminated on at least one surface thereof from a die in a molten state, (Ii) cooling the extruded laminate with the first to third cooling rolls while taking it with the take-up roll; It can be manufactured by each process.
  • Extrusion process (i) This is a step of extruding from a die a molten body containing a resin layer (A) and a resin layer (B) laminated on at least one surface thereof.
  • This step is a coextrusion molding method in which the thermoplastic resin (A) and the thermoplastic resin (B) are melted by an extruder and laminated using a feed block method or a multi-manifold method.
  • the thermoplastic resin (A) and the thermoplastic resin (B) are melted, and the multilayer integrated resin is brought into close contact with the roll to perform molding. Specifically, it can be extruded from a multi-manifold die or a feed block die.
  • thermoplastic resin (A) and the thermoplastic resin (B) are transparent even if they are mixed, the cut part at the end that occurs during the molding of the laminated sheet is collected, crushed, and specified as the resin layer (A) Ratio, preferably 50 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin (A) before recovery, thereby reducing the material loss without deteriorating the properties as a laminated sheet. Can be put out.
  • Cooling step (ii) This step is a step of cooling the extruded laminate with the first to third cooling rolls while taking it with the take-up roll. As shown in FIG. 1, the first to third cooling rolls are parallel to each other, are on the same plane, and are arranged close to each other.
  • the interval between the first to third cooling rolls corresponds to the thickness of the laminate.
  • the extruded laminate is sandwiched between the first cooling roll and the second cooling roll, (b) is then wound around the second cooling roll, and (c) the third cooling roll is then placed. It is done by wrapping around.
  • the peripheral speed of the take-up roll relative to the second roll peripheral speed In the present invention, the peripheral speed of the take-up roll with respect to the second roll peripheral speed is set to 0.996 to 1.010 times, so that it is left for 120 hours in a high-temperature and high-humidity environment with a temperature of 85 ° C. and a humidity of 85% RH.
  • the warp rate after the treatment can be 0.2% or less.
  • the peripheral speed of the take-up roll relative to the second roll peripheral speed is set to about 0.990 to 0.995 times due to shrinkage due to cooling of the resin.
  • the present invention is based on the finding that the warpage rate under a high-temperature and high-humidity environment is reduced by slightly stretching the laminate.
  • the peripheral speed of the take-up roll with respect to the second roll peripheral speed is preferably 0.997 to 1.005 times, more preferably 0.998 to 1.000 times.
  • the peripheral speed of the take-up roll with respect to the second roll peripheral speed is less than the lower limit of the above range, distortion at the time of molding in the sheet traveling direction (MD direction) increases, and warpage fluctuation due to distortion relaxation occurs in a high temperature and high humidity environment.
  • the peripheral speed of the take-up roll with respect to the second roll peripheral speed exceeds the upper limit of the above range, the sheet appearance is adversely affected. For example, the thickness unevenness of the sheet increases and the phase difference increases, which adversely affects the optical characteristics.
  • the peripheral speed of the third roll relative to the peripheral speed of the second roll Usually, the peripheral speed of the third roll is the same as the peripheral speed of the second roll.
  • the warp rate can be further reduced by setting the peripheral speed of the third roll with respect to the second roll peripheral speed to a specific range.
  • the peripheral speed of the third roll relative to the peripheral speed of the second roll is preferably 1.001 to 1.030 times, more preferably 1.002 to 1.020 times, and still more preferably 1.003 to 1.010 times. It is. If the peripheral speed of the third roll relative to the peripheral speed of the second roll is within the above range, distortion during molding in the sheet traveling direction (MD direction) is reduced, and warpage fluctuation due to strain relaxation is unlikely to occur in a high-temperature and high-humidity environment. . Further, when the peripheral speed of the take-up roll with respect to the second roll peripheral speed is within the above range, the appearance of the sheet is improved. (Lamination of hard coat layer) A hard coat layer may be laminated on the resin layer (B) of the laminate obtained by cooling. The hard coat layer and the laminating method are as described above. ⁇ Application> The laminate of the present invention can be used as a display cover panel or a touch panel front plate.
