TW201819512A - Method for producing resin laminate - Google Patents

Abstract

Provided is a method for producing a resin laminate excellent in transparency. A method for producing resin laminate comprising the following step (i) and step (ii): step (i): a step of melt-kneading at least a (meth) acrylic resin and a vinylidene fluoride resin to obtain a resin composition (a), wherein the resin composition (a) containing a (meth) acrylic resin by 65 to 55% by weight and a vinylidene fluoride resin by 65 to 55% by weight, based on the total resin contained in the resin composition (a), wherein the weight average molecular weight (Mw) of the (meth) acrylic resin is 100,000 to 300,000, and step (ii): a step of obtaining a resin laminate having at least an intermediate layer (A) formed of the resin composition (a) and thermoplastic resin layers (B) and (C) formed of thermoplastic resins (b) and (c) respectively present on two sides of the intermediate layer (A).

Description

   Manufacturing method of resin laminated body   

The present invention relates to a method for producing a resin laminate suitable for use in a display device and a resin composition used for producing the resin laminate.

In recent years, among display devices such as smart phones, portable game consoles, audio players, and tablet terminals, the number of people with touch screens is increasing. On the surface of such a display device, a glass sheet is generally used. However, in terms of a tendency to reduce the weight of the display device and processability, development of a plastic sheet as a substitute for the glass sheet is being performed. For example, in Patent Document 1, a plastic sheet as a substitute for glass sheets discloses a transparent sheet and a multilayer sheet including the transparent sheet. The transparent sheet includes a methacrylic resin and vinylidene fluoride. Resin, and it is described that these sheets are sufficient to satisfy transparency and specific permittivity.

    [Prior technical literature]         [Patent Literature]    

[Patent Document 1] Japanese Patent Laid-Open No. 2013-244604

However, it is known that if a methacrylic resin and a vinylidene fluoride resin are not uniformly mixed, there may be cases where a transparent portion and a white turbid portion are generated in the manufacture of a sheet, and it is known that even a transparent portion, such as In a high-temperature and high-humidity environment at 60 ° C and a relative humidity of 90%, transparent parts and white turbid parts are easily generated.

Therefore, an object of the present invention is to provide a method for producing a resin laminate having excellent transparency and a resin composition used for producing the resin laminate.

As a result of careful review in order to solve the above problems, the inventors have completed the present invention. That is, the present invention includes the following suitable aspects.

[1] A method for producing a resin laminate, comprising the following steps (i) and (ii): step (i): at least melt-kneading a (meth) acrylic resin and a vinylidene fluoride resin to obtain A step of the resin composition (a), wherein the resin composition (a) contains 35 to 45 mass% of a (meth) acrylic resin and 65 to 55 with respect to all resins contained in the resin composition (a). Mass-% vinylidene fluoride resin, (meth) acrylic resin has a weight average molecular weight (Mw) of 100,000 to 300,000; step (ii): a step of obtaining a resin laminate, the resin laminate having at least: composed of the resin The intermediate layer (A) formed by the object (a), and the thermoplastic resin layers (B) and (C) formed by the thermoplastic resins (b) and (c) respectively present on both sides of the intermediate layer (A) .

[2] The method according to [1], wherein in step (i), a granular resin composition (a) is obtained.

[3] The method according to [1] or [2], wherein in step (ii), a resin laminate is obtained by coextrusion.

[4] The method according to any one of [1] to [3], wherein in step (i), melting is performed so that a composition unevenness of the resin composition (a) becomes 6% by mass or less Mixed.

[5] The method according to any one of [1] to [4], wherein the alkali metal content in the resin composition (a) is 50 ppm with respect to all the resins contained in the resin composition (a) the following.

[6] The method according to any one of [1] to [5], wherein the (meth) acrylic resin is the following (a1) and / or (a2): (a1) The homopolymer and (a2) contain 50 to 99.9% by mass of a structural unit derived from methyl methacrylate with respect to all the structural units constituting the polymer, and 0.1 to 50% by mass of the structural unit derived from the formula (1) A copolymer of at least one building unit of (meth) acrylate;

[Wherein R ₁ represents a hydrogen atom or a methyl group; when R ₁ is a hydrogen atom, R ₂ represents an alkyl group having 1 to 8 carbon atoms; when R ₁ is a methyl group, R ₂ represents an alkyl group having 2 to 8 carbon atoms ].

[7] The method according to any one of [1] to [6], wherein the vinylidene fluoride resin is polyvinylidene fluoride.

[8] The method according to any one of [1] to [7], wherein the melt mass flow rate of the vinylidene fluoride resin is 0.1 to 40 g / 10 minutes measured at 230 ° C with a load of 3.8 kg.

[9] The method according to any one of [1] to [8], wherein an average film thickness of the resin laminate is 100 to 2000 μm, and a film thickness of the thermoplastic resin layers (B) and (C) The average values are 10 to 200 μm, respectively.

[10] The method according to any one of [1] to [9], wherein the Vicat softening temperature of the resins contained in the thermoplastic resins (b) and (c) are 100 to 100, respectively. 160 ° C.

[11] The method according to any one of [1] to [10], wherein the thermoplastic resins (b) and (c) each contain a (meth) acrylic resin or a polycarbonate resin.

[12] The method according to any one of [1] to [11], wherein the thermoplastic resin (b) is contained in the polycarbonate resin and all the resins contained in each of the thermoplastic resins (b) and (c). And (c) each contain 0.005 to 2.0% by mass of an ultraviolet absorbent.

[13] The method according to any one of [1] to [11], wherein the thermoplastic resins (b) and (c) are based on all the resins contained in each of the thermoplastic resins (b) and (c). Each contains 50% by mass or more of a (meth) acrylic resin.

[14] The method according to [13], wherein the weight average molecular weight of the (meth) acrylic resin contained in the thermoplastic resins (b) and (c) is 50,000 to 300,000.

[15] A resin composition comprising a resin composition containing at least a (meth) acrylic resin and a vinylidene fluoride resin, and containing 35 to 45% by mass of the total resin contained in the resin composition. (Meth) acrylic resin and 65 to 55 mass% of vinylidene fluoride resin, the weight average molecular weight (Mw) of the (meth) acrylic resin is 100,000 to 300,000, and the composition unevenness of the resin composition is 6 mass% or less .

According to the production method of the present invention, a resin laminate having excellent transparency can be obtained.

1‧‧‧ one-shaft extruder (extrusion of the melt of thermoplastic resin b)

2‧‧‧ one-shaft extruder (extrusion of melt of resin composition a)

3‧‧‧ one-shaft extruder (extrusion of the melt of thermoplastic resin c)

4‧‧‧Feeding Department

5‧‧‧Multi-manifold Die

6‧‧‧ film-like molten resin laminate

7‧‧‧The first cooling roller

8‧‧‧ 2nd cooling roller

9‧‧‧3rd cooling roller

10‧‧‧Resin laminate

10A‧‧‧Intermediate Level (A)

10B‧‧‧Thermoplastic resin layer (B)

10C‧‧‧Thermoplastic resin layer (C)

11‧‧‧ polarizing plate

12‧‧‧ Optical Adhesive Layer

13‧‧‧ LCD cell

14‧‧‧ Liquid crystal display device

FIG. 1 is a schematic diagram of a manufacturing apparatus for a resin laminate obtained according to the present invention used in the example.

FIG. 2 is a schematic cross-sectional view showing a preferred form of a liquid crystal display device including the resin laminate obtained according to the present invention.

The resin laminate obtained by the manufacturing method of the present invention is a resin laminate having at least an intermediate layer (A), and a thermoplastic resin layer (B) and a thermoplastic resin layer (C) that are respectively present on both sides of the intermediate layer (A). The body is obtained by a method including the following steps (i) and (ii). In other words, the present invention is a method for manufacturing a resin laminate having at least a layered thermoplastic resin layer (B) / intermediate layer (A) / thermoplastic resin layer (C), and the method includes the following step (i) and steps (ii).

    <Step (i)>    

Step (i) is a step of at least melt-kneading a (meth) acrylic resin and a vinylidene fluoride resin to obtain a resin composition (a).

Examples of the (meth) acrylic resin include: homopolymers of (meth) acrylic monomers such as (meth) acrylates and (meth) acrylonitrile; and copolymerization of two or more (meth) acrylic monomers. Copolymers of (meth) acrylic monomers and monomers other than (meth) acrylic monomers. In the present specification, the term "(meth) acrylic acid" means "acrylic acid" or "methacrylic acid".

From the viewpoint of easily improving the hardness, weather resistance, and transparency of the resin laminate, a (meth) acrylic resin is preferably a methacrylic resin. The methacrylic resin is a polymer of monomers mainly composed of methacrylate (alkyl methacrylate), and examples thereof include homopolymers (polyalkyl methacrylate) of methacrylate, and two or more kinds Copolymers of methacrylate, copolymers of monomers other than 50% by mass of methacrylate and monomers other than 50% by mass of methacrylate, and the like. The copolymer of methacrylate and a monomer other than methacrylate is preferably 70% by mass or more with respect to the total amount of monomers from the viewpoint of easily improving the optical properties and weather resistance of the resin laminate. The copolymer of methacrylate and 30% by mass or less of other monomers is more preferably a copolymer of 90% by mass or more of methacrylate and 10% by mass or less of other monomers.

Examples of the monomer other than the methacrylate include an acrylate and a monofunctional monomer having one polymerizable carbon-carbon double bond in the molecule.

Examples of the monofunctional monomer include: styrene monomers such as styrene, α-methylstyrene, and vinyltoluene; cyanoolefins such as acrylonitrile and methacrylonitrile; acrylic acid; methacrylic acid; maleic anhydride ; N-substituted maleimidine and the like.

From the standpoint of heat resistance, (meth) acrylic resins can be copolymerized with N-substituted maleimines such as phenylmaleimide, cyclohexylmaleimide, and methylmaleimide. It is also possible to introduce a lactone ring structure, a glutaric anhydride structure, or a glutarimide structure into the molecular chain (also referred to as the main skeleton or the main chain in the polymer).

