JP6712926B2 - Transparent resin laminate - Google Patents

Description

INDUSTRIAL APPLICABILITY The present invention is used for a transparent base material or a protective material, has a polycarbonate-based resin layer and a specific thermoplastic resin layer in a specific total thickness, and in a specific ratio, even when exposed to high temperature and high humidity. The present invention relates to a resin laminate having excellent warp deformation resistance.

Acrylic resin is excellent in surface hardness, transparency, scratch resistance and weather resistance. On the other hand, polycarbonate resin is excellent in impact resistance. From this, a laminate having an acrylic resin layer and a polycarbonate resin layer is excellent in surface hardness, transparency, scratch resistance, weather resistance and impact resistance, and is suitable for automobile parts, home appliances, electronic devices and portable information terminals. It is used for display windows. However, a laminate having an acrylic resin layer and a polycarbonate resin layer has a problem that warpage occurs when it is used outdoors or in a vehicle under high temperature and high humidity.

Further, in Patent Document 1 (JP-A-5-59321), a copolymer containing a specific α-methylstyrene monomer, a methyl methacrylate monomer and a monomer copolymerizable therewith is a polycarbonate. There is a description of a laminate coated with a resin, but there is no description of warpage under high temperature and high humidity.

JP-A-5-59321

It is an object of the present invention to provide a resin laminate that can be used as a transparent base material or a transparent protective material and that can prevent warping even in a high temperature and high humidity environment and has excellent shape stability.

As a result of intensive studies to solve the above problems, the present inventors have laminated a thermoplastic resin (B) on at least one surface of a polycarbonate resin (A) sheet containing a polycarbonate resin as a main component, The thermoplastic resin (B) contains 5 to 25% by mass of an aromatic vinyl monomer unit, 3 to 18% by mass of an unsaturated dicarboxylic acid anhydride monomer unit, and 57 to 92% by mass of an acrylic compound monomer unit. % Of the copolymer (b), the total thickness of the polycarbonate resin (A) layer and the thermoplastic resin (B) layer is 700 μm or more, and the polycarbonate resin (A) layer and the thermoplastic resin (B). The ratio of the thickness of the layer of the thermoplastic resin (B) to the total thickness of the layer) of 0.1) is 0.1 to 25%, so that it is possible to prevent warping even in a high temperature and high humidity environment and is excellent in shape stability. They have found that a resin laminate can be obtained and have reached the present invention.

That is, the present invention has the features described below.
[1] A resin laminated body in which a thermoplastic resin (B) is laminated on at least one surface of a polycarbonate resin (A) sheet containing a polycarbonate resin as a main component,
Thermoplastic resin (B)
A copolymer containing 5 to 25 mass% of an aromatic vinyl monomer unit, 3 to 18 mass% of an unsaturated dicarboxylic acid anhydride monomer unit, and 57 to 92 mass% of an acrylic compound monomer unit (b ), and
The total thickness of the polycarbonate resin (A) layer and the thermoplastic resin (B) layer is 700 μm or more,
The resin laminate has a ratio of the thickness of the thermoplastic resin (B) layer to the total thickness of the polycarbonate resin (A) layer and the thermoplastic resin (B) layer of 0.1 to 25%.
[2] The resin laminate according to the above [1], wherein the unsaturated dicarboxylic acid anhydride monomer unit contained in the copolymer (b) is maleic anhydride.
[3] The resin laminate according to the above [1] or [2], wherein the acrylic compound monomer unit contained in the copolymer (b) is a (meth)acrylic acid ester.
[4] The resin laminate according to any one of the above [1] to [3], wherein the aromatic vinyl monomer unit contained in the copolymer (b) is styrene.
[5] The resin laminate according to any one of the above [1] to [4], wherein the copolymer (b) has a weight average molecular weight (Mw) of 50,000 to 250,000.
[6] The resin laminate according to any one of [1] to [5], wherein the polycarbonate resin (A) has a weight average molecular weight of 25,000 to 75,000.
[7] The resin laminate according to any one of the above [1] to [6], wherein the resin laminate has a total light transmittance of 75% or more and a haze of 10% or less.
[8] The resin laminate according to any one of the above [1] to [7], wherein at least one of the thermoplastic resin (B) layer and the polycarbonate resin (A) layer contains an ultraviolet absorber. ..
[9] The resin laminate according to any one of the above [1] to [8], further including a hard coat layer on the surface of the layer of the thermoplastic resin (B).
[10] One or both surfaces of the resin laminate are subjected to at least one of fingerprint resistance treatment, antireflection treatment, antiglare treatment, weather resistance treatment, antistatic treatment and antifouling treatment. [1] ~ The resin laminate according to any one of [9].
[11] A transparent substrate material containing the resin laminate according to any one of the above [1] to [10].
[12] A transparent protective material including the resin laminate according to any one of the above [1] to [10].
[13] A touch panel front protection plate including the resin laminate according to any one of the above [1] to [10].
[14] A front plate for an OA device or a portable electronic device, which includes the resin laminate according to any one of the above [1] to [10].

According to the present invention, there is provided a resin laminate having shape stability such as warp prevention under a high temperature and high humidity environment, and the resin laminate can be used as a transparent substrate material or a transparent protective material. Specifically, in portable display devices such as mobile phone terminals, portable electronic playground equipment, portable information terminals, and mobile PCs, and stationary display devices such as notebook PCs, desktop PC liquid crystal monitors, and liquid crystal televisions, for example, these Can be suitably used as a front plate that protects the equipment.

Hereinafter, the present invention will be described in detail by exemplifying production examples and examples, but the present invention is not limited to the exemplified production examples and examples, and the scope of the present invention is not largely deviated. If so, the method can be changed to an arbitrary method.

