WO2010024217A1 - 熱可塑性樹脂積層体 - Google Patents
熱可塑性樹脂積層体 Download PDFInfo
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- WO2010024217A1 WO2010024217A1 PCT/JP2009/064723 JP2009064723W WO2010024217A1 WO 2010024217 A1 WO2010024217 A1 WO 2010024217A1 JP 2009064723 W JP2009064723 W JP 2009064723W WO 2010024217 A1 WO2010024217 A1 WO 2010024217A1
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- WIPO (PCT)
- Prior art keywords
- resin
- layer
- thermoplastic resin
- thermoplastic
- meth
- Prior art date
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Classifications
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31507—Of polycarbonate
Definitions
- the present invention relates to a thermoplastic resin laminate, and more specifically, a thermoplastic resin laminate that is used for a transparent substrate material and a protective material, and has excellent weather resistance, scratch resistance, interlayer adhesion, and the like in a high temperature and high humidity environment. About the body.
- Resin transparent plates are used in a wide variety of applications, including soundproofing partitions, carports, signboards, and front panels of display units for office automation equipment and portable electronic devices.
- the front panel has a weather resistance, scratch resistance, There is an increasing demand for improvement in interlayer adhesion and the like.
- Patent Document 1 discloses a laminate in which a polycarbonate resin layer having excellent impact resistance is laminated with a methacrylic resin layer containing a crosslinked acrylate polymer
- Document 2 discloses a transparent resin laminate in which a methacrylic resin layer containing a fatty acid ester or the like is laminated.
- the heat resistance of the methacrylic resin layer is poor, and there are problems such as deformation in a high temperature environment and warpage due to humidity change due to high water absorption.
- Patent Document 3 discloses a hydrogenated resin obtained by polymerizing a (meth) acrylic acid ester monomer and an aromatic vinyl monomer. The performance is not sufficient and further improvement is required.
- the present invention provides a thermoplastic resin laminate excellent in weather resistance, scratch resistance, interlayer adhesion, etc. for high temperature and high humidity environments, which is used for transparent substrate materials and protective materials.
- the purpose is to provide.
- thermoplastic resin laminate having these characteristics by forming a laminate using a specific vinyl copolymer resin as a surface layer.
- the present invention was reached. That is, the present invention provides the following thermoplastic resin laminate and a transparent material using the thermoplastic resin laminate.
- thermoplastic transparent resin (A) layer a thermoplastic resin (B) layer comprising a methyl methacrylate-styrene copolymer and / or an acrylonitrile-styrene copolymer, and a thermoplastic resin (C) layer comprising a polycarbonate resin;
- thermoplastic resin laminate in which the (B) layer is laminated on one or both sides of the (C) layer, and the (A) layer is laminated on the surface of the (B) layer,
- the thermoplastic transparent resin (A) is a (meth) acrylic acid ester structural unit (a) represented by the following general formula (1) and an aliphatic vinyl structural unit (b) represented by the following general formula (2).
- a vinyl copolymer resin having a molar ratio of the (meth) acrylic ester structural unit (a) and the aliphatic vinyl structural unit (b) of 15:85 to 85:15.
- Thermoplastic resin laminate is a (meth) acrylic acid ester structural unit (a)
- R1 is hydrogen or a methyl group
- R2 is an alkyl group having 1 to 16 carbon atoms.
- R3 is hydrogen or a methyl group
- R4 is a cyclohexyl group that may have an alkyl substituent of 1 to 4 carbon atoms.
- thermoplastic transparent resin (A) was obtained by polymerizing at least one (meth) acrylate monomer and at least one aromatic vinyl monomer, and then hydrogenating 70% or more of the aromatic double bonds.
- thermoplastic resin laminate according to 1 or 2 above wherein one or both of hard coating treatment, antireflection treatment, and antiglare treatment are applied to one side or both sides. 6). 6. A transparent substrate material comprising the thermoplastic resin laminate according to any one of 1 to 5 above. 7). A transparent protective material comprising the thermoplastic resin laminate according to any one of 1 to 5 above.
- thermoplastic resin laminate excellent in weather resistance, scratch resistance, interlayer adhesion and the like in a high-temperature and high-humidity environment
- thermoplastic resin laminate comprises a transparent substrate material, a transparency It is used for optical articles as a protective material, and is particularly suitably used for portable display devices such as mobile phone terminals, portable electronic play equipment, and PDAs.
- the thermoplastic resin laminate of the present invention comprises a thermoplastic transparent resin (A) layer, a copolymer of methyl methacrylate and styrene and / or a thermoplastic resin (B) layer made of acrylonitrile-styrene copolymer, and a polycarbonate-based material.
- the thermoplastic transparent resin (A) is composed of a (meth) acrylate structural unit (a) represented by the following general formula (1) and an aliphatic vinyl structural unit (b) represented by the following general formula (2).