From the viewpoint of easily improving the hardness, weather resistance, and transparency of the resin laminate, the (meth) acrylic resin is preferably the following (a1) and / or (a2) copolymer: (a1) methyl A homopolymer of methyl acrylate and (a2) a copolymer containing a structural unit derived from methyl methacrylate and at least one structural unit derived from a (meth) acrylate represented by formula (1) constitute a copolymer. For all the structural units of the substance, the aforementioned structural unit derived from methyl methacrylate is 50 to 99.9% by mass, preferably 70.0 to 99.8% by mass, and more preferably 80.0 to 99.7% by mass. The foregoing is derived from the formula (1 ) At least one structural unit of the (meth) acrylate is 0.1 to 50% by mass, preferably 0.2 to 30% by mass, and more preferably 0.3 to 20% by mass;

[Wherein R ₁ represents a hydrogen atom or a methyl group; when R ₁ is a hydrogen atom, R ₂ represents an alkyl group having 1 to 8 carbon atoms; when R ₁ is a methyl group, R ₂ represents an alkyl group having 2 to 8 carbon atoms ].

Among them, the content of each structural unit can be analyzed by thermal decomposition gas chromatography, and can be calculated by measuring the peak area corresponding to each monomer.

In formula (1), R ₁ represents a hydrogen atom or a methyl group; when R ₁ is a hydrogen atom, R ₂ represents an alkyl group having 1 to 8 carbons; when R ₁ is a methyl group, R ₂ represents 2 to 8 carbons Of alkyl. Examples of the alkyl group having 2 to 8 carbon atoms include ethyl, propyl, isopropyl, butyl, second butyl, third butyl, pentyl, hexyl, heptyl, and octyl. From the viewpoint of heat resistance, R _{2 is} preferably an alkyl group having 2 to 4 carbon atoms, and more preferably an ethyl group.

The weight average molecular weight (hereinafter also referred to as Mw) of the (meth) acrylic resin contained in the resin composition (a) is 100,000 to 300,000. If Mw is lower than the lower limit described above, the transparency of the resin laminate is insufficient when exposed to a high-temperature and high-humidity environment. If Mw is higher than the upper limit described above, film-forming properties cannot be obtained when the resin laminate is produced. From the viewpoint of easily improving the transparency of the resin laminate when exposed to a high temperature and high humidity environment, the Mw of the (meth) acrylic resin is preferably 120,000 or more, and more preferably 150,000 or more. From the viewpoint of film-forming properties when producing a resin laminate, the Mw of the (meth) acrylic resin is preferably 250,000 or less, and more preferably 200,000 or less. The weight average molecular weight is measured by colloidal permeation chromatography (GPC) measurement.

When measured with a load of 3.8 kg at 230 ° C, the melt mass flow rate (hereinafter referred to as MFR) of the (meth) acrylic resin is usually 0.1 to 20 g / 10 minutes, preferably 0.2 to 5 g / 10 minutes, and more preferably It is 0.5 to 3 g / 10 minutes. When MFR is below the above upper limit, the strength of the obtained film can be easily increased, so it is preferable. From the viewpoint of the film-forming property of the resin laminate, it is preferably above the above lower limit. MFR can be measured in accordance with the method specified in JIS K 7210: 1999 "Test Methods for Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Plastics-Thermoplastics". Poly (methyl methacrylate) -based materials are measured at a temperature of 230 ° C and a load of 3.80 kg (37.3 N) in accordance with the JIS standards.

From the viewpoint of heat resistance, the Ficca softening temperature (hereinafter referred to as VST) of the (meth) acrylic resin is preferably 90 ° C or higher, more preferably 100 ° C or higher, and even more preferably 102 ° C or higher. The upper limit of VST is not particularly limited, but it is usually 150 ° C or lower. VST can be measured according to JIS K 7206: 1999 by the B50 method described therein. VST can be adjusted to the above range by adjusting the type of monomer and its ratio.

The (meth) acrylic resin can be prepared by polymerizing the monomers by a known method such as suspension polymerization or bulk polymerization. At this time, MFR, Mw, VST, etc. can be adjusted to a preferable range by adding an appropriate chain transfer agent. As a chain transfer agent, a suitable commercial item can be used. The amount of the chain transfer agent to be added may be appropriately determined depending on the type of monomer, its ratio, the desired characteristics, and the like.

Examples of the vinylidene fluoride resin contained in the resin composition (a) include a homopolymer of vinylidene fluoride and a copolymer of vinylidene fluoride and other monomers. From the viewpoint of easily improving the transparency of the obtained film, the vinylidene fluoride resin is preferably made of trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether, and ethylene. A copolymer of at least one monomer selected from the group with vinylidene fluoride; and / or a homopolymer of polyvinylidene fluoride (polyvinylidene fluoride), more preferably polyvinylidene fluoride.

The weight average molecular weight (Mw) of the vinylidene fluoride resin contained in the resin composition (a) is preferably 100,000 to 500,000, more preferably 150,000 to 450,000, still more preferably 200,000 to 450,000, and particularly preferably 350,000 to 450,000 . If Mw is above the lower limit, it is preferred that the resin laminate of the present invention is easily exposed to a high temperature and high humidity environment (for example, 60 ° C. and a relative humidity of 90%) to improve the transparency of the resin laminate. Moreover, if Mw is below the said upper limit, it is easy to improve the film-forming property of a resin laminated body, and it is preferable. The weight average molecular weight is measured by a colloidal permeation chromatography (GPC) measurement.

Measured at a load of 3.8 kg at 230 ° C, the melt mass flow rate (MFR) of the vinylidene fluoride resin is preferably from 0.1 to 40 g / 10 minutes, more preferably from 0.1 to 30 g / 10 minutes, and even more preferably from 0.1 to 25g / 10 minutes. MFR is more preferably 0.2 g / 10 minutes or more, and still more preferably 0.5 g / 10 minutes or more. The MFR is more preferably 20 g / 10 minutes or less, still more preferably 5 g / 10 minutes or less, and particularly preferably 2 g / 10 minutes or less. When MFR is below the above-mentioned upper limit, it is easy to suppress a decrease in transparency when the resin laminate is used for a long period of time, so it is preferable. If MFR is more than the said lower limit, since it is easy to improve the film-forming property of a resin laminated body, it is preferable. MFR can be measured in accordance with the method specified in JIS K 7210: 1999 "Test Methods for Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Plastics-Thermoplastics".

Industrially, vinylidene fluoride resin can be produced by a suspension polymerization method or an emulsion polymerization method. Suspension polymerization is carried out by using water as the medium, dispersing the monomers in the medium into droplets and dispersing them, and using the organic peroxide dissolved in the monomers as the polymerization initiator to carry out polymerization. A granular polymer of 100 to 300 μm was obtained. Compared with the emulsified polymer, the suspension polymer is simpler in manufacturing steps and excellent in powder handling properties, and it does not contain an emulsifier or salting-out agent containing an alkali metal such as an emulsified polymer, so it is preferable.

A commercially available vinylidene fluoride resin can be used. Examples of commercially available products include Kureha Corporation's "KFpolymer (registered trademark) T # 1300, T # 1100, T # 1000, T # 850, W # 850, W # 1000, W # 1100 and W # 1300 "," SOLFF (registered trademark) 6012, 6010 and 6008 "manufactured by Solvay.

In step (i), all the resins contained in the resin composition (a) are melt-kneaded at least 35 to 45 mass% of a (meth) acrylic resin and 65 to 55 mass% of a vinylidene fluoride resin. More preferably, 37 to 45% by mass of (meth) acrylic resin and 63 to 55% by mass of vinylidene fluoride resin are melt-kneaded, and more preferably 38 to 45% by mass of (meth) acrylic resin and 62 are melt-kneaded. To 55 mass% of vinylidene fluoride resin, especially 38 to 43 mass% of (meth) acrylic resin and 62 to 57 mass% of vinylidene fluoride resin. When the amount of the (meth) acrylic resin is at least the above-mentioned lower limit, sufficient transparency can be obtained, and when it is at most the above-mentioned upper limit, sufficient dielectric constant can be obtained. When the amount of the vinylidene fluoride resin is at least the above lower limit value, a sufficient dielectric constant can be obtained, and when it is at most the above upper limit value, durability and sufficient transparency can be obtained.

In the present invention, since at least step (i) of melt-kneading the (meth) acrylic resin and the vinylidene fluoride resin in the aforementioned ratio to obtain a resin composition (a) is included, the resin composition (a) can be improved The miscibility of the contained (meth) acrylic resin and vinylidene fluoride resin can obtain a uniform resin composition (a). Therefore, the homogeneity of the intermediate layer (A) formed from the resin composition (a) in the step (ii) can be further improved, and a resin laminate having excellent transparency can be obtained. Furthermore, it can maintain excellent transparency even when used in a high-temperature and high-humidity environment (for example, an environment having a temperature of 60 ° C and a humidity of 90%). Furthermore, according to the manufacturing method of the present invention, even if the production scale of the resin laminate is enlarged, a resin laminate having sufficient transparency can be obtained.

From the viewpoint of easily melting the resin and improving the miscibility, the melting temperature is preferably 150 ° C or higher, more preferably 170 ° C or higher, and still more preferably 200 ° C or higher. From the viewpoint of easily suppressing the thermal decomposition of the resin, It is preferable that the temperature is 350 ° C or lower, more preferably 320 ° C or lower, and even more preferably 300 ° C or lower. In addition, from the viewpoint of easily improving the mixing property, the shear rate during melt kneading is preferably 10 / second or more, more preferably 20 / second or more, and even more preferably 30 / second or more; from the viewpoint of easy suppression From the viewpoint of resin decomposition, it is preferably 1,000 / sec or less, more preferably 700 / sec or less, and still more preferably 500 / sec or less.