TECHNICAL FIELD The present invention relates to a resin laminate in which a thermoplastic resin (B) is laminated on at least one surface of a polycarbonate resin sheet (A) containing a polycarbonate resin as a main component. 5) contains 5 to 25% by mass of an aromatic vinyl monomer unit, 3 to 18% by mass of an unsaturated dicarboxylic acid anhydride monomer unit, and 57 to 92% by mass of an acrylic compound monomer unit. The combined thickness of the polycarbonate resin (A) layer and the thermoplastic resin (B) layer is 700 μm or more, and the polycarbonate resin (A) layer and the thermoplastic resin (B) layer are combined. The ratio of the thickness of the thermoplastic resin (B) layer to the total thickness is 0.1 to 25%.

<Polycarbonate resin (A)>
The polycarbonate resin (A) used in the present invention is a polycarbonate resin containing a polycarbonate resin as a main component. Here, "having a polycarbonate resin as a main component" means that the content of the polycarbonate resin exceeds 50 mass %. The polycarbonate resin (A) preferably contains 75% by mass or more of a polycarbonate resin, more preferably contains 90% by mass or more of a polycarbonate resin, and further preferably consists essentially of a polycarbonate resin. .. The polycarbonate resin (A) contains a carbonic acid ester bond in the main chain of the molecule. That is, a -[O-R-OCO]- unit (in the formula, R contains an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and further has a linear structure or a branched structure) It is not particularly limited as long as it includes the following), but it is particularly preferable to use a polycarbonate containing a structural unit of the following formula [1]. By using such a polycarbonate, a resin laminate having excellent impact resistance can be obtained.
Specifically, as the polycarbonate resin (A), an aromatic polycarbonate resin (for example, Iupilon S-2000, Iupilon S-1000, Iupilon E-2000, which is commercially available from Mitsubishi Engineering Plastics Co., Ltd.) is used. It is possible.

In recent years, there has been an increasing demand for bending the front plate as well. Therefore, the polycarbonate-based resin (A) can be synthesized by using a monohydric phenol represented by the following formula [2] as a terminal stopper. preferable.
(In the formula, R ₁ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms,
R _{2 to} R ₅ each represent hydrogen, halogen, or an optionally substituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, and the substituents are halogen and 1 to It is an alkyl group having 20 or an aryl group having 6 to 12 carbon atoms. )

The monohydric phenol of the general formula [2] is more preferably the monohydric phenol represented by the following formula [3].
(In the formula, R ₁ represents an alkyl group having 8 to 36 carbon atoms or an alkenyl group having 8 to 36 carbon atoms.)

The carbon number of R _{1 in} the general formula [2] or the general formula [3] is more preferably within a specific numerical range. Specifically, 22 is more preferable and 18 is particularly preferable as the upper limit of the carbon number of R ₁ . Moreover, 12 is more preferable as the lower limit of the carbon number of R ₁ .

Among the monohydric phenols (end terminators) represented by the general formula [2] or the general formula [3], one or both of parahydroxybenzoic acid hexadecyl ester and parahydroxybenzoic acid 2-hexyldecyl ester are terminated. It is particularly preferable to use it as an agent.

As R ₁ , for example, when a monohydric phenol having an alkyl group having 16 carbon atoms (end terminating agent) is used, glass transition temperature, melt fluidity, moldability, drawdown resistance, and monohydric value during polycarbonate resin production Phenol has excellent solvent solubility and is particularly preferable as a terminal stopper used in the polycarbonate resin used in the present invention.

On the other hand, when the carbon number of R _{1 in} the general formula [2] or the general formula [3] is excessively increased, the solubility of the monohydric phenol (end terminating agent) in the organic solvent tends to decrease, which may cause a decrease in polycarbonate resin production. Productivity may decrease.
As an example, when the carbon number of R ₁ is 36 or less, the productivity is high and the economical efficiency is good in producing a polycarbonate resin. When the carbon number of R ₁ is 22 or less, the monohydric phenol is particularly excellent in solubility in an organic solvent, the productivity can be made extremely high in producing a polycarbonate resin, and the economical efficiency is also improved.
If the carbon number of R _{1 in} the general formula [2] or the general formula [3] is too small, the glass transition temperature of the polycarbonate resin does not become a sufficiently low value, and the thermoformability may deteriorate.

Another resin contained in the polycarbonate resin (A) is a polyester resin. The polyester resin may contain terephthalic acid as a main component as a dicarboxylic acid component, and may contain a dicarboxylic acid component other than terephthalic acid.
For example, a polyester resin obtained by polycondensing a glycol component containing 20 to 40 (molar ratio, 100 in total) of 1,4-cyclohexanedimethanol to 80 to 60 (molar ratio) of the main component, So-called "PETG" is preferred. Further, the polycarbonate resin (A) may contain a polyester carbonate resin having an ester bond and a carbonate bond in the polymer skeleton.

In the present invention, the weight average molecular weight of the polycarbonate resin (A) affects the impact resistance of the resin laminate and the molding conditions. That is, when the weight average molecular weight is too small, the impact resistance of the resin laminate decreases, which is not preferable. If the weight average molecular weight is too large, an excessive heat source may be required when laminating the resin layer containing the polycarbonate resin (A), which is not preferable. Further, since a high temperature is required depending on the molding method, the polycarbonate resin (A) is exposed to a high temperature, which may adversely affect its thermal stability. The weight average molecular weight of the polycarbonate resin (A) is preferably 15,000 to 75,000, more preferably 20,000 to 70,000. More preferably, it is 25,000 to 65,000.

<Method for measuring weight average molecular weight of polycarbonate resin (A)>
The weight average molecular weight of the polycarbonate resin (A) can be measured based on the description in paragraphs 0061 to 0064 of JP2007-179018A. Details of the measuring method are shown below.

After performing measurement using polystyrene (PS) as a standard polymer, the relationship between the elution time and the molecular weight of polycarbonate (PC) is obtained by the universal calibration method to obtain a calibration curve. Then, the elution curve (chromatogram) of PC is measured under the same conditions as in the case of the calibration curve, and each average molecular weight is obtained from the elution time (molecular weight) and the peak area (number of molecules) of the elution time. When the number of molecules of the molecular weight Mi is Ni, the weight average molecular weight is expressed as follows. The following formula was used as the conversion formula.
(Weight average molecular weight)
Mw=Σ(NiMi ² )/Σ(NiMi)
(Conversion formula)
MPC = 0.47822MPS ^1.01470
MPC indicates the molecular weight of PC, and MPS indicates the molecular weight of PS.

