TW201811562A - Method of manufacturing resin laminate - Google Patents

Abstract

The present invention provides a method for producing a resin laminate excellent in transparency. The method for manufacturing resin laminate of the present invention has at least an intermediate layer (A), and thermoplastic resin layers (B) and (C) present on both sides of the intermediate layer (A); wherein the intermediate layer (A) is formed from a resin composition (a), the thermoplastic resin layers (B) and (C) are each formed from a thermoplastic resin (b) and (c); the method includes a step of discharging a molten resin laminate at least formed from the molten resin composition (a), thermoplastic resin (b) and (c), and cooling it; the resin composition (a) contains 10 to 90% by mass of (meth)acrylic resin and 90 to 10% by mass of vinylidene fluoride resin, based on the total resin contained in the resin composition (a), the weight average molecular weight (Mw) of the (meth)acrylic resin is 100,000 to 300,000; in the step, the average cooling rate from the discharge temperature to 100 DEG C is 2.5 DEG C/s or more.

Description

   Manufacturing method of resin laminated body   

This invention relates to the manufacturing method of the resin laminated body suitable for a display device, for example.

In recent years, display devices such as smart phones, portable game consoles, audio players, and tablet terminals have gradually increased the number of people with touch screens. A glass sheet is generally used on the surface of such a display device. However, from the viewpoint of the tendency of weight reduction and workability of the display device, the development of a plastic sheet as a substitute for the glass sheet is being carried out. For example, in Patent Document 1, a plastic sheet that has become a substitute for a glass sheet is disclosed as a transparent sheet including a methacrylic resin and a vinylidene fluoride resin, and a multilayer sheet including the transparent sheet, and it is described that these sheets sufficiently satisfy transparency And relative dielectric constant.

    [Prior technical literature]         [Patent Literature]    

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

Depending on the method for producing a transparent sheet containing a methacrylic resin and a vinylidene fluoride resin, a part of white turbidity may be seen in the resin laminate, and a transparent resin laminate may not be produced. The present inventors reviewed a method for manufacturing a resin laminate by extrusion, and as a result, it was found that when the molten resin laminate discharged from a die is cooled, the resin laminate may become cloudy and the transparency may be reduced.

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

In order to solve the above problems, the present inventors repeated the results of careful review to complete the present invention. That is, the present invention includes the following suitable aspects.

[1] A method for producing a resin laminate, wherein the resin laminate system has at least an intermediate layer (A) and thermoplastic resin layers (B) and (C) that are respectively present on both sides of the intermediate layer (A); the The intermediate layer (A) is formed of a resin composition (a), and the thermoplastic resin layers (B) and (C) are respectively formed of a thermoplastic resin (b) and (c); the manufacturing method includes: The step of ejecting and cooling the molten resin laminate formed from the resin composition (a), the thermoplastic resin (b), and (c) from the die; based on all the resins contained in the resin composition (a), the resin composition The object (a) contains 10 to 90% by mass of a (meth) acrylic resin and 90 to 10% by mass of a vinylidene fluoride resin, and the weight average molecular weight (Mw) of the (meth) acrylic resin is 100,000 to 300,000; and In this step, the average cooling rate from the discharge temperature to 100 ° C is 2.5 ° C / second or more.

[2] The method according to the above [1], wherein the molten resin laminate is cooled by a cooling roller.

[3] The method according to the above [1] or [2], wherein the discharge temperature is 220 to 300 ° C.

[4] The method according to any one of the above [1] to [3], wherein the resin composition (a) contains 35 to 45% by mass based on the entire resin contained in the resin composition (a) (Meth) acrylic resin and 65 to 55 mass% of vinylidene fluoride resin.

[5] The method according to any one of the above [1] to [4], wherein the content of the alkali metal in the resin composition (a) is based on all resins contained in the resin composition (a) 50ppm or less.

[6] The method according to any one of the above [1] to [5], wherein the (meth) acrylic resin is a homopolymer of (a1) methyl methacrylate; and / or (a2) is based on a constitution The total structural unit of the polymer contains 50 to 99.9% by mass of a structural unit derived from methyl methacrylate and 0.1 to 50% by mass of at least one structural unit derived from a (meth) acrylate represented by formula (1). Copolymer: [Wherein, R ₁ represents a hydrogen atom or a methyl group, R ₁ is a hydrogen atom when R ₂ represents an alkyl group having 1 to 8 carbon atoms, and R ₁ is methyl R ₂ represents an alkyl group having a carbon number of 2-8].

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

[8] The method according to any one of the above [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 under a 3.8 kg load. .

[9] The method according to any one of the above [1] to [8], wherein the average film thickness of the resin laminate is 100 to 2000 μm, and the 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 the above [1] to [9], wherein the Vicat softening temperature of the resin contained in each of the thermoplastic resins (b) and (c) is 100 to 160 ° C.

[11] The method according to any one of the above [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 the above [1] to [11], wherein the thermoplastic resins (b) and (c) include a polycarbonate resin, and the thermoplastic resins (b) and (c) The total amount of the resin contained is 0.005 to 2.0% by mass of the ultraviolet absorber.

[13] The method according to any one of the above [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 (meth) acrylic resin.

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

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

1‧‧‧ Extruder

2‧‧‧ Extruder

3‧‧‧ Extruder

4‧‧‧Feed block

5‧‧‧Multi-manifold Die

6‧‧‧ Molten resin laminate

7‧‧‧The first cooling roller

8‧‧‧Second cooling roller

9‧‧‧Third 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

15‧‧‧Single-screw extruder (extrusion of melt of thermoplastic resin b)

16‧‧‧Single-screw extruder (extruded melt of resin composition a)

17‧‧‧Single-screw extruder (extrusion of melt of thermoplastic resin c)

18‧‧‧Feed block

19‧‧‧Multi-manifold Die

20‧‧‧ film-like molten resin laminate

21‧‧‧The first cooling roller

22‧‧‧Second cooling roller

23‧‧‧Third cooling roller

24‧‧‧Fourth cooling roller

25‧‧‧Fifth cooling roller

26‧‧‧Resin laminate

FIG. 1 is a schematic diagram showing an example of a manufacturing apparatus for a resin laminate obtained by the manufacturing method of the present invention.

FIG. 2 is a schematic cross-sectional view showing an aspect of a liquid crystal display device including a resin laminate obtained by the manufacturing method of the present invention.

Fig. 3 is a schematic view showing a manufacturing apparatus for a resin laminate obtained by the present invention and used in Examples.

The present invention is a method for manufacturing a resin laminate having at least an intermediate layer (A) and thermoplastic resin layers (B) and (C) that are present on both sides of the intermediate layer (A); the intermediate layer (A) is composed of The resin composition (a) is formed, and the thermoplastic resin layers (B) and (C) are each formed of a thermoplastic resin (b) and (c).

This resin composition (a) contains a (meth) acrylic resin and a vinylidene fluoride resin.

Examples of the (meth) acrylic resin include homopolymers of (meth) acrylic monomers such as (meth) acrylates and (meth) acrylonitrile, and copolymers of two or more (meth) acrylic monomers. , A copolymer of a (meth) acrylic monomer and a monomer other than the (meth) acrylic monomer, and the like. In addition, in this 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, the (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 a homopolymer of methacrylate (polyalkyl methacrylate) and two or more kinds Copolymers of methacrylates, copolymers of 50% by mass or more of methacrylates and monomers other than 50% by mass of methacrylates, and the like. The copolymer of a methacrylate and a monomer other than methacrylate is preferably 70 with respect to the total amount of the monomer from the viewpoint of easily improving the optical characteristics and weather resistance of the resin laminate. The copolymer of methacrylate and 30% by mass of other monomers is preferably a copolymer of 90% by mass or more of methacrylate and 10% by mass of other monomers.

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

Monofunctional monomers include, for example, styrene monomers such as styrene, α-methylstyrene, and vinyl toluene; cyanoolefins such as acrylonitrile and methacrylonitrile; acrylic acid; methacrylic acid; maleic anhydride; N-substituted maleimine and the like.