- a vinyl copolymer resin having a molar ratio of the (meth) acrylic ester structural unit (a) and the aliphatic vinyl structural unit (b) of 15:85 to 85:15.
- R1 is hydrogen or a methyl group
- R2 is an alkyl group having 1 to 16 carbon atoms.
- R3 is hydrogen or a methyl group
- R4 is a cyclohexyl group having an alkyl substituent of 1 to 4 carbon atoms.
- R2 of the (meth) acrylic ester structural unit represented by the general formula (1) is an alkyl group having 1 to 16 carbon atoms, and is a methyl group, an ethyl group, a butyl group, a lauryl group, a stearyl group, a cyclohexyl group, or isobornyl. Examples include groups. These can be used alone or in combination of two or more. Of these, a (meth) acrylic acid ester structural unit in which R2 is a methyl group and / or an ethyl group is preferable, and a methacrylic acid ester structural unit in which R1 is a methyl group and R2 is a methyl group is more preferable.
- Examples of the aliphatic vinyl structural unit represented by the formula (2) used in the present invention are R3 is hydrogen or a methyl group, R4 is a cyclohexyl group, and a cyclohexyl group having an alkyl group having 1 to 4 carbon atoms. Things can be mentioned. These can be used alone or in combination of two or more. Of these, preferred are aliphatic vinyl structural units in which R3 is hydrogen and R4 is a cyclohexyl group.
- thermoplastic transparent resin (A) used in the present invention is mainly composed of a (meth) acrylic acid ester structural unit (a) represented by the general formula (1) and an aliphatic vinyl structural unit represented by the general formula (2).
- the molar composition ratio of the (meth) acrylate structural unit (a) represented by the formula (1) and the aliphatic vinyl structural unit (b) represented by the formula (2) is (a) Is in the range of 15:85 to 85:15, preferably in the range of 25:75 to 75:25, and more preferably in the range of 30:70 to 70:30.
- the mechanical strength is low. Since it becomes too brittle, it is not practical. If it exceeds 85%, the heat resistance may be insufficient.
- thermoplastic transparent resin (A) is not particularly limited, but a thermoplastic transparent resin (A) obtained by copolymerizing a (meth) acrylic acid ester monomer and an aromatic vinyl monomer and then hydrogenating the aromatic ring is preferable.
- (meth) acrylic acid shows methacrylic acid and / or acrylic acid.
- aromatic vinyl monomer used at this time include styrene, ⁇ -methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and derivatives thereof. Of these, styrene is preferred.
- (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate.
- (Meth) acrylic acid cyclohexyl (meth) acrylic acid alkyl (meth) acrylates such as isobornyl, etc., but from the balance of physical properties, alkyl methacrylate is used alone, or alkyl methacrylate and It is preferable to use alkyl acrylate together.
- alkyl methacrylates methyl methacrylate and ethyl methacrylate are particularly preferable.
- a known method can be used for the polymerization of the (meth) acrylic acid ester monomer and the aromatic vinyl monomer, and for example, it can be produced by a bulk polymerization method or a solution polymerization method.
- a monomer composition containing a monomer, a chain transfer agent, and a polymerization initiator is continuously supplied to a complete mixing tank and is continuously polymerized at 100 to 180 ° C.
- solvent used in this case examples include hydrocarbon solvents such as toluene, xylene, cyclohexane and methylcyclohexane, ester solvents such as ethyl acetate and methyl isobutyrate, ketone solvents such as acetone and methyl ethyl ketone, tetrahydrofuran and dioxane. And ether solvents such as methanol and alcohol solvents such as methanol and isopropanol.
- the hydrogenation reaction after polymerizing the (meth) acrylic acid ester monomer and the aromatic vinyl monomer is performed in a suitable solvent.
- the solvent used for the hydrogenation reaction may be the same as or different from the polymerization solvent.
- hydrocarbon solvents such as cyclohexane and methylcyclohexane
- ester solvents such as ethyl acetate and methyl isobutyrate
- ketone solvents such as acetone and methyl ethyl ketone
- ether solvents such as tetrahydrofuran and dioxane
- alcohol solvents such as methanol and isopropanol A solvent etc.
- the method for hydrogenation is not particularly limited, and a known method can be used. For example, it can be carried out batchwise or continuously with a hydrogen pressure of 3 to 30 MPa and a reaction temperature of 60 to 250 ° C. When the temperature is 60 ° C. or higher, the reaction time does not take too long, and when it is 250 ° C. or lower, the molecular chain is not broken and the ester moiety is not hydrogenated.
- Examples of the catalyst used in the hydrogenation reaction include metals such as nickel, palladium, platinum, cobalt, ruthenium and rhodium or oxides or salts or complex compounds of these metals, carbon, alumina, silica, silica / alumina, diatomaceous earth. And a solid catalyst supported on a porous carrier.