The method for producing the polycarbonate resin (A) used in the present invention can be appropriately selected depending on the monomers to be used, such as the well-known phosgene method (interfacial polymerization method) and transesterification method (melting method).

<Thermoplastic resin (B)>
The thermoplastic resin (B) used in the present invention is the below-mentioned copolymer (b). The constituents of the copolymer (b) will be described below.

[Copolymer (b)]
The thermoplastic resin (B) according to the present invention contains 5 to 25% by mass of an aromatic vinyl monomer unit, 3 to 18% by mass of an unsaturated dicarboxylic acid anhydride monomer unit, and 57 to 5% of an acrylic compound monomer unit. It is a copolymer (b) containing 92% by mass.

The aromatic vinyl monomer is not particularly limited, and any known aromatic vinyl monomer can be used, but from the viewpoint of easy availability, styrene, α-methylstyrene, o-methylstyrene. , M-methylstyrene, p-methylstyrene, t-butylstyrene and the like. Among these, styrene is particularly preferable from the viewpoint of compatibility. Two or more kinds of these aromatic vinyl monomers may be mixed.

Examples of the unsaturated dicarboxylic acid anhydride monomer include acid anhydrides such as maleic acid, itaconic acid, citraconic acid and aconitic acid, and maleic anhydride is preferable from the viewpoint of compatibility with acrylic resins. Two or more kinds of these unsaturated dicarboxylic acid anhydride monomers may be mixed.

In the present specification, the “acrylic compound monomer” includes acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid and (meth)acrylic acid ester. Examples of the (meth)acrylic acid ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and 2-ethylhexyl methacrylate. To be Among them, (meth)acrylic acid ester is preferable from the viewpoint of compatibility with acrylic resin, and among them, methyl methacrylate (MMA) is more preferable. Two or more kinds of these acrylic compound monomers may be mixed.

The weight average molecular weight (Mw) of the copolymer (b) is preferably 50,000 to 250,000, more preferably 100,000 to 200,000. When the weight average molecular weight is 50,000 to 250,000, poor appearance such as flow marks is less likely to occur in lamination with the polycarbonate resin (A). The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw/Mn) can be measured using gel permeation chromatography using THF or chloroform as a solvent.

<Method of manufacturing various materials>
The method for producing the synthetic resin laminate of the present invention is not particularly limited. For example, a method of laminating an individually formed thermoplastic resin layer (B) and a polycarbonate-based resin layer (A) and thermocompression-bonding them, individually formed thermoplastic resin layer (B) and polycarbonate-based resin layer A method of laminating (A) and adhering both with an adhesive, a method of coextrusion molding a thermoplastic resin (B) layer and a polycarbonate resin (A) layer, and a thermoplastic resin previously formed There are various methods such as a method of in-molding and integrating the polycarbonate-based resin (A) using the layer (B), but from the viewpoint of manufacturing cost and productivity, the co-extrusion method is preferable. ..

In the present invention, the method for producing the thermoplastic resin (B) is not particularly limited, and necessary components are preliminarily mixed using a mixer such as a tumbler, a Henschel mixer, or a super mixer, and then a Banbury mixer, A known method such as melt-kneading with a machine such as a roll, a Brabender, a single-screw extruder, a twin-screw extruder or a pressure kneader can be applied.

<Resin laminate>
The resin laminate of the present invention is a resin laminate in which a thermoplastic resin (B) is laminated on at least one surface of a polycarbonate resin (A) sheet containing a polycarbonate resin as a main component.

In the present invention, the total thickness of the polycarbonate resin (A) layer and the thermoplastic resin (B) layer, the total thickness of the polycarbonate resin (A) layer and the thermoplastic resin (B) layer in the resin laminate (sheet) The ratio of the thickness of the layer of the thermoplastic resin (B) to the composition and the composition of the layer of the thermoplastic resin (B) influence the warpage of the resin laminate in a high temperature and high humidity environment. That is, the thermoplastic resin (B) contains 5 to 25% by mass of aromatic vinyl monomer units, 3 to 18% by mass of unsaturated dicarboxylic acid anhydride monomer units, and 57 to 5% of acrylic compound monomer units. The copolymer (b) containing 92% by mass, the total thickness of the layer of the polycarbonate resin (A) and the layer of the thermoplastic resin (B) is 700 μm or more, and the layer of the polycarbonate resin (A) and the heat Since the ratio of the thickness of the layer of the thermoplastic resin (B) to the total thickness of the layer of the thermoplastic resin (B) is 0.1 to 25%, warp can be suppressed even in a high temperature and high humidity environment. .. Therefore, if the total thickness of the polycarbonate-based resin (A) layer and the thermoplastic resin (B) layer is too thin, the warp in the high temperature and high humidity environment becomes large, and when the total thickness is large, the warp in the high temperature and high humidity environment occurs. Get smaller. Specifically, the total thickness of the polycarbonate resin (A) layer and the thermoplastic resin (B) layer is preferably 700 μm or more, more preferably 800 μm or more, and further preferably 1,000 μm or more. The total thickness is preferably 4,000 μm or less, more preferably 3,000 μm or less, and even more preferably 2,000 μm or less.

In the present invention, the thickness of the thermoplastic resin (B) layer affects the surface hardness and impact resistance of the resin laminate. That is, if the ratio of the thickness of the thermoplastic resin (B) layer to the total thickness of the polycarbonate resin (A) layer and the thermoplastic resin (B) layer is too small, the surface hardness becomes low, which is not preferable. If the ratio of the thickness of the thermoplastic resin (B) layer to the total thickness of the polycarbonate resin (A) layer and the thermoplastic resin (B) layer is too large, the impact resistance deteriorates, which is not preferable. The ratio of the thickness of the thermoplastic resin (B) layer to the total thickness is preferably 1 to 25%, more preferably 2 to 20%. It is more preferably 2 to 11%, and particularly preferably 3 to 11%.

