JP2009196125A - Thermoplastic resin laminated body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin laminated body superior in impact resistance, heat resistance, weather resistance, low water absorbability, and abrasion resistance, a transparent substrate material and a transparent protection material using the thermoplastic resin laminated body. <P>SOLUTION: In the thermoplastic resin laminated body, a vinyl copolymer resin (A) which contains at least one kind of specified (meth) acrylic acid ester constituent unit (a) and at least one kind of a specified aliphatic vinyl constituent unit (b), and where a mol constituent ratio of the (meth) acrylic acid ester constituent unit (a) and the aliphatic vinyl constituent unit (b) is 15:85 to 85:15 is laminated on the one side or both sides of the thermoplastic resin (B), and the transparent substrate material and the transparent protection material are composed of the laminated body. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin laminate excellent in impact resistance, heat resistance, weather resistance, low water absorption and scratch resistance, and a molded body using the thermoplastic resin laminate.

Resin-made transparent plates are used in a wide variety of applications, including soundproofing partitions, carports, signboards, and display unit front plates for OA devices and portable electronic devices. In particular, in the case of portable display devices such as mobile phone terminals, portable electronic play equipment, and PDAs, the front panel has impact resistance, heat resistance, weather resistance, low water absorption, and scratch resistance due to the functionality that the user carries around. Improvements are increasingly required. As a method for improving these, for example, a laminated sheet in which a polycarbonate resin layer having excellent impact resistance and a methacrylic resin layer having excellent weather resistance are laminated is disclosed (Patent Documents 1 and 2). However, the heat resistance of the methacrylic resin layer is poor, and there is a problem that deformation occurs in a high temperature environment or warpage due to humidity change due to high water absorption.
Japanese Patent No. 3499972 JP 2006-205478 A

  The present invention relates to a thermoplastic resin laminate excellent in impact resistance, heat resistance, weather resistance, low water absorption, and scratch resistance, and a transparent substrate material and a transparent protective material using the thermoplastic resin laminate. The purpose is to provide.

（式中、Ｒ１は水素、あるいはメチル基であり、Ｒ２は炭素数１〜１６の炭化水素基である。）

（式中、Ｒ３およびＲ４は独立して水素または炭素数１〜１０の脂肪族炭化水素基である。） As a result of intensive studies to solve the above problems, the present inventors have achieved impact resistance, heat resistance, weather resistance, low water absorption, and scratch resistance by using a specific vinyl copolymer resin for the surface layer. The inventors have found that an excellent thermoplastic resin laminate can be formed, and have reached the present invention. That is, the present invention includes a (meth) acrylic ester structural unit (a) represented by the formula (1) and an aliphatic vinyl structural unit (b) represented by the formula (2), wherein the (meth) One side of the thermoplastic resin (B) is a vinyl copolymer resin (A) in which the molar constitution ratio of the acrylic ester structural unit (a) and the aliphatic vinyl structural unit (b) is 15:85 to 85:15. Or it is related with the thermoplastic resin laminated body laminated | stacked on both surfaces.

(In the formula, R1 is hydrogen or a methyl group, and R2 is a hydrocarbon group having 1 to 16 carbon atoms.)

(In the formula, R3 and R4 are independently hydrogen or an aliphatic hydrocarbon group having 1 to 10 carbon atoms.)

  According to the thermoplastic resin laminate of the present invention, it is possible to solve the above-described problems and provide a thermoplastic resin laminate excellent in impact resistance, heat resistance, weather resistance, low water absorption, and scratch resistance. Can do. Moreover, the optical article suitable for a transparent substrate material, a transparent protective material, etc. can be manufactured by using it.

The vinyl copolymer resin (A) used in the present invention is mainly composed of a (meth) acrylic acid ester structural unit (a) represented by the formula (1) and an aliphatic vinyl structural unit (b) represented by the formula (2). ).
In the present invention, 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. Mechanical strength when the molar composition ratio of the (meth) acrylate structural unit (a) to the total of the (meth) acrylic ester structural unit (a) and the aliphatic vinyl structural unit (b) is less than 15%. Becomes too low, or the adhesiveness with the thermoplastic resin (B) becomes too bad, which is not practical. Moreover, heat resistance may become inadequate that it is the range exceeding 85%. Preferably it is 25 to 75% of range, More preferably, it is 40 to 70% of range.