  • thermoplastic resin molding plate (length 80 mm, width 10 mm, thickness 4 mm) for each layer was prepared and used as a test piece.
  • the test piece was left in a constant temperature and humidity chamber at a temperature of 85 ° C. and a humidity of 0% RH for 24 hours. It was taken out later and further allowed to stand at room temperature for 10 minutes, and then the weight was measured with a balance to obtain a dry weight.
  • the weight is measured with a balance, It was.
  • the water absorption was determined by the following formula.
  • the laminate was cut into three pieces each having a size of 50 mm long ⁇ 100 mm wide so that the sheet advancing direction at the time of production was the long side and 50 mm long ⁇ 100 mm wide so that the sheet width direction was the long side. After leaving the test pieces for 4 hours in an environment of 23 ° C. and 50% humidity, place them flat so that the resin layer (B) side is up, and lift up to a total of 8 points at the four corners and the middle point. It was measured. The maximum floating amount (maximum warpage amount) was obtained from the 6 sheets measured, and the value calculated by the following equation was used as the warpage rate (%).
  • Warpage rate (%) 100 ⁇ maximum warpage amount (mm) / 100 (mm)
  • the floating amount in which the resin layer (B) side is concave was defined as positive.
  • the laminate was cut into three pieces each having a size of 50 mm long ⁇ 100 mm wide so that the sheet advancing direction at the time of production was the long side and 50 mm long ⁇ 100 mm wide so that the sheet width direction was the long side.
  • the test pieces were left in an environment of 85 ° C. and humidity 85% RH for 120 hours, and then left in an environment of temperature 23 ° C. and humidity 50% RH for 4 hours, so that the resin layer (B) side was up.
  • Warpage rate (%) 100 ⁇ maximum warpage amount (mm) / 100 (mm)
  • the floating amount in which the resin layer (B) side is concave was defined as positive.
  • this solution is passed through a filter having an aperture of 0.3 ⁇ m, and further dropped into warm water in a kneader with an isolation chamber having a foreign matter outlet at the bearing, and the polycarbonate resin is flaked while distilling off methylene chloride.
  • the liquid-containing flakes were pulverized and dried to obtain a powder.
  • tris (2,4-di-tert-butylphenyl) phosphite is added to the powder so as to be 0.0025% by weight, and stearic acid monoglyceride is added to 0.05% by weight.
  • the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and further washed with water until the conductivity of the aqueous phase becomes substantially the same as that of ion-exchanged water. Obtained.
  • this solution is passed through a filter having an aperture of 0.3 ⁇ m, and further dropped into warm water in a kneader with an isolation chamber having a foreign matter outlet at the bearing, and the polycarbonate resin is flaked while distilling off methylene chloride.
  • the liquid-containing flakes were pulverized and dried to obtain a powder.
  • a dispersing agent As a dispersing agent, a mass ratio of a polymer obtained by copolymerizing 70 parts of potassium methacrylate and 30 parts of methyl methacrylate, and a polymer obtained by copolymerizing 65 parts of sodium 2-sulfoethyl methacrylate, 10 parts of potassium methacrylate, and 25 parts of methyl methacrylate.
  • the mixture was mixed 1: 1 and a 10% aqueous solution of the mixed polymer was used.
  • the obtained acrylic copolymer and polycarbonate resin Teijin Chemicals Co., Ltd. bisphenol A type polycarbonate resin, viscosity average molecular weight 22,200
  • a twin screw extruder [Kobe Steel Works KTX-46].
  • Example 1 The first and second extruders 1A and 1B, the die 2, the first to third rolls 4 to 6, and the pair of take-up rolls 7 are arranged as shown in FIG. Was arranged such that the resin layer (A) was in contact with the second roll.