From the viewpoint 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 specifically preferably: (a1) a homopolymer of methyl methacrylate; and / or (a2) 50 to 99.9% by mass, preferably 70.0 to 99.8% by mass, more preferably 80.0 to 99.7% by mass, based on all the structural units constituting the copolymer, and 0.1 to 50% by mass , Preferably from 0.2 to 30% by mass, more preferably from 0.3 to 20% by mass, a copolymer derived from at least one structural unit of the (meth) acrylate represented by formula (1): [Wherein, R ₁ represents a hydrogen atom or a methyl group, R ₁ is a hydrogen atom when R ₂ represents an alkyl group having 1 to 8 carbon atoms, and R ₁ is methyl R ₂ represents an alkyl group having a carbon number of 2-8]. Here, the content of each structural unit can be calculated by analyzing the obtained polymer by thermal decomposition gas chromatography and measuring the peak area corresponding to each monomer.

In the formula _(1), R 1 represents a hydrogen atom or a methyl group, R ₁ is a hydrogen atom when R ₂ represents an alkyl group of 1 to 8 carbon atoms, R ₁ is a methyl group R ₂ represents alkyl of 2-8 carbon atoms, base. 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 sometimes referred to as Mw) of the (meth) acrylic resin contained in the resin composition (a) is 100,000 to 300,000. When 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, and when Mw is higher than the upper limit described above, the film-forming property at the time of manufacturing the resin laminate cannot be obtained. 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 was measured by gel permeation chromatography (GPC).

(Meth) acrylic resin, measured at a load of 3.8 kg at 230 ° C, usually has 0.1 to 20 g / 10 minutes, preferably 0.2 to 5 g / 10 minutes, and more preferably 0.5 to 3 g / 10 minutes. Rate (hereinafter sometimes referred to as MFR). Since it is easy to increase the strength of the obtained film, the MFR is preferably at most the above upper limit, and from the viewpoint of the film-forming property of the resin laminate, it is preferably at least the above lower limit. MFR can be measured according to the method specified in JIS K 7210: 1999 "Test methods for the melt mass flow rate (MFR) and melt volume flow rate (MVR) of plastics-thermoplastics". The JIS provides that poly (methyl methacrylate) -based materials are measured at a temperature of 230 ° C and a load of 3.80 kg (37.3 N).

From the viewpoint of heat resistance, the (meth) acrylic resin preferably has a temperature of 90 ° C or higher, more preferably 100 ° C or higher, and even more preferably a Ficca softening temperature (hereinafter sometimes referred to as VST) of 102 ° C or higher. Although the upper limit of VST is not particularly limited, it is usually 150 ° C or lower. VST can be measured according to JIS K 7206: 1999 and 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 above-mentioned monomers by a known method such as suspension polymerization or bulk polymerization. In this case, MFR, Mw, VST, etc. can be adjusted to a preferable range by adding an appropriate chain transfer agent. As the chain transfer agent, an appropriate commercially available product can be used. The amount of the chain transfer agent to be added may be appropriately determined depending on the type of the monomer and its ratio, required 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 selected from the group consisting of trifluoroethylene, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluoroalkyl vinyl ether, and ethylene. The copolymer of at least one of the monomers and vinylidene fluoride in the formed group, 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, even more preferably 200,000 to 450,000, and particularly preferably 350,000 to 450,000. . When the resin laminate of the present invention is exposed to a high-temperature and high-humidity environment (for example, 60 ° C. and a relative humidity of 90%), it is easy to improve the transparency of the resin laminate. Therefore, it is preferable that Mw is the above lower limit. Moreover, since it is easy to improve the film-forming property of a resin laminated body, it is preferable that Mw is below the said upper limit. The weight average molecular weight was measured by gel permeation chromatography (GPC).

The vinylidene fluoride resin, measured at 3.8 kg load and 230 ° C, preferably has a melt quality of 0.1 to 40 g / 10 minutes, more preferably 0.1 to 35 g / 10 minutes, and still more preferably 0.1 to 30 g / 10 minutes. Flow rate (MFR). The MFR is more preferably 0.2 g / 10 minutes or more, and even more preferably 0.5 g / 10 minutes or more. The MFR is more preferably 20 g / 10 minutes or less, even more preferably 5 g / 10 minutes or less, and particularly preferably 2 g / 10 minutes or less. Since it is easy to suppress a decrease in transparency when the resin laminate is used for a long time, it is preferable that the MFR is equal to or less than the above upper limit. Since it is easy to improve the film-forming property of the resin laminate, the MFR is preferably at least the above lower limit. MFR can be measured according to the method specified in JIS K 7210: 1999 "Test methods for the melt mass flow rate (MFR) and melt volume flow rate (MVR) of plastics-thermoplastics".

The vinylidene fluoride resin is industrially manufactured by a suspension polymerization method or an emulsion polymerization method. Suspension polymerization method is carried out by using water as a medium, dispersing a monomer as a droplet in a medium with a dispersant, and polymerizing an organic peroxide dissolved in the monomer as a polymerization initiator to obtain 100 to 300 μm. Granular polymer. Suspended polymers are preferred because they have simpler manufacturing steps and better powder handling properties than emulsified polymers, and they do not include alkali metal-containing emulsifiers and salting-out agents, which would be included in emulsified polymers.

A commercially available vinylidene fluoride resin can be used. Examples of preferred commercially available products include, for example, "KF POLYMER (registered trademark) T # 1300, T # 1100, T # 1000, T # 850, W # 850, W # 1000, W # 1100 and W # 1300 "and" SOLEF (registered trademark) 6012, 6010 and 6008 "manufactured by Solvay.

The resin composition (a) contains 10 to 90% by mass of the aforementioned (meth) acrylic resin and 90 to 10% by mass of the aforementioned vinylidene fluoride resin based on the entire resin contained in the resin composition (a). When the amount of the (meth) acrylic resin is lower than the lower limit, sufficient transparency cannot be obtained, and when the amount of the (meth) acrylic resin is higher than the upper limit, sufficient dielectric constant cannot be obtained. When the vinylidene fluoride resin is below the lower limit, a sufficient dielectric constant cannot be obtained, and when the vinylidene fluoride resin is above the upper limit, durability or sufficient transparency cannot be obtained.

From the viewpoint of easily increasing the dielectric constant and improving the transparency of the resin laminate, the resin composition (a) preferably contains 30 to 60% by mass based on the entire resin contained in the resin composition (a). (Meth) acrylic resin and 70 to 40 mass% of vinylidene fluoride resin, more preferably 35 to 45 mass% of (meth) acrylic resin and 65 to 55 mass% of vinylidene fluoride resin, and More preferably, it contains 37 to 45% by mass of (meth) acrylic resin and 63 to 55% by mass of vinylidene fluoride resin, and particularly preferred is 38 to 45% by mass of (meth) acrylic resin and 62 to 55% by mass % Vinylidene fluoride resin, an excellent system containing 38 to 43% by mass of (meth) acrylic resin and 62 to 57% by mass of vinylidene fluoride resin.

The resin composition (a) may further include another resin different from the (meth) acrylic resin and vinylidene fluoride resin. 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 the other resins is preferably 15% by mass or less, more preferably 10% by mass or less, based on 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. Although the resin composition (a) may further contain other resins, from the viewpoint of transparency, it is preferable that the amount of other resins is 1% by mass or less. The resin contained in the resin composition (a) is only (A). ) Acrylic resin and vinylidene fluoride resin are more preferred.

The resin composition (a) may further contain various additives that are generally used, as long as the effects of the present invention are not hindered. Additives include, for example, stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, foaming agents, lubricants, release agents, antistatic agents, flame retardants, release agents, polymerization inhibitors, 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 phthalocyanine skeleton. Among these, from the viewpoint of heat resistance, a compound having an anthraquinone skeleton is preferred.