- thermoplastic transparent resin (A) is preferably obtained by hydrogenating 70% or more of the aromatic ring of the aromatic vinyl monomer. That is, the ratio of the aromatic vinyl structural unit in the thermoplastic transparent resin (A) is preferably 30% or less in the thermoplastic transparent resin (A), and if it exceeds 30%, the thermoplastic transparent resin (A). Transparency may be reduced. More preferably, it is the range of 20% or less, More preferably, it is the range of 10% or less.
- thermoplastic transparent resin (A) can be blended with other resins as long as the transparency is not impaired.
- examples thereof include methyl methacrylate-styrene copolymer resin, polymethyl methacrylate, polystyrene, and polycarbonate.
- the glass transition temperature of the thermoplastic transparent resin (A) is preferably in the range of 110 to 140 ° C.
- the glass transition temperature in the present invention is a temperature when a differential scanning calorimeter is used to measure a sample at 10 mg and a heating rate of 10 ° C./min and calculate by the midpoint method.
- the thermoplastic resin (B) used in the present invention is a resin comprising a methyl methacrylate-styrene copolymer and / or an acrylonitrile-styrene copolymer.
- methyl methacrylate-styrene copolymer resin examples include MS200, MS300, and MS600 manufactured by Nippon Steel Chemical Co., Ltd.
- examples of the acrylonitrile-styrene copolymer resin include styrac manufactured by Asahi Kasei Chemicals Corporation. AS can be mentioned.
- thermoplastic resin (C) used in the present invention is a polycarbonate resin.
- This thermoplastic resin (C) is the central layer of the resin laminate, and is selected depending on the use of the resin laminate, but is preferably polycarbonate because it generally has excellent impact resistance, strength, and transparency. Resin is used.
- thermoplastic transparent resin (A), the thermoplastic resin (B) and the thermoplastic resin (C) can be used by mixing various additives.
- the additive include an antioxidant, an ultraviolet absorber, an anticolorant, an antistatic agent, a release agent, a lubricant, a dye, and a pigment.
- the method of mixing is not particularly limited, and a method of compounding the whole amount, a method of dry blending the master batch, a method of dry blending the whole amount, and the like can be used.
- thermoplastic resin laminate of the present invention As a method for producing the thermoplastic resin laminate of the present invention, a method by co-extrusion, a method of bonding through an adhesive, or the like can be used.
- the coextrusion method is not particularly limited.
- the feed block method the feed block is formed by laminating the (B) layer on one or both of the (C) layer and the (A) resin layer on the (B) layer. After extruding into a sheet with a T-die, it is cooled while passing through a forming roll to form a desired laminate.
- the (B) layer is laminated on one or both of the (C) layer in the multi-manifold die, and the (A) layer is laminated on the (B) layer, and then extruded into a sheet shape. Cooling while passing through a roll forms a desired laminate.
- the method of bonding through an adhesive agent is not particularly limited, and a known method can be used. For example, an adhesive layer is applied to one plate-like molded body using a spray, a brush, a gravure roll, etc., and the other plate-shaped molded body is stacked thereon and pressure-bonded until the adhesive layer is cured, and a desired laminate Form.
- an arbitrary adhesive resin (D) layer can be sandwiched between the (A) layer and the (B) layer and / or between the (B) layer and the (C) layer during the coextrusion.
- the thickness of the thermoplastic resin laminate of the present invention is preferably in the range of 0.1 to 10.0 mm. When the thickness is 0.1 mm or more, transfer defects and thickness accuracy defects do not occur, and when the thickness is 10.0 mm or less, thickness accuracy defects and appearance defects due to uneven cooling after molding may occur. Absent.
- the range is more preferably 0.3 to 5.0 mm, and still more preferably 0.5 to 3.0 mm.
- the thickness of the thermoplastic transparent resin (A) layer of the thermoplastic resin laminate of the present invention is preferably in the range of 10 to 500 ⁇ m. If it is less than 10 ⁇ m, scratch resistance and weather resistance may be insufficient. If it exceeds 500 ⁇ m, the impact resistance may be insufficient. Preferably it is in the range of 30-100 ⁇ m.
- the thickness of the thermoplastic resin (B) layer is preferably in the range of 5 to 50 ⁇ m. By setting the thickness of the (B) layer within this range, the adhesion between the (A) layer and the (C) layer can be improved without impairing the performance of the (A) layer.
- the thickness of the thermoplastic resin (C) layer varies depending on the use of the laminate, but is usually about 500 to 2000 ⁇ m.
- the thermoplastic resin laminate of the present invention can be subjected to any one or more of a hard coat treatment, an antireflection treatment and an antiglare treatment on one side or both sides.
- the methods of hard coat treatment, antireflection treatment and antiglare treatment are not particularly limited, and known methods can be used. For example, a method of applying a thermosetting or photocurable film, a method of vacuum-depositing a dielectric thin film, and the like can be mentioned.