The melt-kneading time is not particularly limited as long as it can be sufficiently melt-kneaded, and is preferably 10 to 1,000 seconds, more preferably 20 to 600 seconds, and even more preferably 30 to 300 seconds. Further, the melt-kneading may be performed under normal pressure or reduced pressure, or may be performed under vacuum.

The equipment used for the melt-kneading can be a common mixer or a kneader, and examples thereof include a one-axis kneader, a multi-axis kneader (e.g., a two-axis kneader, etc.), a Henschel mixer, a Banbury mixer, Kneader, roll mill, etc. When the shear rate is increased within the above range, a high-shear processing device or the like can be used. In particular, melt-kneading using an extruder pelletizer, an extruder, etc., especially a biaxial extruder pelletizer, a biaxial extruder, etc., can improve the mixing property or the kneading property, and the obtained resin laminate is easy to appear It is preferable because it has excellent transparency. Further, two or more types of mixing machines and kneading machines may be used in combination to perform melt kneading.

In a preferred aspect, an extrusion granulator (e.g., a two-shaft) Extruder pelletizer, etc.) or extruder (for example, biaxial extruder, etc.) for melt kneading.

The shear rate can be adjusted by conventional methods. When using an extruder pelletizer or extruder, it can be controlled by changing conditions such as the shape of the spiral, the ratio of the spiral length (L) to the spiral diameter (D) (L / D), and the number of spiral revolutions.

The resin composition (a) can also be obtained by melt-kneading a (meth) acrylic resin and a vinylidene fluoride resin, and one or more other resins different from these resins. When other resins are contained, the type of the resin laminate is not particularly limited as long as the transparency of the resin laminate is not significantly impaired. From the viewpoint of the hardness and weather resistance of the resin laminate, the amount of other resins is preferably 15% by mass or less, more preferably 10% by mass or less, with respect to all the resins contained in the resin composition (a). Still more preferably, it is 5 mass% or less. Other resins include, for example, polycarbonate resin, polyamide resin, acrylonitrile-styrene copolymer, methyl methacrylate-styrene copolymer, polyethylene terephthalate, and the like. The resin composition (a) may further include other resins, but from the viewpoint of transparency, the amount of other resins is preferably 1% by mass or less, and more preferably, the resin contained in the resin composition (a) is only (Meth) acrylic resin and vinylidene fluoride resin.

The resin composition (a) may further include various additives generally used within a range not hindering the effects of the present invention. Examples of the additives include stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, foaming agents, smoothing agents, mold release agents, antistatic agents, flame retardants, mold release agents, polymerization inhibitors, and flame retardant additives. , Reinforcing agents, nucleating agents, blueing agents and other coloring agents.

Examples of the colorant include a compound having an anthraquinone skeleton and a compound having a phenol blue pigment skeleton. From the viewpoint of heat resistance, among these, a compound having an anthraquinone skeleton is particularly preferable.

When the resin composition (a) further contains a colorant, the content of the colorant is appropriately selected depending on the purpose, the type of the colorant, and the like. When a bluing agent is used as a coloring agent, the content of the bluing agent may be about 0.01 to 10 ppm for all resins contained in the resin composition (a) containing the bluing agent. The content is preferably 0.01 ppm or more, more preferably 0.05 ppm or more, and still more preferably 0.1 ppm or more; more preferably, 7 ppm or less, more preferably 5 ppm or less, still more preferably 4 ppm or less, and particularly preferably 3 ppm or less . The bluing agent can be suitably used by a conventional person, and examples of each trade name include: Macrolex (registered trademark) Blue RR (manufactured by BAYER), Macrolex (registered trademark) Blue 3R (manufactured by BAYER), Sumiplast (registered trademark) Viloet B (Made by Sumika chemtex) and Polysynthren (registered trademark) Blue RLS (made by CLARIANT), Diaresin Violet D, Diaresin Blue G, and Diaresin Blue N (the above are made by Mitsubishi Chemical Corporation).

The ultraviolet absorber is not particularly limited, and various conventionally known ultraviolet absorbers can be used. For example, an ultraviolet absorber having a maximum absorption at 200 to 320 nm or 320 to 400 nm can be listed. Specifically, three UV absorber, benzophenone UV absorber, benzotriazole UV absorber, benzoate UV absorber, cyanoacrylate UV absorber. The ultraviolet absorber can be used alone or in combination of two or more of them. From the viewpoint of more effective protection against damage caused by ultraviolet rays, it is preferable to use at least one ultraviolet absorber having a large absorption at 200 to 320 nm and at least one ultraviolet absorbent having a maximum absorption at 320 to 400 nm. As the ultraviolet absorber, a commercially available product can be used, and examples thereof include "Kemisorb 102" (2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4- (N-octyloxyphenyl) -1,3,5-tri ) (Absorbance 0.1), "ADK STAB LA-F70" (2,4,6-ginseng (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5 manufactured by ADEKA Corporation -three ) (Absorbance 0.6), "ADK STAB LA-31, LA-31RG, LA-31G"(2,2'-methylenebis (4- (1,1,3,3-tetramethylbutyl)- 6- (2H-benzotriazol-2-yl) phenol (absorbance 0.2), "ADK STAB LA-46" (2- (4,6-diphenyl-1, 3,5-three 2-yl) -5- (2- (2-ethylhexyloxy) ethoxy) phenol) (absorbance 0.05) or "TINUVIN 1577" (2,4-diphenyl) manufactured by BASF JAPAN Co., Ltd. 6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-tri ) (Absorbance 0.1) and so on. The illustrated absorbance of the ultraviolet absorbent is a value obtained by dissolving the ultraviolet absorbent in chloroform so as to have a concentration of 10 mg / L, and measuring the value at 380 nm with a spectrophotometer U-4100 manufactured by HITACHI.

When the resin composition (a) further contains an ultraviolet absorber, the content of the ultraviolet absorber in each layer may be appropriately selected depending on the purpose, the type of the ultraviolet absorber, and the like. For example, for all the resins contained in the resin composition (a) containing an ultraviolet absorber, the content of the ultraviolet absorber may be about 0.005 to 2.0% by mass. The content of the ultraviolet absorber is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and still more preferably 0.03% by mass or more. The content of the ultraviolet absorber is preferably 1.5% by mass or less, and more preferably 1.0% by mass or less. From the viewpoint of easily improving the ultraviolet absorption effect, it is preferable that the content of the ultraviolet absorbent is at least the above lower limit, and when it is below the above upper limit, it is easy to prevent the color tone (for example, yellowness YI) of the resin laminate from changing. It is better. For example, it is preferable to use the above-mentioned commercially available "ADK STAB LA-31, LA-31RG, LA-31G" in the above-mentioned amount.

When the resin composition (a) contains the other resin and / or the additive, the other resin and / or additive can be melt-kneaded with the (meth) acrylic resin and vinylidene fluoride resin to obtain the resin composition (a). The resin composition (a) can also be obtained by melt-kneading the (meth) acrylic resin and vinylidene fluoride resin and adding other resins and / or additives. From the viewpoint of improving the homogeneity of the resin composition (a) and improving the transparency of the resin laminate, the other resins and / or additives are melt-kneaded with (meth) acrylic resin and vinylidene fluoride resin together. Better.

When the resin composition (a) contains other resins and / or additives, the resin composition (a) may be melt-kneaded under conditions that sufficiently melt the (meth) acrylic resin and vinylidene fluoride resin with other resins and / or additives. For example, the kneading machine or the kneading machine exemplified above may be used to perform the melt kneading at the melting temperature, the melting time, the shear rate, and the like exemplified above. When the resin composition (a) contains other resins and / or additives, the preferable melting temperature, melting time, shear rate, and mixing machine or kneading machine exemplified above are also suitable.

For all the resins contained in the intermediate layer (A), the alkali metal content in the resin composition (a) is preferably 50 ppm or less, more preferably 30 ppm or less, still more preferably 10 ppm or less, and particularly preferably 1 ppm or less. If the content of the alkali metal in the resin composition (a) is equal to or less than the above-mentioned upper limit, it is easy to suppress the decrease in transparency of the resin laminate when it is used for a long time in a high-temperature and high-humidity environment. The lower limit value of the content of the alkali metal in the resin composition (a) is 0, and from the viewpoint of easily suppressing the decrease in the transparency of the resin laminate, it is excellent that the alkali metal is not substantially contained. Among them, the (meth) acrylic resin and / or vinylidene fluoride resin contained in the resin composition (a) are trace amounts of emulsifiers and the like used in the manufacturing process. Therefore, alkali metals such as sodium and potassium derived from the remaining emulsifier contained in the resin composition (a) are, for example, 0.05 ppm or more. In particular, when the (meth) acrylic resin and / or vinylidene fluoride resin contained in the resin composition (a) is obtained by emulsion polymerization, the amount of the emulsifier remaining in the resin increases, and the resin composition ( The alkali metal content in a) will also increase. From the viewpoint of easily suppressing a decrease in the transparency of the resin laminate, it is preferable to use a resin having a low alkali metal content as the (meth) acrylic resin and vinylidene fluoride resin contained in the resin composition (a).

In order to keep the alkali metal content in the resin within the above range, it is only necessary to reduce the amount of the alkali metal-containing compound used in the resin during polymerization, or increase the washing step after polymerization to remove the alkali metal-containing compound. The alkali metal content can be obtained, for example, by inductively coupled plasma mass spectrometry (ICP / MS). As an inductively coupled plasma mass analysis method, for example, the sample particles to be measured may be subjected to a high-temperature ash melting method, a high-temperature ash acid dissolving method, a Ca-added ash acid dissolving method, a combustion absorption method, or a low-temperature ash acid dissolving method A suitable method is to ash the sample and dissolve it in acid, make the volume of the obtained dissolving solution, and measure the content of alkali metal by inductively coupled plasma mass analysis.

In step (i), the resin composition (a) obtained by melt-kneading is preferably formed into a solid shape, a powder shape, or the like before being supplied to step (ii). The specific shape of the solid shape can be exemplified: granular, ring-shaped, sheet-like, honeycomb-shaped and the like. Among these, especially when the intermediate | middle layer (A) is formed from the resin composition (a) shape | molded in a granular form, handling property can be improved, and it is preferable.