  • the polycarbonate resin constituting the resin layer (A) is a single screw extruder (1A in FIG. 1) having a screw diameter of 40 mm, and the thermoplastic resin constituting the resin layer (B) is a single screw extruder having a screw diameter of 30 mm.
  • each was melted, laminated into two layers by a feed block method, and extruded through a die having a set temperature of 280 ° C. It rolled with the 1st roll and the 2nd roll, and it took up, making it cool with the 3rd roll.
  • a polycarbonate resin a bisphenol A type polycarbonate resin manufactured by Teijin Chemicals Ltd., viscosity average molecular weight 23,300
  • resin 1 a laminate was produced so that the total thickness of the laminate was 1.0 mm and the thickness of the resin layer (B) was 100 ⁇ m.
  • Example 2 A laminate was obtained in the same manner as in Example 1 except that the resin 2 was used as the resin layer (B).
  • Table 1 shows the evaluation results of the obtained laminate.
  • Example 3 A laminate was obtained in the same manner as in Example 1 except that the resin 3 was used as the resin layer (B).
  • Example 4 A laminate was obtained in the same manner as in Example 1 except that the resin 4 was used as the resin layer (B). Table 1 shows the evaluation results of the obtained laminate.
  • Example 5 A laminate was obtained in the same manner as in Example 1 except that the resin 5 was used as the resin layer (B). Table 1 shows the evaluation results of the obtained laminate.
  • Example 6 A laminate was obtained in the same manner as in Example 1 except that the thickness of the resin layer (B) was 60 ⁇ m.
  • Table 1 shows the evaluation results of the obtained laminate.
  • Example 7 A laminate was obtained in the same manner as in Example 1 except that the total thickness of the laminate was 2.0 mm. Table 1 shows the evaluation results of the obtained laminate.
  • Example 8 A laminate was obtained in the same manner as in Example 1, except that the peripheral speed ratio of the third roll to the second roll during molding was 1.005 times. Table 1 shows the evaluation results of the obtained laminate.
  • Example 9 The laminated body was made in the same manner as in Example 1 except that the circumferential speed ratio of the third roll to the second roll during molding was 1.003 times and the circumferential speed ratio of the take-up roll to the second roll was 0.996 times. Obtained. Table 1 shows the evaluation results of the obtained laminate.
  • Example 10 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- [2H-benzotriazol-2-yl] phenol as an ultraviolet absorber with respect to 100 parts by weight of the resin 1 ]]
  • a laminate was obtained in the same manner as in Example 1 except that 1.0 part by weight of ADEKA (trade name: ADK STAB LA-31) was added. Table 1 shows the evaluation results of the obtained laminate.
  • Comparative Example 1 A commercially available acrylic resin (trade name: Acrypet VH001 manufactured by Mitsubishi Rayon Co., Ltd.) was used as the resin layer (B), and a laminate was obtained in the same manner as in Example 1 except that the thickness of the resin layer (B) was 60 ⁇ m. It was.
  • Table 1 shows the evaluation results of the obtained laminate.
  • Comparative Example 2 A commercially available acrylic resin (manufactured by Arkema, trade name: Altglas HT-121) was used as the resin layer (B), and a laminate was obtained in the same manner as in Example 1 except that the thickness of the resin layer (B) was 60 ⁇ m. It was. Table 1 shows the evaluation results of the obtained laminate.
  • Comparative Example 3 A laminate was obtained in the same manner as in Example 1 except that the peripheral speed ratio of the take-up roll to the second roll during molding was 0.992 times. Table 1 shows the evaluation results of the obtained laminate. As is clear from Table 1, in Examples 1 to 10, both the warpage rate after the normal temperature and normal humidity test and the warpage rate after the wet heat test were 0.2% or less.
  • thermoplastic resin molding plate (length 80 mm, width 10 mm, thickness 4 mm) for each layer was prepared and used as a test piece.
  • the test piece was left in a constant temperature and humidity chamber at a temperature of 85 ° C. and a humidity of 0% RH for 24 hours. It was taken out later and further allowed to stand at room temperature for 10 minutes, and then the weight was measured with a balance to obtain a dry weight.