When the resin composition (a) further contains a colorant, the content of the colorant can be appropriately selected depending on the purpose, the type of the colorant, and the like. In the case where a bluing agent is used as the colorant, the content may be about 0.01 to 10 ppm based on the entire resin 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, still more preferably 0.1 ppm or more, still more preferably 7 ppm or less, even more preferably 5 ppm or less, even more preferably 4 ppm or less, and particularly preferably 3 ppm or less. . The bluing agent can be appropriately used by a person skilled in the art, and is represented by a trade name, for example, MACROLEX (registered trademark) Blue RR (manufactured by Bayer), MACROLEX (registered trademark) Blue 3R (manufactured by Bayer), Sumiplast (registered (Trademark) Violet B (manufactured by Sumika Chemtex) and Polysynthren (registered trademark) Blue RLS (manufactured by Clariant), Diaresin Violet D, Diaresin Blue G, and Diaresin Blue N (manufactured 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 great absorption at 200 to 320 nm or 320 to 400 nm can be mentioned. Specifically, for example, three UV absorber, benzophenone UV absorber, benzotriazole UV absorber, benzoate UV absorber, cyanoacrylate UV absorber. As an ultraviolet absorber, 1 type of these ultraviolet absorbers can be used individually or in combination of 2 or more types. 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 absorber having a maximum absorption at 320 to 400 nm. As the ultraviolet absorber, a commercially available product may be used, and for example, "Kemisorb 102" (2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4) manufactured by Chemipro Chemical Co., Ltd. may be used. -N-octyloxyphenyl) -1,3,5-tri ) (Absorbance 0.1), "Adekastab LA-F70" (2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5 manufactured by ADEKA Corporation -three ) (Absorbance 0.6), "Adekastab LA-31, LA-31RG, LA-31G"(2,2'-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6 -(2H-benzotriazol-2-yl) phenol) (absorbance 0.2), "Adekastab 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. Phenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-tri ) (Absorbance 0.1) and so on. The absorbance of the exemplified ultraviolet absorber is a value obtained by dissolving the ultraviolet absorbent in chloroform at a concentration of 10 mg / L and measuring it at 380 nm using 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 can be appropriately selected depending on the purpose, the type of the ultraviolet absorber, and the like. For example, the content of the ultraviolet absorber may be about 0.005 to 2.0% by mass based on the entire resin contained in the resin composition (a) containing the ultraviolet absorber. 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 absorbing effect, it is preferable that the content of the ultraviolet absorbent is not less than the above-mentioned lower limit, and since it is easy to prevent the color tone (for example, yellowness YI) of the resin laminate from changing, it is preferably not more than the above-mentioned upper limit. For example, it is preferable to use the above-mentioned "Adekastab LA-31, LA-31RG, LA-31G" in the aforementioned amount.

The content of the alkali metal in the resin composition (a) is preferably 50 ppm or less, more preferably 30 ppm or less, even more preferably 10 ppm or less, and particularly preferably 1 ppm based on the total resin contained in the resin composition (a). the following. Since it is easy to suppress a decrease in transparency when the resin laminate is used for a long time under a high temperature and high humidity environment, the content of the alkali metal in the resin composition (a) is preferably not more than the above upper limit. 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 it is not substantially contained. Here, the (meth) acrylic resin and / or vinylidene fluoride resin contained in the resin composition (a) contains a small amount of an emulsifier and the like used in the production step. Therefore, alkali metals such as sodium and potassium derived from the remaining emulsifier are contained in the resin composition (a) at, 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 content of the alkali metal of (a) also becomes high. From the viewpoint of easily suppressing the 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 / or vinylidene fluoride contained in the resin composition (a). Resin.

In order to make the content of the alkali metal in the resin fall within the above range, it is only necessary to reduce the amount of the alkali metal-containing compound used during the polymerization of the resin or increase the washing step after the polymerization to remove the alkali metal-containing compound. The content of the alkali metal can be obtained by, for example, inductively coupled plasma mass spectrometry (ICP / MS). In the case of inductively coupled plasma mass spectrometry, for example, as long as the measurement sample particles are subjected to a high-temperature ash melting method, a high-temperature ash acid dissolution method, a Ca-added ash acid dissolution method, a combustion absorption method, and a low-temperature ash acid dissolution method The sample may be subjected to an appropriate method such as ashing, dissolving the sample in an acid, and measuring the volume of the dissolving solution. The content of the alkali metal may be measured using an inductively coupled plasma mass spectrometry.

The resin composition (a) is usually obtained by kneading a (meth) acrylic resin and a vinylidene fluoride resin. The kneading can be performed by a method including a step of melt-kneading at a temperature of 150 to 350 ° C. and a shear rate of 10 to 1000 / sec.

Since the resin can be sufficiently melted and the miscibility can be improved, the temperature during melt-kneading is preferably 150 ° C or higher, and the thermal decomposition of the resin is easily suppressed, so it is preferably 350 ° C or lower. Furthermore, since the miscibility of the resin can be improved, the shear rate during melt-kneading is preferably 10 / sec or more, and the decomposition of the resin is easily suppressed, so it is preferably 1000 / sec or less.

In order to obtain a resin composition (a) which is more homogeneously (or uniformly) mixed with resins, additives, etc., the melt-kneading is preferably performed at a temperature of 180 to 300 ° C, more preferably 200 to 300 ° C, and preferably 20 to 700. / Sec, more preferably at a shear rate of 30 to 500 / sec.

As a machine used for melt-kneading, a general mixer or kneader can be used. Specifically, for example, a single-shaft kneading machine, a multi-shaft kneading machine (e.g., a double-shaft kneading machine, etc.), a Henschel mixer, a Banbury mixer, a kneader, a roll mill, etc. . When the shear rate is increased within the above range, a high-shear processing device or the like can be used.

When the resin composition (a) contains an additive, the additive may be contained in the resin contained in the resin composition (a) in advance, or it may be added during the melt-kneading of the resin, or it may be added after the resin is melt-kneaded, or It can be added when a resin laminate is produced using the resin composition (a).

The resin composition (a) obtained by melt-kneading can be directly supplied to the step for forming the intermediate layer (A), or it can be formed into solid, powdery shapes such as pellets, rings, flakes, honeycombs, etc. After that, it is supplied to the step for forming the intermediate layer (A). The solid state can be formed by a conventional method, for example, using an extrusion granulator or the like.

The thermoplastic resins (b) and (c) forming the thermoplastic resin layers (B) and (C) include at least one type of thermoplastic resin. From the viewpoint of easily improving the moldability, the thermoplastic resins (b) and (c) are preferably contained in an amount of 60% by mass or more based on all the resins contained in each of the thermoplastic resins (b) and (c), and more preferably 70% by mass or more, and more preferably 80% by mass or more of a thermoplastic resin. 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 different thermoplastic resins. From the viewpoint of improving the transparency of the resin laminate and the viewpoint of easily suppressing bending, it is preferred that the thermoplastic resins (b) and (c) include the same thermoplastic resin.

From the viewpoint of the heat resistance of the resin laminate, each of the resins contained in the thermoplastic resins (b) and (c) preferably has a temperature of 100 to 160 ° C, more preferably 102 to 155 ° C, and even more preferably 102 to 152 ° C. Fica softening temperature. Here, the above-mentioned Feika softening temperature is the Feika softening temperature of the resin when the thermoplastic resin contains one resin, and the Feika softening temperature of a mixture of a plurality of resins when the thermoplastic resin contains two or more resins. The Feika 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-Feika Softening Temperature (VST) Test Method". The Ficca softening temperature can be measured using a thermal deformation tester (for example, "148-6 continuous type" manufactured by Yasuda Seiki Seisakusho Co., Ltd.). The measurement can be performed using each raw material by press-molding a test piece having a thickness of 3 mm.

The thermoplastic resins (b) and (c) may further contain other resins (for example, thermosetting resins such as fillers and resin particles) other than the thermoplastic resin for the purpose of improving the strength and elasticity of the thermoplastic resin layer. In this case, based on all the resins contained in the respective thermoplastic resins (b) and (c), the amount of the other resins is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass. %the following. 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 (b) and (c) may be the same as the range of additives and ratios contained in the resin composition (a), and the ranges of preferred additives and ratios may also be 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 in which the thermoplastic resins (b) and (c) include a (meth) acrylic resin will be described below. In this aspect, each of the thermoplastic resins (b) and (c) includes 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) are preferred based on all the resins contained in the respective thermoplastic resins (b) and (c). It contains 50 mass% or more, more preferably 60 mass% or more, and even more preferably 70 mass% or more (meth) acrylic resin.

Examples of the (meth) acrylic resin include those described for the (meth) acrylic resin contained in the resin composition (a). The preferable (meth) acrylic resin described with respect to the resin composition (a) is similar to the (meth) acrylic resin contained in the thermoplastic resins (b) and (c) unless otherwise specified. good. 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 was measured by gel permeation chromatography (GPC).

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, for example, a methyl methacrylate-styrene-maleic anhydride copolymer (for example, "RESISFY" manufactured by Denki Chemical Industry), a methyl methacrylate-methacrylic acid copolymer (for example, "ALTUGLAS" manufactured by ARKEMA) HT121 "), polycarbonate resin. From the viewpoint of heat resistance, thermoplastic resins other than (meth) acrylic resins are preferably measured in accordance with JIS K7206: 1999, preferably 115 ° C or higher, more preferably 117 ° C or higher, and even more preferably 120 ° C or higher. Fica softening temperature. Furthermore, from the viewpoints of heat resistance and surface hardness, the thermoplastic resins (b) and (c) are preferably those which do not substantially contain vinylidene fluoride resin.