In the present invention, in terms of the appearance of the resin laminate (sheet), the total light transmittance is preferably 75% or more, more preferably 80% or more, still more preferably 85% or more. The upper limit of the total light transmittance is preferably 95%. The haze of the resin laminate (sheet) is preferably 30% or less, more preferably 25% or less, and further preferably 20% or less. The lower limit of Haze is preferably 0%.

<Arbitrary additives>
In the present invention, the polycarbonate-based resin (A) forming the base material layer and/or the thermoplastic resin (B) forming the surface layer may contain components other than the main components described above.

For example, the polycarbonate resin (A) and/or the thermoplastic resin (B) may be mixed with an ultraviolet absorber and used. If the content of the ultraviolet absorber is too large, the excessive ultraviolet absorber may be scattered due to a high temperature depending on the molding method, and the molding environment may be contaminated, causing a problem. From this, the content ratio of the ultraviolet absorber is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, and further preferably 0 to 1% by mass. Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy. -4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, etc. Benzophenone-based UV absorber, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-t-butylphenyl)benzotriazole, 2-(2-hydroxy-3) Benzotriazole-based UV absorbers such as -t-butyl-5-methylphenyl)benzotriazole and (2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, salicylic acid Benzoate-based ultraviolet absorbers such as phenyl and 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, bis(2,2,6,6-tetramethylpiperidine-4) -Yl) hindered amine UV absorbers such as sebacate, 2,4-diphenyl-6-(2-hydroxy-4-methoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2- Hydroxy-4-ethoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2-hydroxy-4-propoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-(2- Hydroxy-4-butoxyphenyl)1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-butoxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6- (2-Hydroxy-4-hexyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2, 4-diphenyl-6-(2-hydroxy-4-dodecyloxyphenyl)-1,3,5-triazine, 2,4-diphenyl-6-(2-hydroxy-4-benzyloxyphenyl)-1,3 Examples thereof include triazine-based UV absorbers such as 5-triazine. The mixing method is not particularly limited, and a method of compounding the entire amount, a method of dry blending the masterbatch, a method of dry blending the entire amount, and the like can be used.

In the present invention, the polycarbonate resin (A) forming the base material layer and/or the thermoplastic resin (B) forming the surface layer may be mixed with various additives in addition to the above ultraviolet absorber. You can As such additives, for example, antioxidants and anti-colorants, anti-static agents, mold release agents, lubricants, dyes, pigments, plasticizers, flame retardants, resin modifiers, compatibilizers, organic fillers and Examples include reinforcing materials such as inorganic fillers. The mixing method is not particularly limited, and a method of compounding the entire amount, a method of dry blending the masterbatch, a method of dry blending the entire amount, and the like can be used.

<Arbitrary processing>
In the present invention, the surface of the thermoplastic resin (B) layer or the surface of the polycarbonate resin (A) layer may be subjected to a hard coat treatment. For example, the hard coat layer is formed by a hard coat treatment using a hard coat paint that is cured using heat energy and/or light energy. Examples of the hard coat paint that is cured using heat energy include thermosetting resin compositions such as polyorganosiloxane-based and cross-linked acrylic-based. In addition, as a hard coat coating that is cured using light energy, for example, a photocurable resin obtained by adding a photopolymerization initiator to a resin composition including a monofunctional and/or polyfunctional acrylate monomer and/or oligomer. A composition etc. are mentioned.

Examples of the hard coat paint that is applied on the surface of the thermoplastic resin (B) layer or the surface of the polycarbonate resin (A) layer in the present invention and is cured using light energy include, for example, 1,9-nonanediol diacrylate. 20 to 60% by mass, a bifunctional or higher polyfunctional (meth)acrylate monomer copolymerizable with 1,9-nonanediol diacrylate, and a bifunctional or higher polyfunctional urethane (meth)acrylate oligomer and/or bifunctional or higher 1 to 100 parts by mass of a resin composition consisting of 40 to 80% by mass of a compound composed of the polyfunctional polyester (meth)acrylate oligomer and/or the polyfunctional epoxy (meth)acrylate oligomer having two or more functional groups. Examples of the photocurable resin composition added include 10 parts by mass.

The method for applying the hard coat paint in the present invention is not particularly limited, and a known method can be used. Examples thereof include spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure coating, meniscus coating, flexographic printing, screen printing, beat coating, and sorting. ..

For the purpose of improving the adhesion of the hard coat layer, pretreatment of the coated surface may be performed before the hard coat treatment. Examples of the treatment include known methods such as a sandblast method, a solvent treatment method, a corona discharge treatment method, a chromic acid treatment method, a flame treatment method, a hot air treatment method, an ozone treatment method, an ultraviolet treatment method, and a primer treatment method with a resin composition. Can be mentioned.

Each material of the thermoplastic resin (B) layer, the polycarbonate-based resin (A) layer and the hard coat layer in the present invention, for example, the thermoplastic resin (B) and the polycarbonate-based resin (A) is filtered and purified by a filter treatment. Preferably. By producing or laminating through a filter, it is possible to obtain a synthetic resin laminate having few appearance defects such as foreign matters and defects. The filtration method is not particularly limited, and melt filtration, solution filtration, or a combination thereof can be used.

The filter to be used is not particularly limited, and a known filter can be used, and it is appropriately selected depending on the use temperature of each material, viscosity, and filtration accuracy. The filter material of the filter is not particularly limited, but polypropylene, cotton, polyester, viscose rayon or glass fiber non-woven fabric or roving yarn roll, phenol resin impregnated cellulose, metal fiber non-woven fabric sintered body, metal powder sintered body, breaker plate, Alternatively, any combination of these can be used. Particularly in consideration of heat resistance, durability, and pressure resistance, a type obtained by sintering a metal fiber nonwoven fabric is preferable.

The filtration accuracy of the polycarbonate resin (A) is 50 μm or less, preferably 30 μm or less, more preferably 10 μm or less. The filtration accuracy of the hard coat agent is 20 μm or less, preferably 10 μm or less, more preferably 5 μm or less because it is applied to the outermost layer of the resin laminate.