Granular means spherical, cylindrical, elliptical, polygonal (such as triangular, quadrangular, pentagonal, hexagonal, etc.) solid shapes with a certain thickness, and their cross-sections are circular, oval, polygonal, etc. . The surface of the granular resin composition (a) may be uneven, or may be a slightly spherical shape, a slightly cylindrical shape, a slightly elliptical column shape, a slightly polygonal column, or the like. The granular resin composition (a) has, for example, a particle diameter of 1 to 5 mm, preferably a particle diameter of 1.5 to 4 mm, and a particle length of, for example, 2 to 10 mm, and preferably a particle length of 3 to 8 mm. The particle diameter refers to the average value of the short and long diameters, and the particle length refers to the maximum length of the particles in a direction perpendicular to the cross section.

The method for forming the melt-kneaded resin composition (a) into pellets is not particularly limited, and may be a conventional method. For example, an extruder pelletizer (such as a biaxial extruder pelletizer) can be used to melt the pellets. The kneaded resin composition (a) is spit out of a water layer by a die lip to cool and cut into pellets.

In the present invention, in step (i), the components contained in the resin composition (a), that is, the aforementioned (meth) acrylic resin and the aforementioned vinylidene fluoride resin, and other resins as necessary, and Additives are melt-kneaded so that the composition unevenness of the resin composition (a) is preferably 6% by mass or less. The composition unevenness of the resin composition (a) is more preferably 5.5% by mass or less, and more preferably 5 mass% or less, still more preferably 4 mass% or less, particularly preferred is 3 mass% or less, and even more preferably 2 mass% or less. In addition, the lower limit of the composition unevenness is not particularly limited, but may be, for example, 0% by mass or more, 0.5% by mass or more, or 1% by mass or more. When melt-kneading is performed so that the composition unevenness falls within the aforementioned range, a uniform intermediate layer (A) can be obtained, and the transparency of the resin laminate can be further improved. In addition, even when used for a long time in an environment of high temperature and high humidity (for example, an environment of a temperature of 60 ° C and a humidity of 90%), excellent transparency can be maintained. Moreover, even if the production scale of a resin laminated body is expanded, a resin laminated body which has sufficient transparency can be obtained. In addition, the non-uniform composition (mass%) indicates that the resin composition (a) was measured by Fourier transform infrared spectrometry (FT-IR method), nuclear magnetic resonance spectrometry (NMR method), and the like. When the content of vinylidene fluoride resin (% by mass) is contained, the content of resin composition (a) with the highest content of vinylidene fluoride resin (upper limit) and the content of resin composition (a) with the lowest amount (lower limit) )Difference.

The ratio of the resin and the additive contained in the resin composition (a) is described based on the resin contained in the resin composition (a). However, the resin composition (a) in step (ii) can form an intermediate The layer (A), in other words, the resin and additives contained in the above-mentioned resin composition (a), and the ratio thereof are also the resin and additives contained in the intermediate layer (A), and the ratio thereof. The same applies to the content of the alkali metal. The amount of the alkali metal contained in the resin composition (a) may also be referred to as the amount of the alkali metal contained in the intermediate layer (A).

    <Step (ii)>    

Step (ii) is a step of obtaining a resin laminate, the resin laminate having at least: an intermediate layer (A) formed of the foregoing resin composition (a), and two sides of the intermediate layer (A). The thermoplastic resin layers (B) and (C) formed by the aforementioned thermoplastic resins (b) and (c), respectively.

The thermoplastic resins (b) and (c) include at least one thermoplastic resin. From the viewpoint of easily improving the moldability, it is preferable that the thermoplastic resins (b) and (c) contain 60% by mass or more of all the resins contained in each of the thermoplastic resins (b) and (c). The thermoplastic resin is preferably 70% by mass or more, and even more preferably 80% by mass or more. The upper limit of the amount of the thermoplastic resin is 100% by mass. Examples of the thermoplastic resin include (meth) acrylic resin, polycarbonate resin, and cycloolefin resin. From the viewpoint of easily improving the adhesion between the thermoplastic resin layers (B) and (C) and the intermediate layer (A), the thermoplastic resin is preferably a (meth) acrylic resin or a polycarbonate resin. The thermoplastic resins (b) and (c) may include the same thermoplastic resin, or may include thermoplastic resins that are different from each other. From the viewpoint of improving the transparency of the resin laminated body and from the viewpoint of easily suppressing warpage, it is preferred that the thermoplastic resin layers (B) and (C) contain the same thermoplastic resin.

From the viewpoint of the heat resistance of the resin laminate, the resins contained in the thermoplastic resins (b) and (c) preferably have a Ficca softening temperature of 100 to 160 ° C, more preferably 102 to 155 ° C, Still more preferably, it is 102 to 152 ° C. Wherein, when the thermoplastic resin contains one kind of resin, the above-mentioned Ficca softening temperature is the Ficca softening temperature of the resin, and when the thermoplastic resin contains two or more kinds of resins, the above-mentioned Ficca softening temperature is a Ficca which is a mixture of plural resin Softening temperature. The Ficca softening temperature of the resins contained in the thermoplastic resins (b) and (c) is measured in accordance with the B50 method specified in JIS K 7206: 1999 "Plastic-Thermoplastic-Ficca Softening Temperature (VST) Test Method". The Ficca softening temperature can be measured using a heat distortion tester (for example, a "148-6 type" manufactured by Yasuda Seiki Seisakusho Co., Ltd.). The measurement system can be performed using a test piece obtained by press-molding each raw material to a thickness of 3 mm.

For the purpose of improving the strength and elasticity of the thermoplastic resin layer, the thermoplastic resins (b) and (c) may further include other resins (for example, thermosetting resins such as fillers and resin particles) other than the thermoplastic resin. At this time, for all the resins contained in the thermoplastic resins (b) and (c), the amount of other resins is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less. . The lower limit of the amount of other resins is 0% by mass.

The thermoplastic resins (b) and (c) may further contain various additives that are generally used, as long as the effects of the present invention are not hindered. The range of additives and ratios contained in each thermoplastic resin may be the same as the range of additives and ratios contained in the resin composition (a), and the ranges of additives and ratios are preferably the same.

The thermoplastic resins (b) and (c) preferably contain a (meth) acrylic resin or a polycarbonate resin from the viewpoint of good moldability and easy improvement in adhesion with the intermediate layer (A).

One aspect of the present invention will be described below. The thermoplastic resins (b) and (c) include a (meth) acrylic resin. In this aspect, the thermoplastic resins (b) and (c) include one or more (meth) acrylic resins. From the viewpoint of the surface hardness of the thermoplastic resin layers (B) and (C), the thermoplastic resins (b) and (c) refer to all the resins contained in each of the thermoplastic resins (b) and (c), respectively. A (meth) acrylic resin containing 50% by mass or more is preferable, 60% by mass or more is more preferable, and 70% by mass or more is even more preferable.

Examples of the (meth) acrylic resin include resins described in the (meth) acrylic resin contained in the resin composition (a). Unless otherwise specified, the (meth) acrylic resin described in the resin composition (a) is preferably the same as the (meth) acrylic resin contained in the thermoplastic resins (b) and (c). The (meth) acrylic resin contained in the thermoplastic resins (b) and (c) may be the same as or different from the (meth) acrylic resin contained in the resin composition (a).

From the viewpoint of good molding processability and easy improvement of mechanical strength, the weight average molecular weight (Mw) of the (meth) acrylic resin is preferably 50,000 to 300,000, and more preferably 70,000 to 250,000. The weight-average molecular weight is measured by colloidal permeation chromatography (GPC) measurement.

In this aspect, the thermoplastic resins (b) and (c) may further include a thermoplastic resin other than a (meth) acrylic resin. The thermoplastic resin other than the (meth) acrylic resin is preferably a thermoplastic resin compatible with the (meth) acrylic resin. Specifically, a methyl methacrylate-styrene-maleic anhydride copolymer (e.g., "RESISFY" manufactured by Denki Chemical Industry) and a methyl methacrylate-methacrylic acid copolymer (e.g., "ALTUGLAS" manufactured by ARKEMA) HT121 "), polycarbonate resin. From the viewpoint of heat resistance, according to JIS K 7206: 1999, the Ficca softening temperature of thermoplastic resins other than (meth) acrylic resins is preferably 115 ° C or higher, more preferably 117 ° C or higher Above 120 ° C is even better. From the viewpoint of heat resistance and surface hardness, it is preferred that the thermoplastic resins (b) and (c) are substantially free of vinylidene fluoride resin.

In this aspect, from the viewpoint of improving the damage resistance, the pencil hardness of the thermoplastic resin layers (B) and (C) formed from the thermoplastic resins (b) and (c), respectively, is preferably HB or more. It is more preferably F or more, and still more preferably H or more.

Next, another aspect of the present invention in which the thermoplastic resins (b) and (c) are polycarbonate resins will be described below. In this aspect, the thermoplastic resins (b) and (c) include one or more polycarbonate resins. From the viewpoint of impact resistance, the polycarbonate resin contained in the thermoplastic resins (b) and (c) is 60% by mass or more with respect to all the resins contained in the respective thermoplastic resins (b) and (c). More preferably, 70% by mass or more is more preferable, and 80% by mass or more is more preferable.

Examples of the polycarbonate resin include a phosgene method in which various dihydroxy diaryl compounds are reacted with phosgene, or a dihydroxy diaryl compound is reacted with a carbonate such as diphenyl carbonate. Specific examples of the polymer obtained by the transesterification method include polycarbonate resins made of 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A).