In this aspect, from the viewpoint of improving the scratch resistance, the pencil hardness of the thermoplastic resin layers (B) and (C) formed of the thermoplastic resins (b) and (c), respectively, is preferably HB or more. More preferably, it is 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) include a polycarbonate resin will be described below. In this aspect, each of the thermoplastic resins (b) and (c) contains one or more polycarbonate resins. From the viewpoint of impact resistance, the thermoplastic resins (b) and (c) are preferably contained in an amount of 60% by mass or more, and more preferably 70%, based on all the resins contained in the respective thermoplastic resins (b) and (c). More than 80% by mass, and more preferably 80% by mass or more of a polycarbonate resin.

The polycarbonate resin can be obtained, for example, by a phosgene method in which various dihydroxydiaryl compounds are reacted with phosgene, or a transesterification method in which dihydroxydiaryl compounds are reacted with carbonates such as diphenyl carbonate. Specific examples of the polymer include polycarbonate resins produced from 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A).

In addition to the bisphenol A, the dihydroxy diaryl compound may be, for example, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 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, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane and other bis (hydroxyaryl) alkanes; such as Bis (hydroxyaromatic) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane; such as 4,4'-dihydroxy Dihydroxy diaryl ethers such as diphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether; dihydroxy groups such as 4,4'-dihydroxydiphenyl sulfide Diaryl sulfides; such as 4,4'-dihydroxydiphenylsulfene, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfene, and other dihydroxydiarylsulfides Class; such as 4,4'-dihydroxydiphenylfluorene, 4,4'-dihydroxy-3,3'-dimethyldiphenylfluorene and other dihydroxydiaryl groups Class.

These can be used singly or as a mixture of two or more kinds. (piperazine), dipiperidyl hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl and the like are used in combination.

The dihydroxydiaryl compound may be mixed with a trivalent or higher phenol compound as shown below. Examples of the trivalent or higher phenol include resorcinol, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene, and 2,4,6-dimethyl-2 , 4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) 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 a polycarbonate synthesized from isosorbide and an aromatic diol. Examples of the polycarbonate include "DURABIO (registered trademark)" manufactured by Mitsubishi Chemical Corporation.

As the polycarbonate resin, a commercially available product such as "CALIBRE (registered trademark) 301-4, 301-10, 301-15, 301-22, 301-30, 301-40" manufactured by SUMIKA STYRON POLYCARBONATE Co., Ltd. may also be used. , 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 was measured by gel permeation chromatography (GPC).

In this aspect, the thermoplastic resin (b) and (c) a polycarbonate resin contained in the set side and at a temperature of 300 deg.] C of 1.2kg weight, preferably having from 3 to 120cm ^3/10 minutes, and more preferably having from 3 to 80cm ^3/10 minutes, and more preferably having from 4 to 40cm ^3/10 min and particularly preferably has a melt volume flow rate of 10 to 40cm ^3/10 min (hereinafter, also referred to as MVR). When the MVR is higher than the lower limit described above, it is preferable because the fluidity is sufficiently high, and it is easy to be formed and processed in melt coextrusion molding, and it is unlikely to cause appearance defects. When the MVR is lower than the above upper limit, mechanical properties such as the strength of the thermoplastic resin layer can be easily improved, so it is preferable. The 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 one having an aromatic ring or a cycloolefin in the structure. Methacrylic resin. Since the thermoplastic resins (b) and (c) contain a polycarbonate resin and the (meth) acrylic resin described above, the thermoplastic resins (b) and (c) can be improved more than when the polycarbonate resin is used only. The surface hardness of the formed thermoplastic resin layers (B) and (C) is preferred.

In another aspect of the present invention, the thermoplastic resins (b) and (c) include a polycarbonate resin, respectively, and the mass is 0.005 to 2.0 mass based on the total resin contained in each of the thermoplastic resins (b) and (c). % Ultraviolet absorber is preferred from the viewpoint of light resistance of the thermoplastic resin layer.

When the thermoplastic resins (b) and (c) contain two or more components such as resins and additives, the resins and additives contained in each of the thermoplastic resins (b) and (c) may be mixed or kneaded. Melt-knead to obtain thermoplastic resin compositions (b) and (c). The thermoplastic resin composition (b) and (c) may be directly supplied to the step for forming the thermoplastic resin layers (B) and (C), or may be formed into solids such as pellets, rings, sheets, honeycombs, etc. After being shaped like powder or powder, it is supplied to the step for forming the thermoplastic resin layers (B) and (C). The solid state can be formed by a conventional method, for example, using an extrusion granulator or the like. The melting temperature and the equipment used for the melt-kneading may be the same as the temperature, equipment, and the like described above for the melt-kneading of the resin composition (a), and the preferred temperature, the equipment, and the like may also be the same.

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), but the intermediate layer (A) is formed from the resin composition (a). ), So in other words, the resin and additives contained in the above-mentioned resin composition (a) and the proportions thereof can also be said to be the resins and additives contained in the intermediate layer (A) and the proportions thereof. The same applies to the content of the alkali metal. The amount of the alkali metal contained in the resin composition (a) can also be said to be the amount of the alkali metal contained in the intermediate layer (A). The same applies to the thermoplastic resins (b) and (c). The resins and additives contained in the above-mentioned thermoplastic resins (b) and (c), and the ratios thereof can also be said to be the thermoplastic resin layers (B) and (C) The resins and additives contained and their proportions.

The production method of the present invention includes a step of ejecting and cooling a molten resin laminate formed from at least the molten resin composition (a), the thermoplastic resin (b), and (c) from a die, and in this step, The average cooling rate from the discharge temperature to 100 ° C is 2.5 ° C / second or more. At such a cooling rate, white turbidity of the obtained resin laminate can be effectively prevented, and a resin laminate having excellent transparency can be obtained. When the average cooling rate is less than 2.5 ° C / sec, it is estimated that the vinylidene fluoride resin of the crystalline resin contained in the molten resin laminate is crystallized (or precipitated) during the cooling of the molten resin laminate, which may cause damage to the resin laminate. Cloudy. On the other hand, when the average cooling rate is 2.5 ° C / sec or more, the cooling rate is higher than the crystallization rate of the vinylidene fluoride resin. It is estimated that the molten resin laminate is cooled and solidified before the crystallization of the vinylidene fluoride resin. A resin laminate having excellent transparency can be obtained.

The discharge temperature of the molten resin laminate discharged from the die is appropriately selected according to the kind of resin contained in the molten resin laminate, and is preferably 220 to 300 ° C, more preferably 220 to 290 ° C, and even more preferably 230 to 280 ° C. When the discharge temperature is equal to or higher than the above upper limit value, decomposition of the molten resin is liable to occur, and when the ejection temperature is equal to or lower than the lower limit value, molding processability is reduced. It should be noted that the discharge temperature refers to the temperature of the molten resin laminate at the discharge opening (or immediately after discharge) of the die.

The average cooling rate from the molten resin laminate discharge temperature to 100 ° C is 2.5 ° C / sec or more, preferably 3.0 ° C / sec or more, more preferably 3.5 ° C / sec or more, and even more preferably 4.0 ° C / sec or more. . When the average cooling rate is at least the above value, it is estimated that the crystallization (or precipitation) of the vinylidene fluoride resin during cooling can be more effectively suppressed, and the transparency of the resin laminate can be further improved. The average cooling rate from the discharge temperature of the molten resin laminate to 100 ° C is preferably 25 ° C / second or less, more preferably 20 ° C / second or less, still more preferably 17 ° C / second or less, and particularly preferably 15 ° C / sec or less. When the average cooling rate is equal to or less than the above value, it is estimated that the residual strain of the resin laminated body due to rapid cooling and the occurrence of warpage can be suppressed. Therefore, the aforementioned average cooling rate is preferably 2.5 to 25 ° C / second, more preferably 3 to 20 ° C / second, even more preferably 3.5 to 17 ° C / second, and particularly preferably 4 to 15 ° C / second. A resin laminate having excellent transparency and less warpage is preferably obtained without warpage. It should be noted that the average cooling rate (° C / sec) shown above is a value obtained by subtracting 100 (° C) from the discharge temperature (° C) of the molten resin laminate and dividing it from the discharge temperature to 100 ° C. Time (in seconds). In addition, the discharge temperature can be measured by installing a thermometer (such as a non-contact thermometer) at the discharge port of the die (or immediately after discharge). The time required for the resin to reach 100 ° C from the discharge temperature can be measured by a cooling device (such as In a cooling roller), a thermometer (for example, a non-contact thermometer) or the like is used to find the place where the molten resin laminate becomes 100 ° C, and measures the time required to reach the place from the ejection port of the die. For example, the method of the embodiment.