  As the (meth) acrylic acid ester structural unit represented by the formula (1) used in the present invention, for example, R2 is a methyl group, an ethyl group, a butyl group, a lauryl group, a stearyl group, a cyclohexyl group, an isobornyl group, or the like. Alkyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, hydroxyalkyl group such as 2-hydroxy-2-methylpropyl group, alkoxyalkyl group such as 2-methoxyethyl group, 2-ethoxyethyl group, benzyl group, The thing which is aryl groups, such as a phenyl group, can be mentioned. These can be used alone or in combination of two or more. Of these, preferred is a (meth) acrylate structural unit in which R2 is a methyl group and / or ethyl group, and more preferred is a methacrylic ester structure in which R1 is a methyl group and R2 is a methyl group and / or an ethyl group. Unit.

  As the aliphatic vinyl structural unit represented by the formula (2) used in the present invention, for example, R3 and R4 are independently hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group. , T-butyl groups, n-pentyl groups, n-hexyl groups and other alkyl groups, cyclohexyl groups, alkylcyclohexyl groups, hydroxycyclohexyl groups, alkoxycyclohexyl groups and the like. 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.

  In the present invention, other aromatic vinyl structural units can be used in combination as long as the transparency of the vinyl copolymer resin (A) is not impaired. For example, styrene, α-methylstyrene, p-hydroxystyrene, alkoxystyrene, chlorostyrene, and the like, and derivatives thereof can be mentioned. Of these, styrene is preferred.

  The ratio of the aromatic vinyl structural unit in the present invention is preferably 30% or less in the vinyl copolymer resin (A). If the content exceeds 30%, the transparency of the vinyl copolymer resin (A) may be lowered. Preferably it is 20% or less of range, More preferably, it is 10% or less of range.

  The vinyl copolymer resin (A) used in the present invention can be blended with other resins as long as the transparency of the vinyl copolymer resin (A) is not impaired. Examples thereof include methyl methacrylate-styrene copolymer resin, polymethyl methacrylate, polystyrene, and polycarbonate.

  The glass transition temperature of the vinyl copolymer resin (A) in the present invention is in the range of 110 to 140 ° C. If the temperature is less than 110 ° C., the heat resistance of the laminate may be insufficient. In addition, when the temperature exceeds 140 ° C., workability such as heat shaping may be inferior. 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 manufacturing method of the vinyl copolymer resin (A) in this invention is not specifically limited, A well-known method can be used. Examples thereof include a bulk polymerization method and a solution polymerization method. In the 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. Examples of the solvent used 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, and ethers such as tetrahydrofuran and dioxane. And alcohol solvents such as methanol and isopropanol.

  Further, the vinyl copolymer resin (A) can be produced by a method in which a vinyl copolymer resin (A ′) having an unsaturated bond is polymerized in advance and the unsaturated hydrocarbon group is subsequently hydrogenated. This hydrogenation reaction is carried out in a suitable solvent. The solvent used for the hydrogenation reaction may be the same as or different from the polymerization solvent for the vinyl copolymer resin (A ′) having an unsaturated bond. For example, 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. can be mentioned.

  The method for hydrogenating the vinyl copolymer resin (A ′) having an unsaturated bond is not particularly limited, and a known method can be used. For example, it can be carried out in a batch system or a continuous flow system at a hydrogen pressure of 3 to 30 MPa and a reaction temperature of 60 to 250 ° C. If the temperature is in the range of less than 60 ° C., it takes too much reaction time and is not practical. If the temperature exceeds 250 ° C., the molecular chain is broken and the ester moiety is 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.

  The thermoplastic resin (B) used in the present invention is a resin other than the vinyl copolymer resin (A), such as a polyester resin, a polycarbonate resin, an acrylic resin, a polyolefin resin, and a polyamide resin. Can be mentioned. These can be used alone or in combination of two or more. Preferable examples include a polycarbonate resin and a copolymer resin of methyl methacrylate and styrene.

  Various additives can be mixed and used in the vinyl copolymer resin (A) and the thermoplastic resin (B) in the present invention. Examples of 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.