Regarding the filtration of the thermoplastic resin (B) and the polycarbonate resin (A), it is preferable to use, for example, a polymer filter used for thermoplastic resin melt filtration. The polymer filter is classified into a leaf disc filter, a candle filter, a pack disc filter, a cylindrical filter and the like depending on its structure, but a leaf disc filter having a large effective filtration area is particularly preferable.

The resin laminate of the present invention may be subjected to one or more of anti-fingerprint treatment, antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment on one side or both sides. The methods of antireflection treatment, antifouling treatment, antistatic treatment, weather resistance treatment and antiglare treatment are not particularly limited, and known methods can be used. For example, a method of applying a reflection reducing paint, a method of depositing a dielectric thin film, a method of applying an antistatic paint and the like can be mentioned.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples.

Measurement of physical properties of the laminated resin obtained in the production example and evaluation of the synthetic resin laminated body obtained in the examples and comparative examples were performed as follows.

<Warping test under high temperature and high humidity environment>
A test piece of the resin laminate was cut into a 10 cm×6 cm square. The test piece was set in a holder of two-point support type, placed in an environmental tester set to a temperature of 23° C. and a relative humidity of 50% for 24 hours or more to adjust the condition, and then the warpage was measured. The value at this time was taken as the value of the amount of warp before processing. Next, the test piece was set in a holder, placed in an environmental tester set to a temperature of 85° C. and a relative humidity of 85%, and kept in that state for 120 hours. Further, the holder was moved into an environmental tester set to a temperature of 23° C. and a relative humidity of 50%, and the warp was measured again after holding the holder for 4 hours in that state. The value at this time was taken as the value of the post-treatment warp amount. To measure the warp, use a three-dimensional shape measuring machine equipped with an electric stage, place the test piece taken out horizontally in a convex state, scan at 1 mm intervals, and measure the bulge in the center as the warp. did. The absolute value of the difference between the warp amounts before and after the treatment, that is, |(warp amount after treatment)-(warp amount before treatment)| was evaluated as the warp change amount. At that time, if the amount of change in the warp exceeds 700 μm, the warp may be recognizable even with the naked eye, and therefore the pass/fail judgment of the warp test was performed according to the following criteria.
○ (Pass): Amount of change in warpage of resin laminate ≦700 μm
X (fail): outside the above range

<Pencil scratch hardness test>
In accordance with JIS K 5600-5-4, the hardest pencil that did not cause a scar by pressing the pencils in order from the lowest hardness to the surface of the thermoplastic resin (B) layer at an angle of 45 degrees to the surface and a load of 750 g. Was evaluated as the pencil hardness. The pencil hardness is indicated by 2B, B, HB, F, H, 2H, 3H and 4H in the order of decreasing rank. The pencil scratch hardness test was judged as pass or fail according to the following criteria, and a mark of Δ or higher was passed.
◯: The pencil hardness of the surface of the thermoplastic resin (B) is 2H or more Δ: The pencil hardness of the surface of the thermoplastic resin (B) is H
X: Pencil hardness of the thermoplastic resin (B) surface is less than H

<Impact resistance test>
A test piece of the resin laminate was cut into a piece of 8 cm×8 cm, and the thermoplastic resin (B) layer of the test piece was placed on the upper surface, and both surfaces were supported by a jig having a circular hole with a diameter of 6 cm. A gun-shaped 4 mm R hemispherical bullet having a weight of 40 g was dropped from the height of 10 cm to the center of the circle, and the test piece was raised by 10 cm until the test piece broke. Then, the maximum height without breaking was evaluated as impact resistance. The impact resistance was evaluated according to the following criteria.
○ (Pass): The maximum height without breakage is 60 cm or more × (Failure): Outside the above range

<Measurement of total light transmittance>
The total light transmittance of the resin laminate was measured according to JIS K7361-1 using a reflectance/transmittance meter HR-100 type (manufactured by Murakami Color Research Laboratory Co., Ltd.), and the total light transmittance test was performed according to the following criteria. The pass/fail judgment was made.
○ (Pass): Total light transmittance of resin laminate ≧75%
X (fail): outside the above range

<Haze measurement>
The Haze of the resin laminate was measured according to JIS K7136 using a reflectance/transmittance meter HR-100 type (manufactured by Murakami Color Research Laboratory Co., Ltd.), and the Haze test was passed or failed based on the following criteria.
◯ (Pass): Haze≦30% of resin laminate
X (fail): outside the above range

<Examples of various materials>
Examples of the polycarbonate resin (A) and the copolymer (b) are shown below, but the materials are not limited thereto.
A-1: Polycarbonate resin: Mitsubishi Engineering Plastics Co., Ltd. Iupilon E-2000, weight average molecular weight: 34,000
b1-1: Acrylic resin: Acrylic resin manufactured by Asahi Kasei Chemicals Corporation Delpet 980N (mass ratio of styrene:maleic anhydride:MMA=16:8:76, weight average molecular weight: 133,000)
b1-2: Acrylic resin: Acrylic resin PLEXIGLAS hw55 (manufactured by Daicel-Evonik Ltd.) (mass ratio of styrene:maleic anhydride:MMA=15:9:76, weight average molecular weight: 141,000)
d1-1: Acrylic resin: methyl methacrylate resin manufactured by Kuraray Co., Ltd. Parapet HR-L (mass ratio of styrene:maleic anhydride:MMA=0:0:100, weight average molecular weight: 90,000)

Production Example 1 [Production of Resin (B11) Pellets]
0.05 mass% of phosphorus-based additive PEP-36 (manufactured by ADEKA CORPORATION) and stearic acid monoglyceride (product name) based on 100 mass parts of Delpet 980N (b1-1) as a copolymer (b). : H-100, manufactured by Riken Vitamin Co., Ltd.) 0.2% by mass, antioxidant 2,6-di-tert-butyl-cresol (Product name: K-NOX, manufactured by Kyodo Pharmaceutical Co., Ltd.) 0.1% by mass , UV absorber Tinuvin 1600 (manufactured by BASF Japan Ltd.) 0.7% by mass, mixed for 20 minutes with a blender, and then a twin screw extruder having a screw diameter of 26 mm (Toshiba Kikai Co., Ltd., TEM-26SS, L/D≈). 40) was melt-kneaded at a cylinder temperature of 240° C., extruded into a strand and pelletized by a pelletizer. The pellets could be manufactured stably.