  • the weight is measured with a balance, It was.
  • the water absorption was determined by the following formula.
  • Water absorption [%] (Water absorption weight [g] ⁇ Dry weight [g]) / Dry weight [g] ⁇ 100 [%] (Pencil hardness)
  • the laminate before and after laminating the hard coat layer is measured in accordance with JIS K5600-5-4, and the pencil hardness is measured with a weight of 750 g applied to the surface of the hard coat layer on the resin layer (B) and the resin layer (B).
  • the hardness of the pencil whose surface was not visually damaged was taken as the evaluation result.
  • the pencil used was Mitsubishi Pencil Uni (trade name).
  • the laminate with the hard coat layer laminated is 3 in size of 50 mm in length and 100 mm in width so that the sheet traveling direction at the time of manufacture is the long side, and 50 mm in length and 100 mm in width so that the sheet width direction is the long side. Cut out 6 sheets each and left them for 4 hours in an environment of temperature 23 ° C. and humidity 50% RH, and then placed them flat with the resin layer (B) side up. The floating amount at 8 points was measured. The maximum floating amount (maximum warpage amount) was obtained from the 6 sheets measured, and the value calculated by the following equation was used as the warpage rate (%).
  • Warpage rate (%) 100 ⁇ maximum warpage amount (mm) / 100 (mm)
  • the floating amount in which the resin layer (B) side is concave was defined as positive.
  • the laminate with the hard coat layer laminated is 3 in size of 50 mm in length and 100 mm in width so that the sheet traveling direction at the time of manufacture is the long side, and 50 mm in length and 100 mm in width so that the sheet width direction is the long side.
  • Each of these six test pieces was cut out for 120 hours in a temperature of 85 ° C. and a humidity of 85% RH, and then left in a temperature of 23 ° C.
  • Warpage rate (%) 100 ⁇ maximum warpage amount (mm) / 100 (mm)
  • the floating amount in which the resin layer (B) side is concave was defined as positive.
  • Example 11 The first and second extruders 1A and 1B, the die 2, the first to third rolls 4 to 6, and the pair of take-up rolls 7 are arranged as shown in FIG. Was arranged such that the resin layer (A) was in contact with the second roll.
  • the polycarbonate resin constituting the resin layer (A) is a single screw extruder (1A in FIG. 1) having a screw diameter of 40 mm
  • the thermoplastic resin constituting the resin layer (B) is a single screw extruder having a screw diameter of 30 mm. (1B in FIG.
  • each is melted and laminated into two layers by the feed block method, extruded through a die having a set temperature of 280 ° C., rolled with a first roll and a second roll, and cooled with a third roll. Then, it was taken up by a pair of take-up rolls.
  • Polycarbonate resin bisphenol A type polycarbonate resin, viscosity average molecular weight 23,300 manufactured by Teijin Chemicals Ltd.
  • resin layer (A) resin 1 as resin layer (B)
  • the laminate was manufactured so that the total thickness of (B) was 1.0 mm and the thickness of the resin layer (B) was 100 ⁇ m.
  • An ultraviolet curable coating (Arakawa Chemical Industries, Ltd.
  • Beam Set 575CL was applied to both sides of the resulting laminate using a metal bar coater to a thickness of 10 ⁇ m, dried, and then exposed to ultraviolet rays.
  • the laminate was cured using an irradiation apparatus so as to have an integrated light amount of 600 mJ / cm 2, and a hard coat layer was laminated.
  • Example 12 A laminate in which the hard coat layer was laminated was obtained in the same manner as in Example 11 except that an ultraviolet curable paint (Arakawa Chemical Industries, Ltd. Beam Set 575CL) was applied so that the thickness of the hard coat layer was 5 ⁇ m. It was. The evaluation results are shown in Table 2.