With reference to the drawings, an embodiment of a method for producing a resin laminate according to the present invention will be described. FIG. 1 is a schematic diagram showing an example of a manufacturing apparatus for a resin laminate obtained by the manufacturing method of the present invention. According to this manufacturing apparatus, a resin laminate having 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) can be obtained. As shown in FIG. 1, the resin composition (a), the thermoplastic resin (b), and the thermoplastic resin (c) are melt-kneaded in the extruder 2, 1, and 3 respectively, and the melt-kneaded resin composition (a) , Thermoplastic resin (b) and thermoplastic resin (c) are supplied to three types of three-layer distribution type feed blocks 4 and distributed in a three-layer configuration. A molten resin layered body 6 made of the molten resin composition (a), the thermoplastic resin (b), and the thermoplastic resin (c) is discharged from the head and lip portion. Then, the discharged molten laminated body 6 is sandwiched between the first cooling roller 7 and the second cooling roller 8, and is wound around the second cooling roller 8 while being sandwiched between the second cooling roller 8 and the third cooling roller 9 After that, it is wound around the third cooling roller 9 and cooled to produce a resin laminate 10.

From the viewpoint of easily melting the resin composition (a) and improving the kneading property, the cylinder temperature (or the melting temperature of the resin composition (a)) of the extruder 2 that melts the resin composition (a), for example, It is 230 to 280 ° C, preferably 230 to 270 ° C. From the viewpoint of easily melting the thermoplastic resins (b) and (c), the cylinder temperatures of the extruders 1 and 3 (or the thermoplastic resin (b) and The melting temperature of (c)) is, for example, 230 to 290 ° C, and preferably 230 to 270 ° C. Furthermore, from the viewpoint of improving the kneading property, the shear rate of the resin composition (a) in the extruder 2 is, for example, 10 to 1,000 / second, preferably 10 to 500 / second, and more preferably 10 to 300 / sec. From the viewpoint of improving the kneadability of the resin, the shear rate of the thermoplastic resins (b) and (c) in the extruders 1 and 3 is, for example, 10 to 1000 / sec, and preferably 10 to 1,000. 500 / second, more preferably 10 to 300 / second. The shear rate can be controlled by changing conditions such as the shape of the screw, the ratio (L / D) of the screw length (L) to the screw diameter (D), and the number of screw rotations.

The extruder may be a single-shaft extruder or a multi-shaft extruder (for example, a double-shaft extruder, etc.). In addition, the lip interval of the die can usually be adjusted by switching the choke bar bolts arranged in the width direction of the die so that the thickness of the resin laminated body 10 is within the range described later. It can be adjusted according to the ground, and is preferably 1.01 to 10 times, more preferably 1.1 to 5 times, with respect to the thickness of the resin laminated body 10. The lip interval of the die may be uniform from one end to the other end, or may have a distribution in the width direction. For example, when the lip interval at both ends is narrower than the lip interval at the center portion, the stretching resonance phenomenon can be more effectively suppressed.

For the extruder 1 to 3 which melts the resin composition (a), the thermoplastic resin (b), and (c), it may be provided to filter and remove the resin composition (a), the thermoplastic resin (b), and (c) Screens for medium and large foreign objects, polymer filters for filtering and removing small foreign materials, gels, etc .; gear pumps for quantifying the amount of resin composition extruded and thermoplastic resins.

From the viewpoint of adjusting the discharge temperature of the molten resin laminate, optimizing the average cooling rate in the subsequent cooling process, and improving the transparency of the resin laminate, the feed block 4 and the multi-manifold die 5 The temperature is, for example, 230 to 280 ° C, preferably 230 to 270 ° C, and more preferably 240 to 270 ° C.

The discharge temperature of the molten resin laminate 6 discharged from the die (multi-manifold die 5) may be, for example, the discharge temperature exemplified above.

The molten resin laminated body 6 discharged from the multi-manifold die 5 is cooled and solidified by the cooling rollers 1 to 3 to obtain a resin laminated body 10. At this time, the average cooling rate from the discharge temperature of the molten resin laminate to 100 ° C. may be, for example, the average cooling rate exemplified above.

When the molten resin laminate is cooled by the cooling roller, it is easy to control the average cooling rate of the molten resin laminate, and a stable and transparent resin laminate can be obtained.

The first cooling roller 7, the second cooling roller 8, and the third cooling roller 9 (hereinafter collectively referred to as a cooling roller) may be, for example, a metal roller, an elastic roller (or a metal elastic roller), and the like. These rollers can be used alone or in combination of two or more. For example, at least one of the three cooling rollers can be an elastic roller. Preferably, the first cooling roller 7 and the third cooling roller 9 can be set as elastic rollers. The two cooling rollers 8 are configured as metal rollers.

The metal roller is not particularly limited as long as it has high rigidity, and examples thereof include a drilling roller and a spiral roller. The surface state of the metal roller is not particularly limited, and may be, for example, a mirror surface, or a pattern, unevenness, or the like.

The elastic roller includes, for example, a substantially cylindrical shaft-shaped roller that is rotatably provided, a cylindrical metal film that contacts the resin laminate and is disposed so as to cover the outer peripheral surface of the shaft-shaped roller, and is sealed to the shaft. The fluid (for example, water, oil, etc.) between the roller and the metal film is composed of the fluid, and the elastic roller exhibits elasticity. The axis roller is not particularly limited, and is made of, for example, stainless steel. The metal thin film is made of, for example, stainless steel, and its thickness is preferably about 2 to 5 mm. It is preferable that the metal thin film has flexibility, flexibility, and the like, and it is more preferable that it has a seamless structure without a welded portion. The metal elastic roller provided with such a metal film has excellent durability and can be treated in the same manner as a normal mirror roller if the metal film is mirror-finished. If a pattern or unevenness is provided on the metal film, it becomes possible because The shape transfer roller has good usability.

The shape of the surface of the cooling roller may be smooth or uneven (for example, the outer peripheral portion of the both ends of the cooling roller may have stepped portions).

By adjusting the gap (roller gap) between the first cooling roller and the second cooling roller and between the second cooling roller and the third cooling roller, the pressure (or line pressure) applied to the molten resin laminate can be set. The pressure (or linear pressure) can be appropriately adjusted according to the desired thickness of the resin laminate.

In a preferred aspect, the aforementioned elastic roller is used for cooling at least one of the rollers. In this aspect, it is possible to suppress accumulation of strain applied to the resin laminated body sandwiched between the cooling rollers, and to prevent cracking easily even when an impact is applied, and it is possible to produce a resin laminated body with excellent surface hardness.

The size of the cooling roller is, for example, 200 to 1000 mm, preferably 250 to 700 mm. The surface temperature of the cooling roller is preferably set to (Th-20 ° C) ≦ Tr ≦ (Th + 20 ° C) with respect to the glass transition temperature (Th) of the molten resin laminate, and more preferably (Th- 15 ° C) ≦ Tr ≦ (Th + 10 ° C), and more preferably (Th-10 ° C) ≦ Tr ≦ (Th + 5 ° C). When the surface temperature (Tr) is above the lower limit value, residual strain and bending of the resin laminate can be suppressed due to rapid cooling of the molten resin laminate. When the surface temperature (Tr) is below the upper limit value, the resin obtained can be prevented from becoming insufficient due to insufficient average cooling rate. The layered body was cloudy and decreased in transparency. The glass transition temperature (Th) of the molten resin laminate is based on the highest resin among the resins contained in the molten resin laminate.

In one embodiment of the present invention, when the resin composition (a) includes a (meth) acrylic resin and a vinylidene fluoride resin, and the thermoplastic resins (b) and (c) each include a (meth) acrylic resin, The surface temperature of the cooling roller is, for example, 30 to 130 ° C, preferably 60 to 130 ° C, more preferably 80 to 130 ° C, and even more preferably 80 to 120 ° C.