Production Example 2 [Production of Resin (B12) Pellets]
100 parts by mass of PLEXIGLAS hw55 (b1-2) as a copolymer (b), 0.05% by mass of phosphorus-based additive PEP-36, and 0.2% by mass of stearic acid monoglyceride, and antioxidant 2 0.1% by mass of 6,6-di-tert-butyl-cresol and 0.7% by mass of UV absorber Tinuvin 1600 were added, and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Comparative Production Example 1 [Production of Resin (D11) Pellets]
Parapet HR-L (d1-1) is used in an amount of 0.05 part by mass of PEP-36, a phosphorus-based additive, and 0.2% by mass of stearic acid monoglyceride per 100 parts by mass of parapet HR-L (d1-1). Ributyl-cresol 0.1% by mass and UV absorber Tinuvin1600 0.7% by mass were added, and mixed and pelletized in the same manner as in Production Example 1. The pellets could be manufactured stably.

Example 1
Each extruder is a multi-layer extruder having a single-screw extruder having a shaft diameter of 32 mm, a single-screw extruder having a shaft diameter of 65 mm, a feed block connected to the whole extruder, and a T-die connected to the feed block. A resin laminate was molded using a multi-layer extruder having a connected multi-manifold die. The resin (B11) obtained in Production Example 1 was continuously introduced into a single-screw extruder having a shaft diameter of 32 mm, and extruded under the conditions of a cylinder temperature of 240° C. and a discharge rate of 2.1 kg/h. A polycarbonate resin (A-1) (manufactured by Mitsubishi Engineering Plastics Co., Ltd., product name: Iupilon E-2000, weight average molecular weight: 34,000) was continuously introduced into a single-screw extruder having a shaft diameter of 65 mm to form a cylinder. The temperature was 280° C. and the discharge rate was 30.0 kg/h. The feed block connected to the whole extruder was equipped with a distribution pin of two types and two layers, and the temperature was set to 270° C. and (B11) and (A-1) were introduced and laminated. It is extruded into a sheet with a T-die at a temperature of 270°C that is connected to the end, and cooled while transferring the mirror surface from the upstream side with three mirror finishing rolls at temperatures of 130°C, 140°C, and 180°C, and a line speed of 0. It was set to 0.8 m/min to obtain a laminate (E11) of (B11) and (A-1). The total thickness of the obtained laminate (E11) was 1000 μm, the thickness of the layer made of B11 was 60 μm near the center, and the thickness of the thermoplastic resin (B) layer with respect to the total thickness of the (B) layer and the (A) layer. Was 6.0%. The amount of change in warp of the laminate (E11) under a high temperature and high humidity environment is 283 μm, the pencil hardness of the thermoplastic resin (B) is 2H, and the maximum height at which it does not break is 100 cm. The total light transmittance was 91.4%, which was acceptable, and the haze was 0.2%, which was acceptable, and the overall judgment was acceptable.

Example 2
The same as the laminate (E11) except that the discharge rate of the resin (B11) was 3.5 kg/h, the discharge rate of the polycarbonate resin (A-1) was 28.6 kg/h, and the line speed was 0.8 m/min. A laminate (E12) was obtained under the molding conditions. The total thickness of the laminate (E12) is 1000 μm, the thickness of the layer made of B11 is 100 μm near the center, and the ratio of the thickness of the thermoplastic resin (B) layer to the total thickness of the (B) layer and the (A) layer is It was 10.0%. The amount of change in warpage of the laminate (E12) under a high temperature and high humidity environment is 425 μm, the pencil hardness of the thermoplastic resin (B) is 2H, and the maximum height without breaking is 80 cm, which is acceptable. The total light transmittance was 91.4%, which was acceptable, and the haze was 0.2%, which was acceptable, and the overall judgment was acceptable.

Example 3
The same as the laminate (E11) except that the discharge rate of the resin (B11) was 2.4 kg/h, the discharge rate of the polycarbonate resin (A-1) was 29.7 kg/h, and the line speed was 1.0 m/min. A laminate (E13) was obtained under the molding conditions. The total thickness of the laminate (E13) was 800 μm, the thickness of the layer composed of B11 was 60 μm near the center, and the ratio of the thickness of the thermoplastic resin (B) layer to the total thickness of the (B) layer and the (A) layer was It was 7.5%. The amount of change in warp of the laminate (E13) under a high-temperature and high-humidity environment is 537 μm, the pencil hardness of the thermoplastic resin (B) is 2H, and the maximum height without breaking is 70 cm. The total light transmittance was 91.4%, which was acceptable, and the haze was 0.1%, which was acceptable, and the overall evaluation was acceptable.

Example 4
A laminate (E14) of (B12) and (A-1) was obtained in the same manner as in Example 1 except that the resin (B12) was used instead of the resin (B11). The total thickness of the laminate (E14) is 1000 μm, the thickness of the layer made of B12 is 60 μm near the center, and the ratio of the thickness of the thermoplastic resin (B) layer to the total thickness of the (B) layer and the (A) layer is It was 6.0%. The amount of change in warpage of the laminate (E14) under a high temperature and high humidity environment is 268 μm, the thermoplastic resin (B) has a pencil hardness of 2H, and the maximum height without breaking is 100 cm. The total light transmittance was 91.2%, the haze was 0.3%, and the haze was 0.3%.