  As a manufacturing method of the laminated body in the present invention, a method by coextrusion, a method of bonding through an adhesive, or the like can be used. The method of coextrusion is not particularly limited, and a known method can be used. For example, in the feed block method, (A) a resin layer is laminated on one or both of the (B) resin layer with a feed block, and a T die After extruding into a sheet shape, it is cooled while passing through a forming roll to form a desired laminate. In the multi-manifold system, the (A) resin layer is laminated on one or both of the (B) resin layers in the multi-manifold die, extruded into a sheet, and then cooled while passing through a forming roll to obtain a desired laminate. Form. Moreover, 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.

  In addition, an adhesive resin (C) layer can be sandwiched between the (A) layer and the (B) layer during coextrusion. It is effective in improving the adhesion between the (A) layer and the (B) layer.

  The thickness of the thermoplastic resin laminate in the present invention is in the range of 0.1 to 10.0 mm. If the thickness is less than 0.1 mm, transfer failure or thickness accuracy failure may occur due to bank omission. In addition, when the thickness exceeds 10.0 mm, a thickness accuracy defect or an appearance defect due to uneven cooling after molding may occur. Preferably it is the range of 0.3-5.0 mm, More preferably, it is the range of 0.5-3.0 mm.

  The thickness of the vinyl copolymer resin (A) layer of the thermoplastic resin laminate in the present invention is in the range of 10 to 500 μm. If the thickness is less than 10 μm, scratch resistance and weather resistance may be insufficient. If the thickness exceeds 500 μm, impact resistance may be insufficient. Preferably it is the range of 30-100 micrometers.

  The thermoplastic resin laminate of the present invention can be subjected to a hard coat treatment and / or an antireflection treatment and / or an antiglare treatment on one side or both sides thereof. 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.

  The thermoplastic resin laminate of the present invention is characterized by excellent impact resistance, heat resistance, weather resistance, low water absorption, and scratch resistance. These are preferable as optical articles such as a transparent substrate material and a transparent protective material, and particularly preferable as a display unit front plate of OA equipment / portable electronic equipment.

Hereinafter, the present invention will be described specifically by way of examples. However, this invention is not restrict | limited at all by these Examples.
The thermoplastic resin laminates obtained in the examples and comparative examples were evaluated as follows.

<Impact resistance test>
In accordance with JIS K 7211-1, a weight of 1 ± 0.05 kg (spherical size 2) is dropped freely from a height of 1 m, and the presence or absence of cracks reaching the back surface of the test piece is evaluated. The one that does not cause cracks reaching the back of the test piece 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.

<Weather resistance test>
Cut the test piece into 15 cm × 7 cm. Using a mercury lamp H400-F for discoloration test by Harrison Toshiba Lighting as a light source, testing was performed at a distance of 30 cm from the light source, an irradiation intensity of 0.8 mW / cm 2 and an irradiation time of 600 hours, and the difference ΔYI between before and after irradiation was evaluated. To do. A range where ΔYI is less than 1 is considered good.

<Steel wool test>
(A) The surface of the resin layer is subjected to a load of 1 kg on # 0000 steel wool and evaluated for the presence or absence of scratches after reciprocating 20 times at a width of 5 cm and a speed of 5 cm per second. A range of 0 to 10 scratches is considered good.

Synthesis example 1
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 blades, and continuous polymerization was carried out at an average residence time of 2.5 hours and a polymerization temperature of 150 ° C. It was continuously extracted from the bottom so that the liquid level in the polymerization tank was constant, and introduced into a solvent removal apparatus to obtain a pellet-shaped methyl methacrylate-styrene copolymer resin (resin A1). The obtained resin A1 was dissolved in methyl isobutyrate to prepare a 10 wt% methyl isobutyrate solution. A 1000 mL autoclave was charged with 500 parts by weight of a 10 wt% methyl isobutyrate solution of resin A1 and 1 part by weight of a 10 wt% Pd / C catalyst, and the hydrogen pressure was maintained at 10 MPa and 200 ° C. for 15 hours to hydrogenate the styrene site. 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
Thermoplastic using a multilayer extrusion apparatus having a single screw extruder with a shaft diameter of 25 mm, a single screw extruder with a shaft diameter of 65 mm, a feed block connected to both extruders, and a T-die connected to the feed block. A resin laminate was molded. The vinyl copolymer resin (resin A2) obtained in Synthesis Example 1 was continuously introduced into a single screw extruder having a shaft diameter of 25 mm and extruded under the conditions of a cylinder temperature of 250 ° C. and a discharge speed of 3 kg / h. Further, polycarbonate resin Iupilon E-2000 (resin B1) 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 40 kg / h. The feed block connected to both extruders was provided with two types and two layers of distribution pins, and the resin A2 and the resin B1 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 and resin B1. At this time, the temperature of the roll was set to 120 ° C, 140 ° C, and 180 ° C from the upstream side. The thickness of the obtained laminate was 1.2 mm, and the thickness of the resin A2 layer was 80 μm near the center. The results of the impact resistance test, the high temperature and high humidity exposure test, the weather resistance test, and the steel wool test were all good.