  • Example 13 A laminate in which the hard coat layer was laminated was obtained in the same manner as in Example 11 except that an ultraviolet curable paint (Arakawa Chemical Industries, Ltd. Beam Set 575CL) was applied so that the thickness of the hard coat layer was 20 ⁇ m. It was. The evaluation results are shown in Table 2.
  • Example 14 A laminate in which a hard coat layer was laminated was obtained in the same manner as in Example 11 except that the resin 2 was used as the resin layer (B).
  • Example 15 A laminate in which a hard coat layer was laminated was obtained in the same manner as in Example 11 except that the resin 3 was used as the resin layer (B). The evaluation results are shown in Table 2.
  • Example 16 A laminate in which a hard coat layer was laminated was obtained in the same manner as in Example 11 except that the resin 4 was used as the resin layer (B). The evaluation results are shown in Table 2.
  • Example 17 A laminate having a hard coat layer laminated thereon was obtained in the same manner as in Example 11 except that the resin 5 was used as the resin layer (B). The evaluation results are shown in Table 2.
  • Example 18 A laminate in which a hard coat layer was laminated was obtained in the same manner as in Example 11 except that the thickness of the resin layer (B) was 60 ⁇ m.
  • Example 19 A laminate in which a hard coat layer was laminated was obtained in the same manner as in Example 11 except that the total thickness of the resin layer (A) and the resin layer (B) was 2.0 mm. The evaluation results are shown in Table 2.
  • Example 20 A laminate in which a hard coat layer was laminated was obtained in the same manner as in Example 11 except that the circumferential speed ratio of the third roll to the second roll during molding was 1.005 times. The evaluation results are shown in Table 2.
  • Example 21 The hard coat layer was the same as in Example 11 except that the circumferential speed ratio of the third roll to the second roll during molding was 1.003 times and the circumferential speed ratio of the take-up roll to the second roll was 0.996 times. As a result, a laminated body was obtained.
  • Example 22 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- [2H-benzotriazol-2-yl] phenol as an ultraviolet absorber with respect to 100 parts by weight of the resin 1 ]
  • a laminate in which a hard coat layer was laminated was obtained in the same manner as in Example 11 except that 1.0 part by weight (manufactured by ADEKA, product name: ADK STAB LA-31) was added.
  • the evaluation results are shown in Table 2.
  • Comparative Example 4 A hard coat layer was formed in the same manner as in Example 11 except that a commercially available acrylic resin (trade name: Acrypet VH001 manufactured by Mitsubishi Rayon Co., Ltd.) was used as the resin layer (B), and the thickness of the resin layer (B) was 60 ⁇ m. A laminated body was obtained. The evaluation results are shown in Table 2. Comparative Example 5 A hard coat layer was prepared in the same manner as in Example 11 except that a commercially available acrylic resin (trade name: Altglas HT-121) manufactured by Arkema was used as the resin layer (B), and the thickness of the resin layer (B) was 60 ⁇ m. A laminated body was obtained. The evaluation results are shown in Table 2.
  • Comparative Example 6 A laminate in which a hard coat layer was laminated was obtained in the same manner as in Example 11 except that the peripheral speed ratio of the take-up roll to the second roll at the time of molding was 0.992 times.
  • the evaluation results are shown in Table 2.
  • Table 2 both the warpage rate after the normal temperature and normal humidity test and the warpage rate after the wet heat test were 0.2% or less.
  • Comparative Example 4 in which a resin having a Tg of less than 115 ° C. and a water absorption rate of 0.7% or more for the resin layer (B) was used, and the Tg was 115 ° C.
  • Comparative Example 5 in which a resin exceeding 100% was used for the resin layer (B), both the warpage rate after the normal temperature and normal humidity test and the warpage rate after the wet heat test were large. Moreover, although the layer structure is the same as that of Example 11, Comparative Example 6 having a low peripheral speed ratio of the take-up roll to the second roll during molding resulted in a large warpage rate after the wet heat test.