Example 5
A laminate (E15) of (B12) and (A-1) was obtained in the same manner as in Example 2 except that the resin (B12) was used instead of the resin (B11). The total thickness of the laminate (E15) is 1000 μm, the thickness of the layer made of B12 is 100 μm near the center, and the ratio of the thickness of the thermoplastic resin (B) layer to the total thickness of the (B) layer and the (A) layer is It was 10.0%. The amount of change in warpage of the laminate (E15) under a high temperature and high humidity environment was 397 μm, the pencil hardness of the thermoplastic resin (B) was 2H, and the maximum height at which breakage was 80 cm was acceptable. The total light transmittance was 91.2%, the haze was 0.3%, and the haze was 0.3%.

Example 6
A laminate (E16) of (B12) and (A-1) was obtained in the same manner as in Example 3 except that the resin (B12) was used instead of the resin (B11). The total thickness of the laminate (E16) was 800 μm, the thickness of the layer made of B12 was 60 μm near the center, and the ratio of the thickness of the thermoplastic resin (B) layer to the total thickness of the (B) layer and the (A) layer was It was 7.5%. The amount of change in warp of the laminate (E15) in a high temperature and high humidity environment is 502 μm, the pencil hardness of the thermoplastic resin (B) is 2H, and the maximum height at which it does not break is 70 cm. The total light transmittance was 91.2%, which was acceptable, and the haze was 0.2%, which was acceptable, and the overall evaluation was acceptable.

Example 7
The same as the laminate (E11) except that the discharge rate of the resin (B11) was 0.4 kg/h, the discharge rate of the polycarbonate resin (A-1) was 31.7 kg/h, and the line speed was 0.8 m/min. A laminate (E17) was obtained under the molding conditions. The total thickness of the laminate (E17) was 1000 μm, the thickness of the layer composed of B11 was 10 μm near the center, and the ratio of the thickness of the thermoplastic resin (B) layer to the total thickness of the (B) layer and the (A) layer was It was 1.0%. The amount of warpage change of the laminate (E17) under high temperature and high humidity environment is 109 μm, the pencil hardness of the thermoplastic resin (B) is H, and the maximum height without breaking is 130 cm, and The total light transmittance was 91.4%, which was acceptable, and the haze was 0.2%, which was acceptable, and the overall judgment was acceptable.

Comparative Example 1
A laminate (F11) of (D11) and (A-1) was obtained in the same manner as in Example 1 except that the resin (D11) was used instead of the resin (B11). The total thickness of the laminate (F11) was 1000 μm, the thickness of the layer composed of D11 was 60 μm near the center, and the ratio of the thickness of the thermoplastic resin (B) layer to the total thickness of the (B) layer and the (A) layer was It was 6.0%. The amount of change in warpage of the laminate (F11) in a high temperature and high humidity environment was 906 μm, which was unacceptable. The pencil hardness of the thermoplastic resin (B) was 2H, which was acceptable, and the maximum height without breaking was 100 cm, which was acceptable. The total light transmittance was 91.6%, the haze was 0.1%, and the haze was 0.1%.

Comparative example 2
A laminate (F12) of (D11) and (A-1) was obtained in the same manner as in Example 2 except that the resin (D11) was used instead of the resin (B11). The total thickness of the laminate (F12) is 1000 μm, the thickness of the layer made of D11 is 100 μm near the center, and the ratio of the thickness of the thermoplastic resin (B) layer to the total thickness of the (B) layer and the (A) layer is It was 10.0%. The amount of change in warpage of the laminate (F12) in a high temperature and high humidity environment was 1157 μm, which was unacceptable, the pencil hardness of the thermoplastic resin (B) was 2H, and the maximum height at which breakage was 80 cm was acceptable. The total light transmittance was 91.6%, the haze was 0.1%, and the haze was 0.1%.

Comparative Example 3
A laminate (F13) of (D11) and (A-1) was obtained in the same manner as in Example 3 except that the resin (D11) was used instead of the resin (B11). The total thickness of the laminate (F13) was 800 μm, the thickness of the layer made of D11 was 60 μm near the center, and the ratio of the thickness of the thermoplastic resin (B) layer to the total thickness of the (B) layer and the (A) layer was It was 7.5%. The amount of change in warpage of the laminate (F13) in a high temperature and high humidity environment was 1491 μm, which was unacceptable, the pencil hardness of the thermoplastic resin (B) was 2H, and the maximum height without breaking was 70 cm, which was unacceptable. Yes, the total light transmittance was 91.6%, and the haze was 0.1%.

Comparative Example 4
The same as the laminate (E11) except that the discharge rate of the resin (D11) was 3.8 kg/h, the discharge rate of the polycarbonate resin (A-1) was 28.6 kg/h, and the line speed was 1.6 m/min. A laminate (F14) was obtained under the molding conditions. The total thickness of the laminate (F14) was 500 μm, the thickness of the layer made of D11 was 60 μm near the center, and the ratio of the thickness of the thermoplastic resin (B) layer to the total thickness of the (B) layer and the (A) layer was It was 12.0%. The amount of change in warpage of the laminate (F14) in a high temperature and high humidity environment was 1959 μm, which was unacceptable, the pencil hardness of the thermoplastic resin (B) was 2H, and the maximum height without breaking was 30 cm, which was unacceptable. Yes, the total light transmittance was 91.6%, and the haze was 0.1%.

Comparative Example 5
A laminate (F15) of (B11) and (A-1) was obtained in the same manner as in Comparative Example 4 except that the resin (B11) was used instead of the resin (D11). The total thickness of the laminate (F15) is 500 μm, the thickness of the layer made of B11 is 60 μm near the center, and the ratio of the thickness of the thermoplastic resin (B) layer to the total thickness of the (B) layer and the (A) layer is It was 12.0%. The amount of change in warpage of the laminate (F15) in a high temperature and high humidity environment was 944 μm, which was unacceptable, the pencil hardness of the thermoplastic resin (B) was 2H, and the maximum height without breaking was 30 cm, which was unacceptable. Yes, the total light transmittance was 91.4%, and the haze was 0.1%.