In another embodiment of the present invention, the resin composition (a) includes a (meth) acrylic resin and a vinylidene fluoride resin, and the thermoplastic resins (b) and (c) each include a polycarbonate resin. The surface temperature of the cooling roller is, for example, 30 to 160 ° C, preferably 60 to 160 ° C, more preferably 80 to 160 ° C, and even more preferably 80 to 140 ° C. The glass transition temperature (Th) of the resin can be measured in accordance with ASTM D-648.

The surface temperature of each cooling roller may be the same, but from the viewpoint of easily controlling the average cooling rate to the above range, it is preferable that the further away from the cooling roller of the die, the lower the surface temperature. That is, it is preferable that the surface temperature becomes lower in the order of the first cooling roller, the second cooling roller, and the third cooling roller.

After the resin laminated body is wound around the third cooling roller 9, it can be pulled by a pulling roller (not shown) and wound into a roll. The average cooling rate can be controlled by adjusting the pulling speed of the pulling roller, the discharging speed of the molten resin laminate discharged from the die lip, the surface temperature of the cooling roller, and the like. The thickness of the resin laminate can also be controlled by adjusting the drawing speed and the ejection speed. The pulling speed of the pulling roller is preferably 0.5 to 10 m / minute, more preferably 1 to 9 m / minute, and even more preferably 1.5 to 8 m / minute.

In FIG. 1, an embodiment of the present invention is described, but the present invention is not limited to this embodiment.

In the manufacturing method shown in FIG. 1, the resin composition (a), the thermoplastic resin (b), and (c) are put into each extruder and melt-kneaded. However, as long as the resin composition passes through the feed block, If a molten resin laminate can be formed, the number of extruders is not limited. For example, when the thermoplastic resins (b) and (c) are the same, the thermoplastic resins (b) and (c) can also be melt-kneaded in an extruder, and then divided into two via the feed block and the like to form Laminated body of molten resin.

Moreover, in the aspect shown in FIG. 1, the feed block and the multi-manifold die are used, but other conventional die such as a T die, a double groove die, and the like can also be used. These dies can be used alone or in combination as long as they can form a resin laminate. For example, the feed block can be used in combination with a T-die, or a multi-manifold die can be used alone.

The method of laminating each layer may be a pre-lamination method in which a molten resin composition (a), thermoplastic resins (b), and (c) are distributed into a three-layer structure with a feed block and flowed into a T-die. ; It is also possible to laminate the molten resin composition (a), thermoplastic resin (b), and (c) into a multi-manifold die, and form a three-layer structure in the die in front of the die lip.

The number of the cooling rollers is not particularly limited, and is, for example, 1 to 10, and preferably 2 to 5. In the case where there are a plurality of cooling rollers, the size of the cooling roller and the type of the cooling roller (for example, an elastic roller, a metal roller, etc.) may be the same or different for each cooling roller. In addition, the arrangement of the cooling rollers may be a horizontal arrangement type arrangement as shown in FIG. 1, or a vertical arrangement type or an oblique arrangement type.

After passing the cooling roller, a heater can also be set to adjust the average cooling speed of the sheet.

Although a cooling method using a cooling roller is described as a preferred embodiment, as long as the molten resin laminate can be cooled at the cooling rate described above, it may be another conventional cooling method different from the method using a cooling roller. For example, cooling methods such as cold air and water cooling.

With the resin laminate obtained by the present invention, the laminate manufactured as described above is cut and distributed in the form of a resin laminate having a width of 500 to 3000 mm and a length of 500 to 3000 mm, for example.

<Resin laminate>

From the viewpoint of improving the transparency of the resin laminate and suppressing the bending, the resin laminate obtained by the production method of the present invention preferably has an average film thickness of the resin laminate of 100 to 2000 μm, and a thermoplastic resin. The average values of the film thicknesses of the layers (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 by the present invention is preferably 100 μm or more, more preferably 200 μm or more, and even 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 even more preferably 1000 μm or less. The film thickness of the resin laminate was measured by a digital micrometer. The average value obtained by performing the above-mentioned measurement at 10 locations of the resin laminate was taken as the average value of the film thickness.

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

From the viewpoint of the 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 even more preferably 300 μm or more. . From the viewpoint of transparency, the thickness 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 the measurement of the average value of the film thickness of the thermoplastic resin layer.

The resin laminate obtained by the present invention is preferably transparent when visually observed. Specifically, the resin laminate obtained by the present invention has a total light transmittance of at least 85%, more preferably at least 88%, and even more preferably at least 90%, as measured in accordance with JIS K7361-1: 1997. Tt). The upper limit of total light transmittance is 100%. After being exposed to the environment of 60 ° C. and a relative humidity of 90% for 120 hours, the resin laminate having the above-mentioned range still has a good total light transmittance.

With the resin laminate obtained by the present invention, the resin laminate is used after being exposed to an environment of 60 ° C. and a relative humidity of 90% for 120 hours. According to JIS K7136: 2000, it is preferably 2.0% or less, and more preferably 1.8% or less. , And even more preferably with a haze of 1.5% or less. In addition, the resin laminate obtained by the present invention uses a resin laminate that has been exposed to an environment of 60 ° C. and a relative humidity of 90% for 120 hours. According to JIS Z8722: 2009, it is preferably 1.5 or less, and more preferably 1.4 or less. , And more preferably has a yellowness (Yellow Index: YI value) of 1.3 or less. The resin laminate obtained by the present invention having the above-mentioned haze and yellowness is preferable because it maintains transparency even when used in an environment such as high temperature and high humidity, and is less prone to warping and yellowing.

From the viewpoint of obtaining sufficient functions when used in a display device such as a touch panel, the resin laminate obtained by the present invention preferably has a dielectric constant of 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 the type and amount of the vinylidene fluoride resin contained in the intermediate layer (A) of the resin laminate of the present invention, or by adding high dielectrics such as ethyl carbonate and propylene carbonate. A constant compound while adjusting to the above range. The dielectric constant is a value measured in accordance with JIS K6911: 1995 by leaving the resin laminate in an environment of 23 ° C. and a relative humidity of 50% for 24 hours, and measuring it at 3 V and 100 kHz by an automatic balance bridge method in this environment. 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 by the present invention may have at least a structure in which a thermoplastic resin layer (B) / intermediate layer (A) / thermoplastic resin layer (C) is sequentially laminated, except for the intermediate layer (A) and the thermoplastic resin layer. In addition to (B) and (C), there may be at least one functional layer. The functional layer is preferably present on the surface of the thermoplastic resin layer (B) and / or (C) on the side opposite to the intermediate layer (A). Examples of the functional layer include a hard coating 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 a resin laminated body via a pressure-sensitive adhesive layer, or may be a coating layer laminated by coating. As the functional layer, for example, a hardened coating film described in Japanese Patent Application Laid-Open No. 2013-86273 can be used. The functional layer may be, for example, one side or both sides of 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 or a sputtering method. A layer further coated with an anti-reflection layer such as a vacuum deposition method or the like may be a layer in which an anti-reflection sheet is bonded to one or both sides of the at least one functional layer. Even in the case of a resin laminate including such functional layers, each layer is separately produced by the above-mentioned forming method, melt extrusion molding method, solution flow casting film method, hot pressing method, injection molding method, etc. It is manufactured by laminating through an adhesive and an adhesive, for example, and it can also be manufactured by lamination and integration by a co-extrusion molding method.

The thickness of the functional layer can be appropriately selected depending on the purpose of each functional layer, but from the viewpoint of easily expressing the function, it is preferably 1 μm or more, more preferably 3 μm or more, and still more preferably 5 μm or more. From the viewpoint of cracking the layer, the thickness is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 70 μm or less.

The resin laminate obtained by 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. The display device may be, for example, a liquid crystal display device, an organic electroluminescent (EL) display device, an inorganic electroluminescent (EL) display device, a touch panel display device, an electron emission display device (such as an electric field emission display device (FED), Surface electric field emission display device (SED)), electronic paper (display device using electronic ink, electrophoretic element), plasma display device, projection display device (e.g. grid light valve (GLV) display device, digital micromirror device (DMD) display devices) and piezoelectric ceramic displays. The liquid crystal display device 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 display devices that display two-dimensional images or stereoscopic display devices that display three-dimensional images. The resin laminate obtained by the present invention is suitable for use in such display devices as, for example, a front panel or a transparent electrode.

When the resin laminate obtained by the present invention is used as a transparent electrode in a touch panel or the like, a transparent conductive film can be formed on at least one surface of the resin laminate to produce a transparent conductive sheet, and a transparent conductive sheet can be produced from the transparent conductive sheet. electrode.