Examples of the dihydroxydiaryl compound other than bisphenol A include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3 -Methylphenyl) propane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2 -Bis (4-hydroxy-3,5-dibromophenyl) propane, bis (hydroxyaryl) alkanes of 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane; such as 1 Bis (hydroxyaryl) cycloalkanes of 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane; such as 4,4'-dihydroxydi Dihydroxy diaryl ethers of phenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether; such as dihydroxydi of 4,4'-dihydroxydiphenyl sulfide Aryl sulfide; such as 4,4'-dihydroxydiphenylarylene, 4,4'-dihydroxy-3,3'-dimethyldiphenylarylene ; Such as 4,4'-dihydroxydiphenylfluorene, 4,4'-dihydroxy-3,3'-dimethyldiphenylfluorene's dihydroxydiarylfluorenes.

These can be used alone or in combination of two or more kinds. , Dipiperidine hydroquinone, resorcinol, 4,4'-dihydroxydibenzene, and the like.

The dihydroxyaryl compound described above can be used in combination with a trivalent or higher phenol compound as shown below. Examples of trivalent or higher phenols include resorcinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, and 2,4,6-dimethyl- 2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxybenzene ) -Ethane and 2,2-bis- [4,4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

Examples of the polycarbonate resin other than the polycarbonate resin include polycarbonates synthesized from isosorbide and an aromatic diol. Examples of the polycarbonate include "DURABIO (registered trademark)" manufactured by Mitsubishi Chemical Corporation.

A commercially available polycarbonate resin can be used, and examples thereof include: "CALIBRE (registered trademark) 301-4, 301-10, 301-15, 301-22, 301-30, 301-40, manufactured by Sumika Styron Polycarbonate Co., Ltd., SD2221W, SD2201W, TR2201 ", etc.

In this aspect, the weight average molecular weight (Mw) of the polycarbonate resin is preferably 20,000 to 70,000, and more preferably 25,000 to 60,000, from the viewpoint of easily improving impact resistance and molding processability. The weight average molecular weight is measured by colloidal permeation chromatography (GPC) measurement.

In this state, the measurement is performed under the conditions of a temperature of 300 ° C and a load of 1.2 kg. The melt volume flow rate (hereinafter also referred to as MVR) of the polycarbonate resin contained in the thermoplastic resins (b) and (c) is in 3 to 120cm ^3/10 divided preferably, 3 to 80cm ^3/10 is divided into more preferably, 4 to 40cm ^3/10 divided and more preferably, 10 to 40cm ^3/10 into particularly preferred. If the MVR is higher than the lower limit described above, the fluidity is sufficiently high, and it is easy to be formed and processed in terms of melt coextrusion and the like, and it is not likely to cause appearance defects, so it is preferable. When MVR is less than the said upper limit, it is easy to improve mechanical characteristics, such as the strength of a thermoplastic resin layer, and it is preferable. MVR can be measured in accordance with JIS K 7210 under conditions of a load of 1.2 kg and 300 ° C.

In this aspect, the thermoplastic resins (b) and (c) may further include a thermoplastic resin other than a polycarbonate resin. The thermoplastic resin other than the polycarbonate resin is preferably a thermoplastic resin compatible with the polycarbonate resin, more preferably a (meth) acrylic resin, and even more preferably a methacrylic acid having an aromatic ring or a cycloolefin in the structure. Resin. In terms of the surface hardness of the thermoplastic resin layers (B) and (C) formed of the thermoplastic resins (b) and (c), respectively, the thermoplastic resins (b) and (c) contain a polycarbonate resin and the aforementioned (a) (Base) Acrylic resins are preferred because they are higher than those containing only polycarbonate resins.

In another aspect of the present invention, from the viewpoint of light resistance of the thermoplastic resin layers (B) and (C), it is preferable that the thermoplastic resins (b) and (c) include a polycarbonate resin, and All the resins contained in each of the thermoplastic resins (b) and (c) are 0.005 to 2.0% by mass of an ultraviolet absorber.

The thermoplastic resins (b) and (c) may have a solid shape (e.g., granular, ring-shaped, sheet-like, honeycomb-like, powdery, bead-like, etc.), and from the viewpoint of handleability, it is preferably granular. .

When the thermoplastic resins (b) and (c) include two or more kinds of resins, additives, etc., the thermoplastic resin composition (the resins, additives, etc. contained in each of the thermoplastic resins (b) and (c) may be mixed or kneaded) b) and (c) are preferably those obtained by melt-kneading the resin contained in each thermoplastic resin to obtain the thermoplastic resin compositions (b) and (c). The equipment and the like used for melt-kneading may be the same as the temperature, time, and equipment described in the melt-kneading of the resin composition (a), and the preferred temperature, time, and equipment may be the same.

In addition, the thermoplastic resin compositions (b) and (c) which have been melt-kneaded can directly form the thermoplastic resin layers (B) and (C), but are usually formed into a solid shape or a powder shape before forming each layer. Specific examples of the solid shape include a granular shape, a ring shape, a sheet shape, a honeycomb shape, a bead shape, and a powder shape. From the viewpoint of handleability, a granular shape is preferred. The pellet shape can be formed, for example, by a conventional method using an extrusion granulator or the like.

When the thermoplastic resin composition (b) and (c) are obtained, the composition of the thermoplastic resin composition (b) and (c) is not uniform, and may be in the same range as the composition unevenness of the resin composition (a) illustrated above. .

The resin laminate system of the present invention can be made of a resin composition (a), a thermoplastic resin (or a thermoplastic resin composition), for example, by a melt extrusion molding method, a solution casting film forming method, a hot pressing method, or an injection molding method. (b) and thermoplastic resin (or thermoplastic resin composition) (c) Prepare intermediate layer (A), thermoplastic resin layer (B), and thermoplastic resin layer (C), respectively, and apply these through, for example, an adhesive and an adhesive It can also be produced by co-extrusion and lamination of a resin composition (a), a thermoplastic resin (or thermoplastic resin composition) (b), and a thermoplastic resin (or thermoplastic resin composition) (c). . When a resin laminate is produced by lamination, it is preferable to use an injection molding method or an extrusion molding method to produce each layer, and it is particularly preferable to use an extrusion molding method. In the method for producing a resin laminate, a resin composition (a), a thermoplastic resin (or thermoplastic resin composition) (b), and a thermoplastic resin (or thermoplastic resin composition) (c) are co-extruded to The method of manufacturing a resin laminated body is preferable. In a more preferred embodiment, the particulate resin composition (a), the particulate thermoplastic resin (or thermoplastic resin composition) (b), and the particulate thermoplastic resin (or thermoplastic resin composition) ) (c) Melt co-extrusion to produce a resin laminate. According to this method, each layer can be formed uniformly, and the resin laminate can obtain good transparency, and at the same time, can be easily and easily manufactured. In the scope of the patent application, the thermoplastic resins (b) and (c) mean a composition including two or more resins and additives, that is, a thermoplastic resin composition (b) and (c).

The melt co-extrusion molding system is, for example, putting two or three resins (a), a thermoplastic resin (or a thermoplastic resin composition) (b), and a thermoplastic resin (or a thermoplastic resin composition) (c) in one shaft or After the two-axis extruder is melt-kneaded, the intermediate layer (A) and the thermoplastic resin layer (B) formed of the resin composition (a) are fed through a feed die, a multi-manifold die, and the like. (C) Extrusion method of lamination integration. When the thermoplastic resin (or thermoplastic resin composition) (b) and (c) are the same composition, they can be melt-kneaded in an extruder to divide one composition into two through the feeding die. The thermoplastic resin layers (B) and (C) are formed. The molten resin laminate extruded from the die lip is preferably cooled and hardened by a roll unit (for example, a cooling roll) or the like.

When a cooling roll is used for the cooling of the molten resin laminate, a winding roll is usually provided after the cooling roll, and the resin laminate is taken up by the winding roll. The number of the cooling rollers is not particularly limited, and may be, for example, 1 to 10, preferably 2 to 5, and particularly preferably 3. The thickness of the resin laminate can be changed by adjusting the winding speed of the winding roller and the discharge speed of the molten resin laminate from the die lip. The winding speed of the winding roller is preferably 0.5 to 10 m / min, more preferably 1 to 9 m / min, and still more preferably 1.5 to 8 m / min.

    <Resin laminated body>    

The resin laminate obtained by the manufacturing method of the present invention has an average film thickness of the resin laminate of 100 to 2000 μm. From the viewpoint of improving the transparency of the resin laminate and suppressing warpage, the thermoplastic resin layer is preferred. The average film thicknesses of (B) and (C) are 10 to 200 μm, respectively.

From the viewpoint of the rigidity of the resin laminate, the average value of the film thickness of the resin laminate obtained according to the present invention is preferably 100 μm or more, more preferably 200 μm or more, and still more preferably 300 μm or more. From the viewpoint of transparency, the thickness is preferably 2000 μm or less, more preferably 1500 μm or less, and still more preferably 1000 μm or less. The film thickness of the resin laminate can be measured by a digital micrometer. The average value of the film thickness is an average value obtained by measuring the ten points of the resin laminate.

From the viewpoint of easily improving the surface hardness, in the resin laminate obtained by the present invention, the average film thickness of the thermoplastic resin layers (B) and (C) is preferably 10 μm or more, and more preferably 30 μm or more. 50 μm or more is more preferable. From the viewpoint of the dielectric constant, the average film thickness of the thermoplastic resin layers (B) and (C) is preferably 200 μm or less, more preferably 175 μm or less, and even more preferably 150 μm or less. The method of measuring the average film thickness of the thermoplastic resin layer is as described above.

From the viewpoint of dielectric constant, in the resin laminate obtained by the present invention, the average film thickness of the intermediate layer (A) is preferably 100 μm or more, more preferably 200 μm or more, and more preferably 300 μm or more. . From the viewpoint of transparency, the average film thickness of the intermediate layer (A) is preferably 1500 μm or less, more preferably 1200 μm or less, and even more preferably 1000 μm or less. The average value of the film thickness of the intermediate layer (A) can be measured by the same method as that of the average film thickness of the thermoplastic resin layer.