- thermoplastic resin laminates obtained in the examples and comparative examples were evaluated as follows.
- ⁇ Adhesion evaluation> A test piece is cut out to 10 cm ⁇ 10 cm, and is pressed against a cylinder having a diameter of 60 mm so that the layer (A) is on the outside, and the adhesion between the layers is evaluated. The one with no change in appearance is considered good.
- ⁇ High temperature and high humidity exposure test> Cut the test piece into a 10 cm square. The test piece is hung in a constant temperature and humidity chamber set at a temperature of 85 ° C. and a relative humidity of 85% with the corner of the test piece as a fulcrum, and held in that state for 72 hours. The specimen is taken out and evaluated for the appearance change. The one with no change in appearance is considered good.
- Synthesis Example 1 [Production of methyl methacrylate-styrene-vinylcyclohexane copolymer resin (resin A2)] A monomer composition comprising 60.188 mol% of methyl methacrylate and 39.9791 mol% of styrene as monomer components and 0.0021 mol% of t-amylperoxy-2-ethylhexanoate as a polymerization initiator, Continuous supply was carried out at 1 kg / h to a 10 L complete mixing tank with wings, and continuous polymerization was carried out at an average residence time of 2.5 hours and a polymerization temperature of 150 ° C.
- the hydrogenation reaction rate at the styrene site was 96%.
- the catalyst was removed by a filter and introduced into a solvent removal apparatus to obtain pellet-shaped methyl methacrylate-styrene-vinylcyclohexane copolymer resin (resin A2).
- Example 1 A single-screw extruder with a shaft diameter of 25 mm, a single-screw extruder with a shaft diameter of 35 mm, a single-screw extruder with a shaft diameter of 65 mm, a feed block connected to all the extruders, and a T-die connected to the feed block
- a thermoplastic resin laminate was molded using a multilayer extrusion apparatus having A methyl methacrylate-styrene (3: 7) copolymer resin [manufactured by Nippon Steel Chemical Co., Ltd., trade name: Estyrene MS300] (resin B1) was continuously introduced into a single screw extruder having a shaft diameter of 25 mm, and the cylinder Extrusion was performed under the conditions of a temperature of 240 ° C.
- the vinyl copolymer resin (resin A2) obtained in Synthesis Example 1 was continuously introduced into a single screw extruder having a shaft diameter of 35 mm and extruded under the conditions of a cylinder temperature of 250 ° C. and a discharge speed of 3 kg / h.
- polycarbonate resin Iupilon E-2000 (resin C) manufactured by Mitsubishi Engineering Plastics Co., Ltd. was continuously introduced into a single screw extruder having a shaft diameter of 65 mm, and extruded at a cylinder temperature of 270 ° C. and a discharge speed of 50 kg / h.
- the feed block connected to the entire extruder was provided with three types and three layers of distribution pins, and the resin A2, the resin B1, and the resin C were introduced and laminated at a temperature of 260 ° C. It was extruded in a sheet form with a T-die having a temperature of 270 ° C. connected to the tip, and cooled while transferring the mirror surface with three mirror finish rolls, to obtain a laminate of resin A2, resin B1, and resin C. At this time, the roll was set to temperatures of 120 ° C., 130 ° C., and 190 ° C. from the upstream side.
- the thickness of the obtained laminate was 1.0 mm, the thickness of the resin A2 layer was 70 ⁇ m near the center, and the thickness of the resin B1 layer was 25 ⁇ m near the center.
- the evaluation results are shown in Table 1. The results of adhesion evaluation, high temperature and high humidity exposure test, and pencil scratch hardness test were all good.
- Example 2 Instead of the methyl methacrylate-styrene (3: 7) copolymer resin (resin B1) used in Example 1, methyl methacrylate-styrene (2: 8) copolymer resin Estyrene MS200 [manufactured by Nippon Steel Chemical Co., Ltd.] , Trade name: Estyrene MS200] (resin B2) was used in the same manner as in Example 1 to obtain a laminate of resin A2, resin B2, and resin C. The thickness of the obtained laminate was 1.0 mm, the thickness of the resin A2 layer was 70 ⁇ m near the center, and the thickness of the resin B2 layer was 25 ⁇ m near the center. The evaluation results are shown in Table 1. The results of adhesion evaluation, high temperature and high humidity exposure test, and pencil scratch hardness test were all good.
- Example 3 Instead of methyl methacrylate-styrene (3: 7) copolymer resin (resin B1) used in Example 1, methyl methacrylate-styrene (6: 4) copolymer resin [manufactured by Nippon Steel Chemical Co., Ltd., product Name: Estyrene MS600] (resin B3) was used in the same manner as in Example 1 to obtain a laminate of resin A2, resin B3, and resin C. The thickness of the obtained laminate was 1.0 mm, the thickness of the resin A2 layer was 70 ⁇ m near the center, and the thickness of the resin B3 layer was 25 ⁇ m near the center. The evaluation results are shown in Table 1. The results of adhesion evaluation, high temperature and high humidity exposure test, and pencil scratch hardness test were all good.