Example 2
Instead of the polycarbonate resin Iupilon E-2000 (resin B1) used in Example 1, methyl methacrylate-styrene copolymer resin Estyrene MS200 (resin B2) manufactured by Nippon Steel Chemical Co., Ltd. was used, and the shaft diameter was 65 mm. A laminate of resin A2 and resin B2 was obtained in the same manner as in Example 1 except that the cylinder temperature of the single screw extruder was 250 ° C., the temperature of the feed block was 250 ° C., and the temperature of the T die was 260 ° C. The thickness of the obtained laminate was 1.2 mm, and the thickness of the resin A2 layer was 80 μm near the center. The results of the impact resistance test, the high temperature and high humidity exposure test, the weather resistance test, and the steel wool test were all good.

Comparative Example 1
Similar to Example 1 except that acrylic resin parapet HR-1000L (resin A3) manufactured by Kuraray Co., Ltd. was used instead of the vinyl copolymer resin (resin A2) used in Example 1, and the cylinder temperature was 240 ° C. Thus, a laminate of resin A3 and resin B1 was obtained. The thickness of the obtained laminate was 1.2 mm, and the thickness of the resin A3 layer was 80 μm near the center. The results of the impact resistance test, weather resistance test, and steel wool test were good, but the results of the high-temperature and high-humidity exposure test were poor (warp, whitening).

Comparative Example 2
Instead of the polycarbonate resin Iupilon E-2000 (resin B1) used in Comparative Example 1, methyl methacrylate-styrene copolymer resin styrene MS200 (resin B2) manufactured by Nippon Steel Chemical Co., Ltd. was used, and the cylinder temperature was 250 ° C. A laminate of Resin A3 and Resin B2 was obtained in the same manner as in Comparative Example 1 except that the temperature of the feed block was 250 ° C. and the temperature of the T die was 260 ° C. The results of the impact resistance test, the weather resistance test, and the steel wool test were good, but the results of the high-temperature and high-humidity exposure test were poor (distortion, whitening).

Claims (8)

The (meth) acrylate structural unit (a) represented by the formula (1) and the aliphatic vinyl structural unit (b) represented by the formula (2), the (meth) acrylic ester structural unit ( A vinyl copolymer resin (A) having a molar composition ratio of a) to the aliphatic vinyl structural unit (b) of 15:85 to 85:15 was laminated on one side or both sides of the thermoplastic resin (B). Thermoplastic resin laminate.

(In the formula, R1 is hydrogen or a methyl group, and R2 is a hydrocarbon group having 1 to 16 carbon atoms.)

(In the formula, R3 and R4 are independently hydrogen or an aliphatic hydrocarbon group having 1 to 10 carbon atoms.)   The thermoplastic resin laminate according to claim 1, wherein R3 in formula (2) is hydrogen and R4 is a cyclohexyl group.   The thermoplastic resin laminate according to claim 1 or 2, wherein the vinyl copolymer resin (A) has a glass transition temperature in the range of 110 to 140 ° C.   The thermoplastic resin laminate according to any one of claims 1 to 3, wherein the thermoplastic resin (B) is a polycarbonate resin.   The thermoplastic resin laminate according to any one of claims 1 to 3, wherein the thermoplastic resin (B) is a copolymer resin of methyl methacrylate and styrene.   The thermoplastic resin laminate according to any one of claims 1 to 5, wherein one or more of a hard coat treatment, an antireflection treatment, and an antiglare treatment are performed on one side or both sides.   The transparent substrate material which consists of a thermoplastic resin laminated body in any one of Claims 1-6.   The transparency protective material which consists of a thermoplastic resin laminated body in any one of Claims 1-6.