The resin laminate obtained according to the present invention can obtain a uniform intermediate layer (A) by including step (i). Therefore, the composition unevenness of the intermediate layer (A) is small, preferably 5.5 mass% or less, more preferably 5 mass% or less, still more preferably 4.5 mass% or less, and still more preferably 4 mass% or less. It is preferably 3% by mass or less, particularly preferably 2% by mass or less. In addition, the lower limit of the composition unevenness is not particularly limited, and may be, for example, 0% by mass or more, 0.5% by mass or more, or 1% by mass or more. In addition, the composition unevenness (mass%) of the intermediate layer (A) is determined by Fourier transform infrared spectroscopy (FT-IR method), nuclear magnetic resonance spectroscopy (NMR method), and the like. The content (mass%) of the vinylidene fluoride resin contained in the intermediate layer (A) represents the content (upper limit) and minimum content of the intermediate layer (A) of the resin laminate having the most vinylidene fluoride resin content. Difference in the content (lower limit value) of the intermediate layer (A) of the resin laminate.

The resin laminate obtained according to the present invention is preferably transparent when viewed by eye. Specifically, the resin laminate obtained according to the present invention has a total light transmittance (Tt) measured in accordance with JIS K7361-1: 1997, preferably 85% or more, more preferably 88% or more, and more It is preferably above 90%. The upper limit of total light transmittance is 100%. It is preferable that the resin laminate having the above-mentioned range has a full light transmittance after being exposed to an environment of 60 ° C. and a relative humidity of 90% for 120 hours.

When the resin laminate obtained according to the present invention is used at 60 ° C and a relative humidity of 90%, the resin laminate is used for 120 hours, and the haze is measured in accordance with JIS K7136: 2000. It is preferably 2.0% or less, more preferably 1.8% or less, and still more preferably 1.5% or less. Moreover, when the resin laminate obtained according to the present invention is used at 60 ° C and a relative humidity of 90% for 120 hours, the resin laminate is measured in accordance with JIS Z 8722: 2009 to determine its yellowness (Yellow Index: In the case of YI value), it is preferably 1.5 or less, more preferably 1.4 or less, and still more preferably 1.3 or less. The resin laminate obtained according to the present invention having the above-mentioned haze and yellowness is preferable even if it is used in an environment such as high temperature and high humidity, can maintain transparency, is less prone to warping, and easily inhibits yellowing.

From the viewpoint of obtaining sufficient functions when used in a display device such as a touch panel, the dielectric constant of the resin laminate obtained according to the present invention is preferably 3.5 or more, more preferably 4.0 or more, and even more preferably 4.1 or more. The upper limit of the dielectric constant is not particularly limited, but is usually 20. The dielectric constant can be adjusted by adjusting the kind and content of the vinylidene fluoride resin contained in the intermediate layer (A) of the resin laminate of the present invention, and adding a compound having a high dielectric constant such as ethylene carbonate, propylene carbonate, etc. Adjust to the above range. The dielectric constant is in accordance with JIS K 6911: 1995. The resin laminate is left to stand for 24 hours under an environment of 23 ° C and a relative humidity of 50%. In this environment, 3V is used for the Auto balancing bridge method. , 100kHz. For the measurement, a commercially available device can be used, for example, "precision LCR meter HP4284A" manufactured by Agilent Technologies, Inc. can be used.

The resin laminate obtained according to the present invention may further include at least one functional layer in addition to the intermediate layer (A), the thermoplastic resin layers (B), and (C). The functional layer is preferably a surface existing on the side opposite to the intermediate layer (A) in the thermoplastic resin layer (B) and / or (C). Examples of the functional layer include a hard coat layer, an anti-reflection layer, an anti-glare layer, an anti-static layer, and an anti-fingerprint layer. These functional layers may be laminated on the resin laminate through an adhesive, or may be a coating layer laminated by coating. As the functional layer, for example, a hardened film described in Japanese Patent Application Laid-Open No. 2013-86273 can be used. The functional layer may be, for example, at least one functional layer selected from the group consisting of a hard coating layer, an anti-glare layer, an antistatic layer, and an anti-fingerprint layer by a coating method, a sputtering method, a vacuum evaporation method, or the like. A layer on which one or both sides are further coated with an anti-reflection layer may also be a layer in which an anti-reflection sheet is bonded to one or both sides of the at least one functional layer. When the resin laminated body includes these functional layers, each layer can be separately produced by the above-mentioned forming method, melt extrusion forming method, solution casting film forming method, hot pressing method, injection molding method, etc. The adhesive and the adhesive are bonded and manufactured, and can also be manufactured by co-extrusion and lamination integration.

The thickness of the functional layer can be appropriately selected depending on the purpose of each functional layer. From the standpoint of easy display of functions, the thickness of the functional layer is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 5 μm or more. From the viewpoint of layer cracking, the thickness of the functional layer is preferably 100 μm or less, more preferably 80 μm or less, and still more preferably 70 μm or less.

The resin laminate obtained according to the present invention can be used in various display devices. The display device is a device having a display element, and includes a light emitting element or a light emitting device as a light emitting source. Examples of the display device include a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a touch panel display device, an electron emission display device (such as an electric field emission display device (FED), a surface Electric field emission display device (SED)), electronic paper (display device using electronic printing ink, electrophoretic element), plasma display device, projection display device [such as Grating Light Valve (GLV) display device, Digital Micromirror Device (DMD) display device] and piezoelectric ceramic display. The liquid crystal display device also includes any one of a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, and a projection liquid crystal display device. These display devices may be a display device that displays a two-dimensional image or a stereoscopic display device that displays a three-dimensional image. The resin laminated body obtained according to the present invention is suitably used as a front panel or a transparent electrode in such display devices, for example.

When the resin laminated body obtained according to the present invention is used as a transparent electrode for a touch panel or the like, a transparent conductive film is formed on at least one surface of the resin laminated body to produce a transparent conductive sheet, and the transparent conductive sheet can be used to make transparent electrode.

The method for forming a transparent conductive film on at least one surface of the resin laminate obtained according to the present invention can directly form a transparent conductive film on the surface of the resin laminate, and can also laminate a plastic film formed with a transparent conductive film in advance in the present invention. The surface of the resin laminate.

As a film substrate of a plastic film in which a transparent conductive film is formed in advance, there is no particular limitation as long as it is a transparent film and a substrate capable of forming a transparent conductive film, and examples thereof include polyethylene terephthalate and polynaphthalene. Ethylene formate, polycarbonate, acrylic resin, polyamide, mixtures or laminates of these, etc. In addition, before forming a transparent conductive film, the film may be coated for the purposes of improving surface hardness, preventing Newton rings, and imparting antistatic properties.

The method of laminating a film having a transparent conductive film formed on the surface of the resin laminated body obtained in accordance with the present invention in advance may be any method as long as it can obtain a uniform and transparent sheet without bubbles or the like. Laminating can be performed by using an adhesive that is hardened by normal temperature, heat, ultraviolet light, or visible light, or can be laminated by a transparent adhesive tape.

Known methods for forming a transparent conductive film include a vacuum evaporation method, a sputtering method, a CVD method, an ion plating method, and a spray method. These methods may be suitably used depending on the required film thickness.

In the sputtering method, for example, a general sputtering method using an oxide target, a reactive sputtering method using a metal target, and the like are used. At this time, oxygen, nitrogen, or the like may be introduced as a reactive gas, and means such as adding ozone, irradiating plasma, or ion assist may be used. In addition, if necessary, a bias such as DC, AC, or high frequency can be applied to the substrate. Examples of transparent conductive metal oxides used in transparent conductive films include indium oxide, tin oxide, zinc oxide, indium-tin composite oxide, tin-antimony composite oxide, zinc-aluminum composite oxide, and indium-zinc composite. Oxides, etc. Among these, from the viewpoint of environmental stability and circuit processability, indium-tin composite oxide (ITO) is preferable.

In addition, the method for forming a transparent conductive film can also be applied: a coating agent containing various conductive polymers capable of forming a transparent conductive film is coated on the surface of the resin laminate obtained according to the present invention, and heat or irradiation is applied A method for curing the coating layer by free radiation such as ultraviolet rays. As the conductive polymer, polythiophene, polyaniline, polypyrrole, and the like are known, and these conductive polymers can be used.

Although the thickness of the transparent conductive film is not particularly limited, when a transparent conductive metal oxide is used, it is usually 50 to 2000 Å, preferably 70 to 1000 Å. If it is this range, both electroconductivity and transparency will be excellent.

The thickness of the transparent conductive sheet is not particularly limited, and it can be selected according to the most suitable thickness required for the type of display product.

A touch sensing panel can be manufactured by using the resin laminated body obtained according to the present invention as a display flat panel and using a transparent conductive sheet made of the resin laminated body as a transparent electrode such as a touch screen. Specifically, the resin laminate obtained according to the present invention can be used as a window sheet for a touch screen, and a transparent conductive sheet can be used as an electrode substrate of a resistive film type and a capacitive touch screen. The touch screen is arranged in front of a liquid crystal display device, an organic FL display device, and the like, thereby obtaining an external touch sensing panel having a touch screen function.

The resin laminated body obtained according to the present invention can be used for, for example, the above-mentioned display device, that is, it can be used for a display device including the resin laminated body obtained according to the present invention, and can be used for the resin laminated body obtained according to the present invention. And a polarizing plate with a resin laminated body with a polarizing plate laminated thereon, and a display device including the polarizing plate with the resin laminated body. In the polarizing plate with the resin laminate obtained according to the present invention, the resin laminated system is laminated on the polarizing plate, for example, through an optical adhesive such as an adhesive and an adhesive. As an adhesive or an adhesive, it is only necessary to use an appropriate one.

Fig. 2 is a schematic cross-sectional view showing a preferred form of a liquid crystal display device including the resin laminate obtained according to the present invention. The resin laminated body 10 obtained according to the present invention is laminated on the polarizing plate 11 through the optical adhesive layer 12, and the laminated body can be disposed on the visible side of the liquid crystal cell 13. A polarizing plate 11 is usually arranged on the back side of the liquid crystal cell 13. The liquid crystal display device 14 is composed of such a member. The second figure is an example of a liquid crystal display device, and the display device of the present invention is not limited to such a configuration.