- Example 4 Instead of methyl methacrylate-styrene (3: 7) copolymer resin (resin B1) used in Example 1, acrylonitrile-styrene copolymer resin (trade name: Stylac-AS, manufactured by Asahi Kasei Chemicals Corporation) (resin A laminate of Resin A2, Resin B4 and Resin C was obtained in the same manner as Example 1 except that B4) was used.
- the thickness of the obtained laminate was 1.0 mm
- the thickness of the resin A2 layer was 70 ⁇ m near the center
- the thickness of the resin B4 layer was 25 ⁇ m near the center.
- the evaluation results are shown in Table 1. The results of adhesion evaluation, high temperature and high humidity exposure test, and pencil scratch hardness test were all good.
- Comparative Example 1 Instead of the methyl methacrylate-styrene-vinylcyclohexane copolymer resin (resin A2) used in Example 1, a polymethyl methacrylate resin [manufactured by Kuraray Co., Ltd., trade name: Parapet HR-1000L] (resin A3) was used. A laminated body of Resin A3, Resin B1, and Resin C was obtained in the same manner as Example 1 except that. The thickness of the obtained laminate was 1.0 mm, the thickness of the resin A3 layer was 70 ⁇ m near the center, and the thickness of the resin B1 layer was 25 ⁇ m near the center. The evaluation results are shown in Table 1. The result of the high-temperature and high-humidity exposure test was poor (warp, whitening).
- Comparative Example 2 Instead of the methyl methacrylate-styrene copolymer resin (resin B1) used in Comparative Example 1, a polymethyl methacrylate resin [manufactured by Kuraray Co., Ltd., trade name: Parapet HR-1000L] (resin B5) was used. A laminate of Resin A3, Resin B5, and Resin C was obtained in the same manner as Comparative Example 1 except that the temperature was 250 ° C. The thickness of the obtained laminate was 1.0 mm, the thickness of the resin A3 layer was 70 ⁇ m near the center, and the thickness of the resin B5 layer was 25 ⁇ m near the center. The evaluation results are shown in Table 1. The result of the high-temperature and high-humidity exposure test was poor (warp, whitening).
- Comparative Example 3 Instead of the methyl methacrylate-styrene copolymer resin (resin B1) used in Example 1, a polymethyl methacrylate resin [manufactured by Kuraray Co., Ltd., trade name: Parapet HR-1000L] (resin B5) was used. A laminate of Resin A2, Resin B5 and Resin C was obtained in the same manner as in Example 1 except that the temperature was 250 ° C. The thickness of the obtained laminate was 1.0 mm, the thickness of the resin A2 layer was 70 ⁇ m near the center, and the thickness of the resin B5 layer was 25 ⁇ m near the center. The evaluation results are shown in Table 1. The result of adhesion evaluation was poor (peeling).
- Comparative Example 4 Example 1 except that polystyrene resin [manufactured by PS Japan Ltd .: trade name: PSJ polystyrene] (resin B6) was used instead of the methyl methacrylate-styrene copolymer resin (resin B1) used in Example 1. Similarly, a laminate of Resin A2, Resin B6, and Resin C was obtained. The thickness of the obtained laminate was 1.0 mm, the thickness of the resin A2 layer was 70 ⁇ m near the center, and the thickness of the resin B3 layer was 25 ⁇ m near the center. The evaluation results are shown in Table 1. The result of adhesion evaluation was poor (peeling).