As for the method of forming a transparent conductive film on at least one surface of the resin laminate obtained by the present invention, a transparent conductive film can be directly formed on the surface of the resin laminate, or a plastic film formed with a transparent conductive film in advance can be laminated on The surface of the resin laminated body of this invention.

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

The method of laminating a film on which a transparent conductive film is formed in advance on the surface of the resin laminate of the present invention may be any method as long as it is a method capable of obtaining a uniform transparent sheet without bubbles or the like. A method of laminating an adhesive that is hardened by normal temperature, heating, ultraviolet rays, or visible light can be used, or it can be laminated by a transparent adhesive tape.

As a method for forming a transparent conductive film, a vacuum evaporation method, a sputtering method, a CVD method, an ion plating method, a spray method, and the like are known, and these methods can be appropriately used depending on the required film thickness.

In the case of the sputtering method, for example, a general sputtering method using an oxide target, a reactive sputtering method using a metal target, and the like can be used. At this time, oxygen, nitrogen, or the like may be introduced as a reactive gas, or means such as adding ozone, irradiating plasma, and ion assist may be used in combination. Furthermore, a DC, AC, or high frequency bias may be applied to the substrate as needed. Examples of the transparent conductive metal oxide used for the transparent conductive film 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, indium-tin composite oxide (ITO) is suitable from the viewpoint of environmental stability and circuit processability.

In addition, as a method for forming a transparent conductive film, a coating agent containing various conductive polymers capable of forming a transparent conductive coating film may be applied to the surface of the resin laminated body of the present invention, and heat or ultraviolet rays may be applied. A method of curing the coating by releasing radiation. As the conductive polymer, polythiophene, polyaniline, polypyrrole, and the like are known, and these conductive polymers can be used.

The thickness of the transparent conductive film is not particularly limited, but when a transparent conductive metal oxide is used, it is usually 50 to 2000 Å, preferably 70 to 1000 Å. As long as it is within this range, both conductivity and transparency are good.

The thickness of the transparent conductive sheet is not particularly limited, and the most suitable thickness can be selected according to the requirements of the product specifications of the display.

A touch sensing panel can be manufactured by using the resin laminated body obtained by the present invention as a display panel and using the transparent conductive sheet manufactured by the resin laminated body of the present invention as a transparent electrode of a touch screen or the like. Specifically, the resin laminate obtained by 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 for a touch screen of a resistive film type or a capacitive type. By disposing the touch screen in front of a liquid crystal display device, an organic EL display device, or the like, an external touch sensing panel having a touch screen function can be obtained.

The resin laminated body obtained by the present invention can be used in, for example, the above-mentioned display device, that is, a display device including the resin laminated body obtained by the present invention, and can also be used to laminate the resin laminated body and polarized light obtained by the present invention. A polarizing plate with a resin laminated body of the plate, and a display device including the polarizing plate with the resin laminated body. In the polarizing plate provided with the resin laminate obtained by the present invention, the resin laminated system is laminated on the polarizing plate with an optical adhesive such as an adhesive and an adhesive. As an adhesive agent or an adhesive agent, an appropriate one can be used.

A preferred aspect of a liquid crystal display device including a resin laminate obtained by the present invention is shown in a schematic cross-sectional view in FIG. 2. The resin laminated body 10 obtained by the present invention is laminated on the polarizing plate 11 via the optical adhesive layer 12, and the laminated body can be disposed on the viewing side of the liquid crystal cell 13. The 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 members. The second figure is an example of a liquid crystal display device, and the display device of the present invention is not limited to this configuration.

    [Example]    

Examples and comparative examples are given below to specifically explain the present invention, but the present invention is not limited to these examples.

[Fica softening temperature]

It was measured according to the B50 method specified in JIS K 7206: 1999 "Test method for plastic-thermoplastic-fica softening temperature (VST)". The Ficca softening temperature was measured using a thermal deformation tester ["148-6 continuous type" manufactured by Yasuda Seiki Seisakusho Co., Ltd.]. The test piece at this time was measured by pressing each raw material into a thickness of 3 mm.

[Content of alkali metal]

Determined by inductively coupled plasma mass spectrometry.

〔MFR〕

Measured in accordance with the method specified in JIS K 7210: 1999 "Test method for melt mass flow rate (MFR) and melt volume flow rate (MVR) of plastics-thermoplastics". The JIS specifies that poly (methyl methacrylate) -based materials are measured at a temperature of 230 ° C and a load of 3.80 kg (37.3 N).

[Total light transmittance and haze]

A haze transmittance meter (Murakami Color Research Institute Co., Ltd., "manufactured by Murakami Color Institute" HR-100 ").

〔YI value〕

Measured with "Spectrophotometer SQ2000" manufactured by Nippon Denshoku Industries Co., Ltd.

[Evaluation of Bending]

The sheet-like resin laminate was cut into a size of 100 mm × 56 mm, and a sample for bending evaluation was prepared. The bending evaluation was performed by observing the 4 ends of the sample with a high-precision CCD micrometer manufactured by Keyence, measuring the height of the resulting bend, and calculating the average of the bending height of the 4 ends.

[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 (octanethiol) and 0.1 parts by mass of a release agent (stearyl alcohol) were added to obtain a monomer mixed solution. Furthermore, 0.036 parts by mass of a polymerization initiator [1,1-bis (third butylperoxy) 3,3,5-trimethylcyclohexane] was added to 100 parts by mass of methyl methacrylate, and an initiator mixture was obtained. liquid. Continuously supplied the completely mixed polymerization reactor so that the flow ratio of the monomer mixed liquid to the initiator mixed liquid became 8.8: 1, and polymerized with an average residence time of 20 minutes and a temperature of 175 ° C until the average polymerization rate was 54%. Partial polymer was obtained. Part of the obtained polymer was heated to 200 ° C and introduced into a devolatization extruder with a vent hole. At 240 ° C, the unreacted monomer was devolatized from the vent hole, and the devolatized polymer was melted. It was extruded in a state, and after cooling with water, it was cut to obtain granular methacrylic resin (i).

The obtained particulate methacrylic resin composition was analyzed by thermal decomposition gas chromatography under the conditions shown below, and the respective peak areas corresponding to methyl methacrylate and acrylate were measured. As a result, in the methacrylic resin (i), the 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 sample: Fine-scale methacrylic resin composition (standard 2 to 3 mg), put it in the center of the elongated groove-shaped metal box, fold the metal box, gently press both ends with pliers, and seal.

Thermal decomposition device: CURIE POINT PYROLYZER JHP-22 (manufactured by Japan Analytical Industry Co., Ltd.)

Metal box: Pyrofoil F590 (manufactured by Japan Analytical Industry Co., Ltd.)

Setting temperature of thermostatic bath: 200 ℃

Set temperature of insulation pipe: 250 ℃

Thermal decomposition temperature: 590 ° C

Thermal decomposition time: 5 seconds

(Analysis conditions of gas chromatography)

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

Detection method: FID

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

Filler: FAL-M (manufactured by Shimadzu Corporation)

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

Conditions for temperature rise of the column: After being held at 100 ° C for 15 minutes, the temperature was increased to 150 ° C at 10 ° C / minute, and held at 150 ° C for 14 minutes.

INJ temperature: 200 ℃

DET temperature: 200 ℃

The methacrylic resin composition was thermally decomposed under the above thermal decomposition conditions, and the peak area corresponding to methyl methacrylate (a1) was measured when the generated decomposition product was measured under the above-mentioned analysis conditions of gas chromatography. ) And the peak area (b1) of the corresponding acrylate. Then, a peak area ratio A (= b1 / a1) was obtained from the peak areas. On the other hand, a standard product of a methacrylic resin having a mass ratio of acrylate units to methyl methacrylate units of W ₀ (known) was thermally decomposed under the above-mentioned thermal decomposition conditions, and the decomposition products to be generated were measured to The peak area (a ₀ ) corresponding to methyl methacrylate and the peak area (b ₀ ) corresponding to acrylate detected when the analysis conditions of the above-mentioned gas chromatography were measured, and the peak area ratio was obtained from the peak areas. A ₀ (= b ₀ / a ₀ ). Then, an f coefficient (= W ₀ / A ₀ ) was obtained from the peak area ratio A ₀ and the mass ratio W ₀ .