  • the laminate of the present invention has high pencil hardness, excellent scratch resistance, excellent heat resistance, small warpage deformation under normal temperature and normal humidity environment, and hardly warp deformation under a long-term high temperature and high humidity environment. According to the method for producing a laminate of the present invention, it is possible to produce a laminate that is small in warp deformation under a normal temperature and normal humidity environment and that hardly warps and deforms even under a long-term high temperature and high humidity environment.
  • the laminate of the present invention is useful as a display cover panel or touch panel front plate for OA / electronic devices.
  • thermoplastic resin of the resin layer (A) and the thermoplastic resin of the resin layer (B) are both 0.7% or less, and the difference in water absorption is 0.5% or less.
  • a warp rate after leaving the resin laminate for 120 hours in a high temperature and high humidity environment at a temperature of 85 ° C. and a humidity of 85% RH is 0.2% or less.
  • thermoplastic resin of the resin layer (A) is a polycarbonate resin
  • thermoplastic resin of the resin layer (B) is a structural unit [1] represented by the following formula [1];
  • W represents a single bond, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a cyclic alkyl group having 3 to 8 carbon atoms.
  • the resin laminate as described in 1 above which is a modified polycarbonate resin in which the proportion of the structural unit [1] in all the structural units is 50 to 100 mol% and the viscosity average molecular weight is 1.0 ⁇ 10 4 to 8.0 ⁇ 10 4 body.
  • the thermoplastic resin of the resin layer (A) contains polycarbonate resin
  • the thermoplastic resin of the resin layer (B) contains 5 to 80% by weight of aromatic (meth) acrylate units and 20 to 95% by weight of methyl (meth) acrylate units. 2.
  • the resin laminate according to item 1 which is a polymer blend resin of 20 to 60 parts by weight of an acrylic copolymer having a weight average molecular weight of 5,000 to 30,000 and 40 to 80 parts by weight of a polycarbonate resin. 4). 2. The resin laminate according to item 1 above, containing 0.5 to 5.0 parts by weight of an ultraviolet absorber with respect to 100 parts by weight of the thermoplastic resin of the resin layer (B). 5. 2. The resin laminate according to item 1, wherein the resin layer (B) has a pencil hardness of F or more. 6). 2. The resin laminate according to item 1, wherein the resin laminate has a warpage rate of 0.2% or less after being left in a temperature of 23 ° C. and a humidity of 50% RH for 4 hours. 7).
  • the resin laminate according to item 1 which is used as a display cover panel or a touch panel front plate. Moreover, there exists the following invention as an aspect which has a hard-coat layer. 1.
  • a resin layer (B) made of another thermoplastic resin different from the resin layer (A) having a thickness of 40 to 150 ⁇ m is laminated on at least one surface of the thermoplastic resin layer (A), and further on the resin layer (B).
  • the hard laminate layer is laminated with a resin layer (A) and a resin layer (B) having a total thickness of 0.8 mm to 3.0 mm, and the heat of the resin layer (A)
  • the glass transition points TgA and TgB of the thermoplastic resin and the thermoplastic resin of the resin layer (B) are both 115 ° C. or higher, and the difference between TgA and TgB is 30 ° C. or lower, and the thermoplastic resin of the resin layer (A) And the resin layer (B) both have a water absorption rate of 0.7% or less and a difference in water absorption rate of 0.5% or less.
  • the warpage rate after leaving for 120 hours under high temperature and high humidity of 85% RH A resin laminate in which a hard coat layer is laminated which is 0.2% or less.
  • the thermoplastic resin of the resin layer (A) is a polycarbonate resin
  • the thermoplastic resin of the resin layer (B) is a structural unit [1] represented by the following formula [1];
  • W represents a single bond, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a cyclic alkyl group having 3 to 8 carbon atoms.
  • the thermoplastic resin of the resin layer (A) contains polycarbonate resin
  • the thermoplastic resin of the resin layer (B) contains 5 to 80% by weight of aromatic (meth) acrylate units and 20 to 95% by weight of methyl (meth) acrylate units.