- thermoplastic resin laminate of the present invention is characterized by excellent weather resistance, scratch resistance, interlayer adhesion to high temperature and high humidity environments, and is suitable as an optical article such as a transparent substrate material and a transparent protective material. Used especially as a display unit front plate of OA equipment and portable electronic equipment
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Abstract
Description
しかしながら、メタクリル樹脂層の耐熱性が乏しくて高温環境下で変形を起こしたり、吸水性が高くて湿度変化による反りを起こしたりするなどの問題がある。
なお、透明性などに優れ、光学用部品に使用される樹脂として、特許文献3には(メタ)アクリル酸エステルモノマーと芳香族ビニルモノマーを重合し水素化した樹脂が開示されているが、その性能が十分とは云えず、更なる改善が求められている。
すなわち、本発明は、以下の熱可塑性樹脂積層体および該熱可塑性樹脂積層体を用いた透明性材料を提供するものである。
前記熱可塑性透明樹脂(A)が、下記一般式(1)で表される(メタ)アクリル酸エステル構成単位(a)と、下記一般式(2)で表される脂肪族ビニル構成単位(b)を含み、前記(メタ)アクリル酸エステル構成単位(a)と前記脂肪族ビニル構成単位(b)とのモル比が15:85~85:15であるビニル共重合樹脂であることを特徴とする熱可塑性樹脂積層体。
3.一般式(1)のR1及びR2がメチル基である上記1又は2の熱可塑性樹脂積層体。
4.一般式(2)のR3が水素であり、R4がシクロヘキシル基である上記1又は2の熱可塑性樹脂積層体。
5.片面または両面にハードコート処理、反射防止処理、および防眩処理のいずれか一つ以上を施したものである上記1又は2の熱可塑性樹脂積層体。
6.上記1~5のいずれかの熱可塑性樹脂積層体からなる透明性基板材料。
7.上記1~5のいずれかの熱可塑性樹脂積層体からなる透明性保護材料。
前記熱可塑性透明樹脂(A)が、下記一般式(1)で表される(メタ)アクリル酸エステル構成単位(a)と、下記一般式(2)で表される脂肪族ビニル構成単位(b)を含み、前記(メタ)アクリル酸エステル構成単位(a)と前記脂肪族ビニル構成単位(b)とのモル比が15:85~85:15であるビニル共重合樹脂であることを特徴とするものである。
本発明における式(1)で表される(メタ)アクリル酸エステル構成単位(a)と、式(2)で表される脂肪族ビニル構成単位(b)とのモル構成比は、(a)が15:85~85:15の範囲であり、25:75~75:25の範囲であることが好ましく、30:70~70:30の範囲であることがさらに好ましい。
(メタ)アクリル酸エステル構成単位(a)と脂肪族ビニル構成単位(b)との合計に対する(メタ)アクリル酸エステル構成単位(a)のモル構成比が15%未満であると機械強度が低くなりすぎて脆くなるので実用的ではない。また85%を超えるであると耐熱性が不十分となる場合がある。
この際に使用される芳香族ビニルモノマーとしては、具体的にスチレン、α-メチルスチレン、p-ヒドロキシスチレン、アルコキシスチレン、クロロスチレンなど、およびそれらの誘導体を挙げることができる。これらの中で好ましいのはスチレンである。
溶液重合法では、モノマー、連鎖移動剤、および重合開始剤を含むモノマー組成物を完全混合槽に連続的に供給し、100~180℃で連続重合する方法などにより行われる。
メタクリル酸メチル-スチレン共重合樹脂としては、例えば新日鉄化学(株)製のMS200、MS300、MS600などを挙げることができ、アクリロニトリル-スチレン共重合樹脂としては、例えば旭化成ケミカルズ(株)製のスタイラックASなどを挙げることができる。
共押出の方法は特に限定されず、例えば、フィードブロック方式では、フィードブロックで(C)層の片方あるいは両方に(B)層と、(B)層の上に(A)樹脂層を積層し、Tダイでシート状に押し出した後、成形ロールを通過させながら冷却し所望の積層体を形成する。また、マルチマニホールド方式では、マルチマニホールドダイ内で(C)層の片方あるいは両方に(B)層と、(B)層の上に(A)層を積層し、シート状に押し出した後、成形ロールを通過させながら冷却し所望の積層体を形成する。
また、接着剤を介して貼り合わせる方法も特に限定されず、公知の方法を用いることができる。例えば、一方の板状成形体にスプレー、刷毛、グラビアロールなどを用いて接着層を塗布し、そこへもう一方の板状成形体を重ねて接着層が硬化するまで圧着し、所望の積層体を形成する。