The present invention includes a resin composition, which is a resin composition including at least a (meth) acrylic resin and a vinylidene fluoride resin. The total resin contained in the resin composition is 35 to 45% by mass ( (Meth) acrylic resin and 65 to 55 mass% of vinylidene fluoride resin, the weight average molecular weight (Mw) of the (meth) acrylic resin is 100,000 to 300,000, and the composition unevenness of the resin composition is 6 mass% or less . The resin composition is preferably the above-mentioned resin composition (a) obtained in step (i). If such a resin composition is used, a uniform layer can be formed, for example, the above-mentioned intermediate layer (A) can be formed. Therefore, the obtained resin laminate has excellent transparency. Moreover, the excellent transparency of the resin laminate can be maintained even when used for a long time in an environment of high temperature and high humidity (for example, an environment of a temperature of 60 ° C and a humidity of 90%).

    (Example)    

The following examples and comparative examples are given to illustrate the present invention in detail, but the present invention is not limited to these examples.

    [Fica softening temperature]    

Measured in accordance with the B50 method specified in JIS K 7206: 1999 "Plastic-Thermoplastic-Fica Softening Temperature (VST) Test Method". The Ficca softening temperature was measured with a thermal deformation tester ["148-6 continuous type" manufactured by Yasuda Seiki Co., Ltd.]. The test piece at this time was measured by pressing each raw material into a thickness of 3 mm.

    [Alkali metal content]    

The measurement was performed by inductively coupled plasma mass spectrometry.

    [MFR]    

The measurement was performed in accordance with the method specified in JIS K 7210: 1999 "Test Methods for Melt Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) of Plastics-Thermoplastics". Poly (methyl methacrylate) -based materials are measured at a temperature of 230 ° C and a load of 3.80 kg (37.3 N) in accordance with the JIS standards.

    [Full light transmittance and haze]    

According to JIS K 7361-1: 1997 "Test method for full light transmittance of plastics-transparent materials-Part 1: Single beam method" and haze transmittance (Murakami Color Technology Co., Ltd. "HR-100").

    [YI value]    

The measurement was performed using "Spectrophotometer SQ2000" manufactured by Nippon Denshoku Industries Co., Ltd.

    [Creation of Calibration Line]    

In order to make a calibration curve for FT-IR measurement, the methacrylic resin (i) shown in Table 2 and the vinylidene fluoride resin (i) shown in Table 3 are shown in Table 1 below using a 2-axis granulator. A predetermined amount ratio was sufficiently melt-kneaded at 240 ° C, molten resin was discharged from the die, the obtained strand was cooled, and then cut by a cutter to obtain standard pellets. The standard pellets were made into standard pellets with a thickness of 0.8 mm at 220 ° C. Next, "FT-IR" manufactured by Thermo Fisher was used for measurement under the conditions of a decomposition energy of 4 cm ^-1 , a cumulative number of 128 times, and the ATR method (ATR crystal: diamond). 877cm ^-1 peak area of (S ₂₎ 1725cm ^-1 to the peak area (S ₁₎ derived from PVDF and PMMA was calculated from the peak area ratio (S ₂ / S ₁₎ on the calibration curve, the A calibration curve of Y = 0.0385X-1.7201 can be obtained (Y: spectral peak area ratio (S ₂ / S ₁ ), X: content of vinylidene fluoride resin).

    [Uneven composition of resin composition (a)]    

For the 20 granular resin compositions (a), the content of the vinylidene fluoride resin (mass%) contained in the resin composition (a) was measured by the above-mentioned calibration curve and FT-IR method, and the vinylidene fluoride resin The difference between the content (upper limit value) of the resin composition (a) having the largest content and the content (lower limit value) of the least resin composition (a) is considered to be uneven composition of the resin composition (a).

    [The composition of the intermediate layer (A) is uneven]    

For the 100 sheets (resin laminate) obtained in the examples and comparative examples, the surface layer of the resin laminate was cut off, and the vinylidene fluoride contained in the intermediate layer (A) was measured by the above-mentioned calibration curve and FT-IR method. Resin content (% by mass), and the content of the intermediate layer (A) of the resin laminate having the highest content of vinylidene fluoride resin (upper limit) and the content of the intermediate layer (A) of the least resin laminate ( The difference in the lower limit value) is considered to be uneven in the composition of the intermediate layer (A).

    [Manufacturing example 1]    

97.7 parts by mass of methyl methacrylate and 2.3 parts by mass of methyl acrylate were mixed, and 0.05 parts by mass of a chain transfer agent (octyl mercaptan) and 0.1 parts by mass of a release agent (stearyl alcohol) were added to obtain a monomer mixed solution. In addition, 100 parts by mass of methyl methacrylate was added with 0.036 parts by mass of a polymerization initiator [1,1-bis (third butyl peroxide) 3,3,5-trimethylcyclohexane] to obtain a start.剂 混 液。 Mixing liquid. Continuously supplied to the completely mixed polymerization reactor such that the flow ratio of the monomer mixed liquid to the starter mixed liquid became 8.8: 1, and polymerized with an average residence time of 20 minutes and a temperature of 175 ° C to an average polymerization rate of 54%. Partial polymer was obtained. The obtained part of the polymer was heated to 200 ° C and led to a devolatilizing extruder with pores. Unreacted monomer was devolatilized from the pores at 240 ° C, and the devolatilized polymer was melted at the same time. After being extruded in a state and cooled with water, it was cut to obtain granular methacrylic resin (i).

The obtained granular methacrylic resin composition was analyzed by thermal cracking gas chromatography under the conditions shown below, and the peak area of each spectrum corresponding to methyl methacrylate and acrylate was measured. As a result, the methacrylic resin (i) -based structural unit derived from methyl methacrylate was 97.0% by mass, and the structural unit derived from methyl acrylate was 3.0% by mass.

    (Thermal decomposition conditions)    

Preparation of the sample: A methacrylic resin composition fine scale (standard: 2 to 3 mg) was placed in the center of a metal basin made into a pot shape, the metal pool was folded, and both ends were gently sealed with forceps.

Thermal decomposition device: CURIE POINT PYROLYZER JHP-22 (manufactured by Japan Analytical Industry Corporation)

Metal Pool: Pyrofoil F590 (manufactured by Japan Analytical Industry Corporation)

Setting temperature of constant temperature bath: 200 ℃

Set temperature of insulation pipe: 250 ℃

Thermal decomposition temperature: 590 ° C

Thermal decomposition time: 5 seconds

    (Gas chromatography analysis conditions)    

Gas chromatography analysis device: GC-14B (manufactured by Shimadzu Corporation)

Detection method: FID

String: 7G 3.2m × 3.1mm (Shimadzu Corporation)

Filler: FAL-M (made by Shimadzu Corporation)

Carrier gas: Air / N2 / H2 = 50/100/50 (kPa), 80ml / min

Heating conditions of the column: After being kept at 100 ° C for 15 minutes, the temperature was raised to 150 ° C at 10 ° C / minute and kept at 150 ° C for 14 minutes.

INJ temperature: 200 ℃

DFT temperature: 200 ℃

When the methacrylic resin composition is thermally decomposed under the above-mentioned thermal decomposition conditions, and the generated decomposition product is measured under the above-mentioned gas chromatography analysis conditions, the peak area corresponding to the detected methyl methacrylate ( a1) and the peak area (b1) corresponding to the acrylate. Then, the spectral peak area ratio A (= b1 / a1) was obtained from the spectral peak areas. On the other hand, a standard product of a methacrylic resin having a mass ratio of W ₀ (known) to a methyl methacrylate unit is thermally decomposed under the above-mentioned thermal decomposition conditions, and the resulting decomposition product is converted to When performing the measurement using the above-mentioned gas chromatography analysis conditions, the detected peak area (a ₀ ) of the spectral peak corresponding to methyl methacrylate and the peak area (b ₀ ) of the acrylic ester were measured, and the spectral peaks were determined from these peaks. Determine the area ratio of the spectral peak area A ₀ (= b ₀ / a ₀ ). Then, a factor f (= W ₀ / A ₀ ) is obtained from the spectral peak area ratio A ₀ and the mass ratio W ₀ .

The spectral peak area ratio A is multiplied by the factor f, thereby obtaining the mass ratio W of the copolymer contained in the methacrylic resin composition relative to the acrylate unit of the methyl methacrylate unit. The ratio W calculates the ratio (mass%) of the methyl methacrylate unit to the total of the methyl methacrylate unit and the acrylate unit to the ratio (mass%) of the acrylate unit to the total.

    [Manufacturing example 2]    

Except changing to 98.9 parts by mass of methyl methacrylate, 1.1 parts by mass of methyl acrylate, and 0.16 parts by mass of a chain transfer agent, a granular methacrylic resin (ii) was obtained in the same manner as in Production Example 1, and the structural unit was measured. content. The methacrylic resin (ii) has a structural unit system derived from methyl methacrylate of 97.5% by mass, and a structural unit system derived from methyl acrylate of 2.5% by mass.

The physical properties of the methacrylic resins (i) and (ii) obtained in Production Examples 1 and 2 are shown in Table 2.

    [Manufacturing example 3]    

In order to make the bluing agent masterbatch (MB), 99.99 parts by mass of the methacrylic resin (i) obtained in Production Example 1 and 0.01 parts by mass of the coloring agent were dry blended, and 40 mm was used. A one-axis extruder (manufactured by Tanabe Plastic Machinery Co., Ltd.) was melt-mixed at a set temperature of 250 to 260 ° C to obtain colored masterbatch pellets (MB (i)). As the colorant, a bluing agent ("Sumiplast (registered trademark) Violet B" manufactured by Sumika chemtex Co., Ltd.) was used.

In Examples and Comparative Examples, commercially available products shown below were used as the vinylidene fluoride resin. The physical properties of the resin are shown in Table 3.