  • the hard coat layer according to item 1 above which is a polymer blend resin of 20 to 60 parts by weight of an acrylic copolymer having a weight average molecular weight of 5,000 to 30,000 and 40 to 80 parts by weight of a polycarbonate resin, was laminated. Resin laminate. 4).
  • a resin laminate in which the hard coat layer according to the preceding item 1 containing 0.5 to 5.0 parts by weight of an ultraviolet absorber is laminated to 100 parts by weight of the thermoplastic resin of the resin layer (B). 5.
  • a resin laminate in which the hard coat layer is laminated with the hard coat layer according to item 1 described above. 8).
  • the hard coat layer according to the preceding item 1 comprising a step of obtaining a resin laminate by setting the ratio to 996 to 1.010, and a step of laminating a hard coat layer on the resin layer (B) of the obtained resin laminate.
  • laminated resin laminates Production method. 10.

Abstract

La présente invention concerne un stratifié, qui comprend une couche (A) de résine, obtenue à partir d'une couche (A) de résine thermoplastique et d'une couche (B) de résine stratifiée sur au moins l'un de ses côtés et obtenue à partir d'une résine thermoplastique différente. (i) L'épaisseur de la couche (B) de résine est comprise entre 40 µm et 150 µm et l'épaisseur totale de la couche (A) de résine et de la couche (B) de résine est comprise entre 0,8 mm et 3,0 mm, (ii) les points de transition respectifs du verre (TgA et TgB) de la résine thermoplastique (A) et de la résine thermoplastique (B) sont tous deux de 115 °C minimum et la différence entre TgA et TgB est de 30 °C maximum, (iii) les taux d'absorption de l'eau de la résine thermoplastique (A) et de la résine thermoplastique (B) sont tous deux de 0,7 % maximum et la différence des taux d'absorption d'eau est de 0,5 % maximum, (iv) le taux de déformation, après que le stratifié de résine a été laissé pendant 120 heures dans un environnement à haute humidité et haute température de 85 °C et de 85 % d'humidité relative est de 0,2 % maximum.
PCT/JP2013/078395 2012-10-15 2013-10-11 Stratifié WO2014061817A1 (fr)

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CN108778675A (zh) * 2016-03-23 2018-11-09 株式会社可乐丽 挤出树脂板的制造方法和挤出树脂板
WO2017164276A1 (fr) * 2016-03-23 2017-09-28 株式会社クラレ Procédé de fabrication de feuille de résine extrudée et feuille de résine extrudée
CN108778675B (zh) * 2016-03-23 2020-06-23 株式会社可乐丽 挤出树脂板的制造方法和挤出树脂板
JP2017177553A (ja) * 2016-03-30 2017-10-05 三菱エンジニアリングプラスチックス株式会社 積層体
JP2019136994A (ja) * 2018-02-14 2019-08-22 三菱瓦斯化学株式会社 樹脂積層体およびそれを用いた樹脂成形体
JP7065633B2 (ja) 2018-02-14 2022-05-12 三菱瓦斯化学株式会社 樹脂積層体およびそれを用いた樹脂成形体
WO2021241426A1 (fr) * 2020-05-27 2021-12-02 三菱瓦斯化学株式会社 Corps multicouche en résine
JP7427731B1 (ja) 2022-08-23 2024-02-05 三菱瓦斯化学株式会社 多層体、および、成形品
JP7427730B1 (ja) 2022-08-23 2024-02-05 三菱瓦斯化学株式会社 多層体、および、成形品
WO2024043180A1 (fr) * 2022-08-23 2024-02-29 三菱瓦斯化学株式会社 Corps multicouche et article moulé

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JPWO2014061817A1 (ja) 2016-09-05
KR20150070136A (ko) 2015-06-24
CN104703796A (zh) 2015-06-10
TW201429714A (zh) 2014-08-01
KR102139840B1 (ko) 2020-07-30
TWI617445B (zh) 2018-03-11

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