また、共押出の際に(A)層と(B)層の間、及び/または(B)層と(C)層の間に任意の接着樹脂(D)層を挟むこともできる。
また、熱可塑性樹脂(C)層の厚みは積層体の用途により異なるが、通常500~2000μm程度である。
実施例および比較例で得られた熱可塑性樹脂積層体の評価は以下のように行った。
試験片を10cm×10cmに切り出し、(A)層が外側となるように直径60mmの円筒に押し付け、層間の密着性を評価する。外観に変化のないものを良好とする。
試験片を10cm四方に切り出す。温度85℃、相対湿度85%に設定した恒温恒湿槽の中に、試験片の角を支点として吊り下げ、その状態で72時間保持する。試験片を取り出し、外観変化の有無を評価する。外観変化のないものを良好とする。
JIS K 5600-5-4に準拠し、表面に対して角度45度、荷重750gで(A)樹脂層の表面に次第に硬度を増して鉛筆を押し付け、きず跡を生じなかった最も硬い鉛筆の硬度を鉛筆硬度として評価する。鉛筆硬度3H以上を良好とする。
モノマー成分としてメタクリル酸メチル60.0188モル%とスチレン39.9791モル%、重合開始剤として0.0021モル%のt-アミルパーオキシ-2-エチルヘキサノエートからなるモノマー組成物を、ヘリカルリボン翼付き10L完全混合槽に1kg/hで連続的に供給し、平均滞留時間2.5時間、重合温度150℃で連続重合を行った。重合槽の液面が一定となるよう底部から連続的に抜き出し、脱溶剤装置に導入してペレット状のメタクリル酸メチル-スチレン共重合樹脂(樹脂A1)を得た。
得られた樹脂A1をイソ酪酸メチルに溶解し、10質量%イソ酪酸メチル溶液を調整した。1000mLオートクレーブ装置に樹脂A1の10質量%イソ酪酸メチル溶液を500重量部、10質量%Pd/C触媒を1重量部仕込み、水素圧10MPa、200℃で15時間保持してスチレン部位を水素化した。スチレン部位の水素化反応率は96%であった。フィルターにより触媒を除去し、脱溶剤装置に導入してペレット状のメタクリル酸メチル-スチレン-ビニルシクロヘキサン共重合樹脂(樹脂A2)を得た。
軸径25mmの単軸押出機と、軸径35mmの単軸押出機と、軸径65mmの単軸押出機と、全押出機に連結されたフィードブロックと、フィードブロックに連結されたTダイとを有する多層押出装置を用いて熱可塑性樹脂積層板を成形した。軸径25mmの単軸押出機にメタクリル酸メチル-スチレン(3:7)共重合樹脂〔新日鐵化学(株)製、商品名:エスチレンMS300〕(樹脂B1)を連続的に導入し、シリンダ温度240℃、吐出速度0.5kg/hの条件で押し出した。また軸径35mmの単軸押出機に合成例1で得たビニル共重合樹脂(樹脂A2)を連続的に導入し、シリンダ温度250℃、吐出速度3kg/hの条件で押し出した。また軸径65mmの単軸押出機に三菱エンジニアリングプラスチックス(株)製のポリカーボネート樹脂ユーピロンE-2000(樹脂C)を連続的に導入し、シリンダ温度270℃、吐出速度50kg/hで押し出した。全押出機に連結されたフィードブロックは3種3層の分配ピンを備え、温度260℃として樹脂A2と樹脂B1と樹脂Cを導入し積層した。その先に連結された温度270℃のTダイでシート状に押し出し、3本の鏡面仕上げロールで鏡面を転写しながら冷却し、樹脂A2と樹脂B1と樹脂Cの積層体を得た。このときロールは上流側から温度120℃、130℃、190℃とした。得られた積層体の厚みは1.0mm、樹脂A2層の厚みは中央付近で70μm、樹脂B1層の厚みは中央付近で25μmであった。評価結果を第1表に示す。密着性評価、高温高湿曝露試験、鉛筆引っかき硬度試験の結果は全て良好であった。
実施例1で使用したメタクリル酸メチル-スチレン(3:7)共重合樹脂(樹脂B1)の代わりにメタクリル酸メチル-スチレン(2:8)共重合樹脂エスチレンMS200〔新日鐵化学(株)製、商品名:エスチレンMS200〕(樹脂B2)を使用した以外は実施例1と同様にして樹脂A2と樹脂B2と樹脂Cの積層体を得た。得られた積層体の厚みは1.0mm、樹脂A2層の厚みは中央付近で70μm、樹脂B2層の厚みは中央付近で25μmであった。評価結果を第1表に示す。密着性評価、高温高湿曝露試験、鉛筆引っかき硬度試験の結果は全て良好であった。
実施例1で使用したメタクリル酸メチル-スチレン(3:7)共重合樹脂(樹脂B1)の代わりにメタクリル酸メチル-スチレン(6:4)共重合樹脂〔新日鐵化学(株)製、商品名:エスチレンMS600〕(樹脂B3)を使用した以外は実施例1と同様にして樹脂A2と樹脂B3と樹脂Cの積層体を得た。得られた積層体の厚みは1.0mm、樹脂A2層の厚みは中央付近で70μm、樹脂B3層の厚みは中央付近で25μmであった。評価結果を第1表に示す。密着性評価、高温高湿曝露試験、鉛筆引っかき硬度試験の結果は全て良好であった。
実施例1で使用したメタクリル酸メチル-スチレン(3:7)共重合樹脂(樹脂B1)の代わりにアクリロニトリル-スチレン共重合樹脂〔旭化成ケミカルズ(株)製、商品名:スタイラック-AS〕(樹脂B4)を使用した以外は実施例1と同様にして樹脂A2と樹脂B4と樹脂Cの積層体を得た。得られた積層体の厚みは1.0mm、樹脂A2層の厚みは中央付近で70μm、樹脂B4層の厚みは中央付近で25μmであった。評価結果を第1表に示す。密着性評価、高温高湿曝露試験、鉛筆引っかき硬度試験の結果は全て良好であった。