Vinylidene fluoride resin (i): polyvinylidene fluoride made by suspension polymerization

Vinylidene fluoride resin (ii): polyvinylidene fluoride made by emulsion polymerization

The weight average molecular weight (Mw) of the vinylidene fluoride resin is measured by GPC. When preparing a GPC calibration curve, polystyrene was used as a standard reagent, and a calibration curve was prepared from the dissolution time and molecular weight to determine the weight average molecular weight of each resin. Specifically, 40 mg of the resin was dissolved in 20 ml of N-methylpyrrolidone (NMP) solvent to prepare a measurement sample. The measuring device is provided by arranging two strings of "TSKgel SuperHM-H" made by Tosoh Corporation and one "SuperH2500" in series. The detector is a RI detector.

    [Example 1]    

39 parts by mass of methacrylic resin (i), 60 parts by mass of vinylidene fluoride resin (i), and 1 part by mass of MB (i) were supplied from each feeder to the preparation tank (1), The aforementioned feed resin is mixed in the tank and sent to the preparation tank (2). It was put into the hopper from the preparation tank (2), and it was fully melt-kneaded with a 46mm Φ 2-axis granulator under a vacuum condition at a barrel temperature of 230 ° C and a rotation speed of 270rpm. The molten resin was discharged from the die mouth, and the obtained strand After the material was cooled, it was cut with a cutter to obtain pellets of the resin composition (a) for forming the intermediate layer (A). In addition, the composition of the vinylidene fluoride resin of the granular resin composition (a) is uneven, with an upper limit value of 61.5 mass% and a lower limit value of 60.1 mass% to 1.4 mass%.

As the thermoplastic resins (b) and (c) for forming the thermoplastic resin layers (B) and (C), the methacrylic resin (ii) shown in Table 1 was used. From these resin compositions (a), thermoplastic resins (b), and (c), a resin laminated body is manufactured using the manufacturing apparatus shown in FIG. Specifically, at 65mm One-shaft extruder 2 [manufactured by Toshiba Machinery Co., Ltd.] melts the resin composition (a) at 45 mm The one-shaft extruders 1 and 3 [manufactured by Hitachi Shipbuilding Co., Ltd.] melt the thermoplastic resins (b) and (c). Next, the layers were laminated through a feed section 4 [made by Hitachi Shipbuilding Co., Ltd.] with a set temperature of 250 to 270 ° C so as to have the structure shown in the above-mentioned layer B / A layer / C layer, and a multi-manifold mold was used. A multi-manifold die 5 [manufactured by Hitachi Shipbuilding Co., Ltd.] was extruded to obtain a film-like molten resin laminate 6. In this embodiment, the B layer and the C layer are layers having the same composition. Then, the obtained film-like molten resin 6 is sandwiched between the first cooling roll 7 and the second cooling roll 8 arranged in opposite directions, and then wound around the second roll 8 and sandwiched between the second roll 8 and the third After the rolls 9 are wound, they are wound around a third cooling roll 9 and formed / cooled to obtain a resin laminate 10 having three layers. The obtained resin laminate 10 had a total film thickness of about 800 μm, and the thermoplastic resin layers (B) and (C) were 100 μm, respectively, and were colorless and transparent when visually observed.

    [Example 2]    

Except that 60 parts by mass of vinylidene fluoride resin (ii) was used instead of 60 parts by mass of vinylidene fluoride resin (i), a total film thickness of about 800 μm and thermoplasticity were obtained by the same method as in Example 1. The resin layers (B) and (C) were each a resin laminate of 100 μm. The resin laminate was colorless and transparent when visually observed. In addition, the non-uniform composition of the vinylidene fluoride resin in the particulate resin composition (a) has an upper limit value of 61.7 mass% and a lower limit value of 59.9 mass% to 1.8 mass%.

    [Comparative Example 1]    

Except that 39 parts by mass of methacrylic resin (i), 60 parts by mass of vinylidene fluoride resin (i), and 1 part by mass of MB (1) were dry-blended in a drum to obtain an intermediate layer (A). Except for the particulate resin composition (a), a resin laminate having a total film thickness of about 800 μm was obtained in the same manner as in Example 1. The obtained resin laminated body (sheet) has a transparent part and a cloudy part periodically.

In the resin laminates of Example 1 and Comparative Example 1, the content of alkali metals (Na and K) in the intermediate layer (A) was 0.3 ppm, and in Example 2 was 100 ppm.

The dielectric constant of the resin laminates of Examples 1 and 2 was 4.9. It was confirmed that when used in a display device such as a touch panel, any resin laminate has a sufficient dielectric constant.

In Examples 1, 2 and Comparative Example 1, the central portion of 100 pieces of 1500 mm sheet (resin laminated body) obtained continuously was cut into 5 cm2, the surface layer was cut off, and the intermediate layer (A) was peeled off. The content of the vinylidene fluoride resin in each resin laminate was determined by a calibration curve and FT-IR measurement.

Among the 100 pieces (resin laminate), the upper and lower limits of the content of the vinylidene fluoride resin in the intermediate layer (A), the uneven composition, and the total light transmittance (Tt) and fog of the content were measured. Degree (Haze). The obtained results are shown in Table 4.

The sheet (resin laminate) obtained in Example 1 was exposed to an environment at a temperature of 60 ° C. and a relative humidity of 90% for 120 hours. The sheet after the endurance test was also subjected to the same total light transmittance (Tt) and Measurement of Haze. The obtained results are shown in Table 5.

Compared with Comparative Example 1, the resin laminates obtained in Examples 1 and 2 had less uneven composition (difference in the content of vinylidene fluoride resin) of the intermediate layer (A), had excellent transparency, and it was confirmed that The resin laminate obtained in Example 1 maintained excellent transparency even after being exposed for 120 hours in an environment of a temperature of 60 ° C and a relative humidity of 90%.

Claims (15)

    A method for manufacturing a resin laminate, which comprises the following steps (i) and (ii); step (i): melt-kneading at least a (meth) acrylic resin and a vinylidene fluoride resin to obtain a resin composition (a) a step in which the resin composition (a) contains 35 to 45% by mass of a (meth) acrylic resin and 65 to 55% by mass of the total resin contained in the resin composition (a); Vinylidene fluoride resin, (meth) acrylic resin has a weight average molecular weight (Mw) of 100,000 to 300,000; step (ii): a step of obtaining a resin laminate, the resin laminate having at least: the resin composition (a ) And the thermoplastic resin layers (B) and (C) formed from the thermoplastic resins (b) and (c) that are present on both sides of the intermediate layer (A), respectively.         The manufacturing method according to item 1 of the scope of patent application, wherein in step (i), a granular resin composition (a) is obtained.         The manufacturing method according to item 1 or 2 of the scope of patent application, wherein in step (ii), a resin laminate is obtained by coextrusion.         The manufacturing method according to any one of claims 1 to 3 in the scope of patent application, wherein in step (i), the method is performed so that the composition unevenness of the resin composition (a) becomes 6% by mass or less. Melt and mix.         The manufacturing method according to any one of claims 1 to 4 in the scope of patent application, wherein the alkali metal content in the resin composition (a) is relative to all the resins contained in the resin composition (a) is 50ppm or less.     The manufacturing method according to any one of claims 1 to 5, in which the (meth) acrylic resin is the following (a1) and / or (a2): (a1) methyl methacrylate (A2) with respect to all the structural units constituting the polymer, containing 50 to 99.9% by mass of a structural unit derived from methyl methacrylate, and 0.1 to 50% by mass of a unit derived from formula (1) A copolymer of at least one structural unit of (meth) acrylate; In the formula, R ₁ represents a hydrogen atom or a methyl group; when R ₁ is a hydrogen atom, R ₂ represents an alkyl group having 1 to 8 carbon atoms; and when R ₁ is a methyl group, R ₂ represents an alkyl group having 2 to 8 carbon atoms.     The manufacturing method according to any one of claims 1 to 6, wherein the vinylidene fluoride resin is polyvinylidene fluoride.         The manufacturing method according to any one of claims 1 to 7, wherein the melt mass flow rate of the vinylidene fluoride resin measured at 230 ° C with a load of 3.8 kg is 0.1 to 40 g / 10 minutes.         The manufacturing method according to any one of claims 1 to 8 in the scope of patent application, wherein the average film thickness of the resin laminate is 100 to 2000 μm, and the film thicknesses of the thermoplastic resin layers (B) and (C) The average values are 10 to 200 μm, respectively.         The manufacturing method according to any one of claims 1 to 9 in the scope of the patent application, wherein the Feika softening temperature of each of the resins contained in the thermoplastic resins (b) and (c) is 100 to 160 ° C.         The manufacturing method as described in any one of Claims 1 to 10, wherein the thermoplastic resins (b) and (c) each contain a (meth) acrylic resin or a polycarbonate resin.         The manufacturing method according to any one of claims 1 to 11 in the scope of the patent application, wherein the thermoplastic resin (b) is used for the polycarbonate resin and all the resins contained in each of the thermoplastic resins (b) and (c). ) And (c) are UV absorbers containing 0.005 to 2.0% by mass, respectively.         The manufacturing method according to any one of claims 1 to 11 in the scope of patent application, wherein the thermoplastic resins (b) and (c) are relative to all the resins contained in each of the thermoplastic resins (b) and (c). Each contains 50% by mass or more of a (meth) acrylic resin.         The manufacturing method according to item 13 of the scope of patent application, wherein the weight average molecular weight of the (meth) acrylic resin contained in the thermoplastic resins (b) and (c) is 50,000 to 300,000.         A resin composition which is a resin composition containing at least a (meth) acrylic resin and a vinylidene fluoride resin, and contains 35 to 45% by mass of (meth) acrylic acid with respect to all resins contained in the resin composition. Resin and 65 to 55 mass% of vinylidene fluoride resin, the weight average molecular weight (Mw) of the (meth) acrylic resin is 100,000 to 300,000, and the composition unevenness of the resin composition is 6 mass% or less.