Comparative Example 6
A laminate (F16) of (B12) and (A-1) was obtained in the same manner as in Comparative Example 4 except that the resin (B12) was used instead of the resin (D11). The total thickness of the laminate (F16) is 500 μm, the thickness of the layer made of B12 is 60 μm near the center, and the ratio of the thickness of the thermoplastic resin (B) layer to the total thickness of the (B) layer and the (A) layer is It was 12.0%. The amount of change in warpage of the laminate (F16) in a high temperature and high humidity environment was 875 μm, which was unacceptable, the pencil hardness of the thermoplastic resin (B) was 2H, and the maximum height without breaking was 30 cm, which was unacceptable. Yes, the total light transmittance was 91.2%, and the haze was 0.2%.

Comparative Example 7
The same as the laminate (E11) except that the discharge rate of the resin (B11) was 10.5 kg/h, the discharge rate of the polycarbonate resin (A-1) was 21.6 kg/h, and the line speed was 0.8 m/min. A laminate (F17) was obtained under the molding conditions. The total thickness of the laminate (F17) is 1000 μm, the thickness of the layer made of B11 is 300 μm near the center, and the ratio of the thickness of the thermoplastic resin (B) layer to the total thickness of the (B) layer and the (A) layer is It was 30.0%. The warp change amount of the laminated body (F17) under high temperature and high humidity environment was 1528 μm, which was unacceptable, the pencil hardness of the thermoplastic resin (B) was 3H, which was unacceptable, and the maximum height without breaking was 50 cm, which was unacceptable. Yes, the total light transmittance was 91.4% and the result was Haze, and the haze was 0.2%, which was a result of the comprehensive evaluation.

Table 2 shows the results obtained in Examples and Comparative Examples.

As described above, the resin laminate according to the present invention is a resin laminate in which the thermoplastic resin layer is laminated on the polycarbonate resin layer. The thermoplastic resin layer is a copolymer containing an aromatic vinyl monomer unit having a predetermined composition ratio, an unsaturated dicarboxylic acid anhydride monomer unit and an acrylic compound monomer unit, and has a predetermined total thickness. The ratio of the thickness of the thermoplastic resin layer to, and the total thickness of the polycarbonate-based resin layer and the thermoplastic resin layer is a predetermined thickness or more, the resin laminate according to the present invention is exposed to high temperature and high humidity. Also has excellent warpage and deformation resistance.

For example, a copolymer (b1-1 or b1-2) of an aromatic vinyl monomer unit, an unsaturated dicarboxylic acid anhydride monomer unit and an acrylic compound monomer unit having a predetermined composition ratio is used as a thermoplastic resin. The laminates (Examples 1 to 7) used were more warped in a high temperature and high humidity environment than the laminates (Comparative Examples 1 to 3) using the thermoplastic resin (d1-1) consisting only of acrylic compound monomer units. The amount of change is suppressed.
However, even a laminate using a copolymer of an aromatic vinyl monomer unit having a predetermined composition ratio, an unsaturated dicarboxylic acid anhydride monomer unit and an acrylic compound monomer unit as a thermoplastic resin, A laminate having a thin total thickness of the polycarbonate resin layer and the thermoplastic resin layer (Comparative Examples 5 to 6) and a laminate having a high ratio of the thickness of the thermoplastic resin layer to the total thickness (Comparative Example 7) are under high temperature and high humidity environment. The amount of change in the amount of warp has not been suppressed.
As described above, the laminate according to the present invention can suppress the amount of change in warpage of the conventional laminate of acrylic resin and polycarbonate under a high temperature and high humidity environment.

INDUSTRIAL APPLICABILITY As described above, the resin laminate according to the present invention which suppresses the amount of warp change under high temperature and high humidity environment is suitably used as a transparent base material, a transparent protective material, etc., and particularly for a touch panel front protective plate, OA equipment, or It can be suitably used as a front plate for portable electronic devices.

Claims (13)

A resin laminate comprising a polycarbonate resin (A) sheet containing a polycarbonate resin as a main component and a thermoplastic resin (B) laminated on at least one surface of the sheet,
Thermoplastic resin (B)
A copolymer containing 5 to 25 mass% of an aromatic vinyl monomer unit, 3 to 18 mass% of an unsaturated dicarboxylic acid anhydride monomer unit, and 57 to 92 mass% of an acrylic compound monomer unit (b ), and
The total thickness of the polycarbonate resin (A) layer and the thermoplastic resin (B) layer is 700 μm or more,
Layer and proportion from 0.1 to 25% der of the thickness of the layer of thermoplastic resin thermoplastic resin to the total thickness of the layer of (B) (B) of the polycarbonate resin (A) is,
A resin laminate in which the weight average molecular weight (Mw) of the copolymer (b) is 50,000 to 250,000 . The resin laminate according to claim 1, wherein the unsaturated dicarboxylic acid anhydride monomer unit contained in the copolymer (b) is maleic anhydride. The resin laminate according to claim 1, wherein the acrylic compound monomer unit contained in the copolymer (b) is a (meth)acrylic acid ester. The resin laminate according to any one of claims 1 to 3, wherein the aromatic vinyl monomer unit contained in the copolymer (b) is styrene. The weight average molecular weight of the polycarbonate resin (A) is a 25,000～75,000, resin laminate according to any one of claims 1-4. And the total light transmittance of the resin laminate is 75% or more, Haze of 10% or less, the resin laminate according to any one of claims 1-5. At least one thermoplastic layer of resin (B) layer and the polycarbonate resin (A) contains the ultraviolet absorber, the resin laminate according to any one of claims 1-6. Heat the surface of the plastic layer of resin (B) further comprises a hard coat layer, the resin laminate according to any one of claims 1-7. On one or both sides of the resin laminate, fingerprint-resistant treatment, antireflection treatment, anti-glare treatment, weathering processes, any one or more of the antistatic treatment and antifouling treatment is being performed, according to claim 1-8 The resin laminate according to any one of the above. Transparent substrate material comprising a resin laminate according to any one of claims 1-9. Transparent protective material comprising a resin laminate according to any one of claims 1-9. The touch panel Front protection containing resin laminate according to any one of claims 1-9. Containing resin laminate according to any one of claims 1 to 9 or the front plate for a portable electronic device for OA equipment.