実施例1で使用したメタクリル酸メチル-スチレン-ビニルシクロヘキサン共重合樹脂(樹脂A2)の代わりにポリメタクリル酸メチル樹脂〔クラレ(株)製、商品名:パラペットHR-1000L〕(樹脂A3)を使用した以外は実施例1と同様にして樹脂A3と樹脂B1と樹脂Cの積層体を得た。得られた積層体の厚みは1.0mm、樹脂A3層の厚みは中央付近で70μm、樹脂B1層の厚みは中央付近で25μmであった。評価結果を第1表に示す。高温高湿曝露試験の結果は不良(反り、白化)であった。
比較例1で使用したメタクリル酸メチル-スチレン共重合樹脂(樹脂B1)の代わりにポリメタクリル酸メチル樹脂〔クラレ(株)製、商品名:パラペットHR-1000L〕(樹脂B5)を使用し、シリンダ温度を250℃とした以外は比較例1と同様にして樹脂A3と樹脂B5と樹脂Cの積層体を得た。得られた積層体の厚みは1.0mm、樹脂A3層の厚みは中央付近で70μm、樹脂B5層の厚みは中央付近で25μmであった。評価結果を第1表に示す。高温高湿曝露試験の結果は不良(反り、白化)であった。
実施例1で使用したメタクリル酸メチル-スチレン共重合樹脂(樹脂B1)の代わりにポリメタクリル酸メチル樹脂〔クラレ(株)製、商品名:パラペットHR-1000L〕(樹脂B5)を使用し、シリンダ温度250℃とした以外は実施例1と同様にして樹脂A2と樹脂B5と樹脂Cの積層体を得た。得られた積層体の厚みは1.0mm、樹脂A2層の厚みは中央付近で70μm、樹脂B5層の厚みは中央付近で25μmであった。評価結果を第1表に示す。密着性評価の結果は不良(剥離)であった。
実施例1で使用したメタクリル酸メチル-スチレン共重合樹脂(樹脂B1)の代わりにポリスチレン樹脂〔PSジャパン(株)製:商品名:PSJポリスチレン〕(樹脂B6)を使用した以外は実施例1と同様にして樹脂A2と樹脂B6と樹脂Cの積層体を得た。得られた積層体の厚みは1.0mm、樹脂A2層の厚みは中央付近で70μm、樹脂B3層の厚みは中央付近で25μmであった。評価結果を第1表に示す。密着性評価の結果は不良(剥離)であった。
Claims (7)
- 熱可塑性透明樹脂(A)層、メタクリル酸メチル-スチレン共重合体及び/又はアクリロニトリル-スチレン共重合体からなる熱可塑性樹脂(B)層、並びにポリカーボネート系樹脂からなる熱可塑性樹脂(C)層を有し、(C)層の片面または両面に(B)層が積層され、その(B)層の表面に(A)層が積層された熱可塑性樹脂積層体であって、
前記熱可塑性透明樹脂(A)が、下記一般式(1)で表される(メタ)アクリル酸エステル構成単位(a)と、下記一般式(2)で表される脂肪族ビニル構成単位(b)を含み、前記(メタ)アクリル酸エステル構成単位(a)と前記脂肪族ビニル構成単位(b)とのモル比が15:85~85:15であるビニル共重合樹脂であることを特徴とする熱可塑性樹脂積層体。
- 熱可塑性透明樹脂(A)が、少なくとも1種の(メタ)アクリル酸エステルモノマーと少なくとも1種の芳香族ビニルモノマーを重合した後、芳香族二重結合の70%以上を水素化して得られたものであり、前記樹脂のガラス転移温度が110~140℃の範囲である請求項1に記載の熱可塑性樹脂積層体。
- 一般式(1)のR1及びR2がメチル基である請求項1又は2に記載の熱可塑性樹脂積層体。
- 一般式(2)のR3が水素であり、R4がシクロヘキシル基である請求項1又は2に記載の熱可塑性樹脂積層体。
- 片面または両面にハードコート処理、反射防止処理、および防眩処理のいずれか一つ以上を施したものである請求項1又は2に記載の熱可塑性樹脂積層体。
- 請求項1~5のいずれかに記載の熱可塑性樹脂積層体からなる透明性基板材料。
- 請求項1~5のいずれかに記載の熱可塑性樹脂積層体からなる透明性保護材料。
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Also Published As
Publication number | Publication date |
---|---|
JPWO2010024217A1 (ja) | 2012-01-26 |
TW201012651A (en) | 2010-04-01 |
EP2319687A4 (en) | 2011-12-28 |
JP2015013481A (ja) | 2015-01-22 |
JP5850112B2 (ja) | 2016-02-03 |
KR20110074736A (ko) | 2011-07-01 |
US20110244242A1 (en) | 2011-10-06 |
TWI460073B (zh) | 2014-11-11 |
EP2319687B1 (en) | 2013-05-08 |
CN102137756A (zh) | 2011-07-27 |
EP2319687A1 (en) | 2011-05-11 |
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