The mass ratio W of the acrylate unit to the methyl methacrylate unit in the copolymer contained in the methacrylic resin composition is obtained by multiplying the peak area ratio A by the f coefficient. From this mass ratio, W calculates the ratio (mass%) of the methyl methacrylate unit with respect to the total of the methyl methacrylate unit and the acrylate unit, and the ratio (mass%) of the acrylate unit with respect to the total of the above.

[Manufacture 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, granular methacrylic resin (ii) was obtained in the same manner as in Production Example 1, and the structural unit was measured. content. In the methacrylic resin (ii), the structural unit derived from methyl methacrylate is 97.5% by mass, and the structural unit derived from methyl acrylate is 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 1.

[Manufacture example 3]

Except for making 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 colorant were dry blended, and 40 mm was used. A single-shaft 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 2. 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. The production of the calibration curve of GPC uses polystyrene as a standard reagent, and a calibration curve is prepared from the dissolution time and molecular weight, and the weight average molecular weight of each resin is measured. Specifically, 40 mg of the resin was dissolved in 20 ml of an N-methylpyrrolidone (NMP) solvent to prepare a measurement sample. As the measuring device, two Columns "TSKgel SuperHM-H" and one "SuperH2500" made by Tosoh Co., Ltd. were used in series, and an RI detector was used as the 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 respective feeders to the preparation tank (1), where The fed resin is mixed in the preparation tank and transferred to the preparation tank (2). Drop into the feed hopper from here, use 46mm The double-shaft granulator was fully melted and kneaded at a cylinder temperature of 230 ° C. and a rotation number of 270 rpm under vacuum conditions. The molten resin was ejected from the die mouth, and the obtained strand was cooled and cut with a cutter. The resin composition (a) was used to form particles of the intermediate layer (A). As the thermoplastic resins (b) and (c) for forming the thermoplastic resin layers (B) and (C), a methacrylic resin (ii) shown in Table 1 was used. From these resin compositions (a), thermoplastic resins (b), and (c), a resin laminate is manufactured using the manufacturing apparatus shown in FIG. 3. Specifically, the resin composition (a) was 65 mm. Single-shaft extruder 16 [manufactured by Toshiba Machine Co., Ltd.] uses thermoplastic resins (b) and (c) at 45 mm The single-shaft extruders 15 and 17 (made by Hitachi Shipbuilding Co., Ltd.) were melted separately. Then, these are supplied to three types of three-layer distribution-type feed blocks 18 having a set temperature of 230 to 270 ° C, and are distributed into a three-layer structure. From the multi-manifold die 19 Two types and three layers] Extrusion to obtain a film-like molten resin laminate 20. Furthermore, in this embodiment, the B layer and the C layer are layers of the same composition. Then, the obtained film-like molten resin laminated body 20 is sandwiched between the first cooling roller 21 (diameter 350 mm) and the second cooling roller 22 (diameter 450 mm) disposed opposite to each other, and then wound around the second roller 22 At the same time, after being sandwiched between the second roller 22 and the third roller 23, it was wound around the third cooling roller 23 (450 mm in diameter), and further formed and cooled while being wound around the cooling rollers 24 and 25 to obtain a three-layer structure. 'S resin laminate 26. The obtained resin laminate 26 was colorless and transparent when visually observed. Table 3 shows the set temperature of the cooling rollers, the linear velocity (pulling speed), the total film thickness of the resin laminate 26, and the thickness of each layer.

[Examples 2, 3, and 5 and Comparative Example 1]

A resin laminate having the total film thickness and the thickness of each layer shown in Table 3 was obtained by the same method as in Example 1 except that the set temperature and linear velocity of the cooling roller shown in Table 3 were used. The obtained resin laminate was colorless and transparent when visually observed.

[Example 4]

Except that 60 parts by mass of vinylidene fluoride resin (ii) was used instead of 60 parts by mass of vinylidene fluoride resin (i), and the set temperature and linear velocity of the cooling roller shown in Table 3 were used, the same procedure as in Example 1 was used. Method to obtain a resin laminate having the total film thickness shown in Table 3 and the thickness of each layer. The obtained resin laminate was colorless and transparent when visually observed.

In the production of the resin laminates of the examples and comparative examples, a non-contact thermometer was used to measure the temperature at four points shown in FIG. 3 and calculate the cooling temperature.

‧Measuring point 1: Temperature of resin just discharged from die 19

‧Measuring point 2: 22 cooling rollers

‧Measuring point 3: On the third cooling roller 23

‧Measuring point 4: 24th cooling roller

The temperature measurement results of Examples 1 to 5 and Comparative Example 1 are shown in Table 4. Table 5 shows the sheet transfer time between measurement points. Table 6 shows the results of the average cooling rate between the measurement points calculated from the temperatures shown in Table 4 and the transfer time shown in Table 5. Furthermore, the time required for the sheet (molten resin laminate) to become 100 ° C is found by a non-contact thermometer or the like, and the time required to change the sheet (molten resin laminate) from the measurement point 1 to the point of 100 ° C is shown in Table 5 shows the average cooling rate between these values.

In the resin laminates of Examples 1 to 5 and Comparative Example 1, the content of the alkali metal (Na and K) in the intermediate layer (A) was 0.3 ppm in Examples 1 to 3, 5 and Comparative Example 1, and was implemented in Example 4 is 100 ppm.

The appearances of the resin laminates of Examples 1 to 5 and Comparative Example 1 were visually evaluated. In addition, the resin laminates of Examples 1 to 5 and Comparative Example 1 were used to evaluate the total light transmittance (Tt), haze (Haze), and bending. Furthermore, the resin laminates of Examples 1 to 3 and 5 were exposed to an environment of 60 ° C. and a relative humidity of 90% for 120 hours. The resin laminates after the endurance test were similarly subjected to full light transmittance, Evaluation of haze. In addition, the dielectric constants of the resin laminates of Examples 1 to 5 were also measured. The obtained results are shown in Table 7.

It was confirmed that the resin laminates of Examples 1 to 5 had good transparency. In particular, after the resin laminates of Examples 1 to 4 were formed, it was confirmed that there was almost no bending.

Claims (14)

    A method for manufacturing a resin laminate, wherein the resin laminate system has at least an intermediate layer (A) and thermoplastic resin layers (B) and (C) respectively present on both sides of the intermediate layer (A); the intermediate layer ( A) is formed of a resin composition (a), and the thermoplastic resin layers (B) and (C) are respectively formed of a thermoplastic resin (b) and (c); the manufacturing method includes: The step of ejecting and cooling the molten resin laminate formed from the object (a), the thermoplastic resin (b), and (c) from the die; based on all the resins contained in the resin composition (a), the resin composition ( a) containing 10 to 90 mass% of (meth) acrylic resin and 90 to 10 mass% of vinylidene fluoride resin, the weight average molecular weight (Mw) of the (meth) acrylic resin is 100,000 to 300,000; in this step The average cooling rate from the discharge temperature to 100 ° C was 2.5 ° C / second or more.         The manufacturing method according to item 1 of the scope of patent application, wherein the molten resin laminate is cooled by a cooling roller.         The manufacturing method according to item 1 or 2 of the patent application range, wherein the discharge temperature is 220 to 300 ° C.         The manufacturing method according to any one of claims 1 to 3, wherein the resin composition (a) contains 35 to 45 masses based on the entire resin contained in the resin composition (a). % Of (meth) acrylic resin and 65 to 55 mass% of vinylidene fluoride resin.         The manufacturing method according to any one of claims 1 to 4, wherein the content of the alkali metal in the resin composition (a) is based on all resins contained in the resin composition (a). It is 50 ppm or less.     The manufacturing method according to any one of claims 1 to 5, wherein the (meth) acrylic resin is a homopolymer of (a1) methyl methacrylate; and / or (a2) based on All the structural units constituting the polymer include 50 to 99.9% by mass of a structural unit derived from methyl methacrylate and 0.1 to 50% by mass of at least one structural unit derived from a (meth) acrylate represented by formula (1) Copolymer: In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₁ is a hydrogen atom when R ₂ represents an alkyl group having 1 to 8 carbon atoms, and R ₁ is methyl R ₂ represents alkyl having 2 to 8.     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 is measured at 0.1 to 40 g / 10 under a 3.8 kg load at 230 ° C. minute.         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 each of the thermoplastic resins (b) and (c) contains a Ficca softening temperature of 100 to 160 ° C.         The manufacturing method according to 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, wherein the thermoplastic resins (b) and (c) include a polycarbonate resin, and the thermoplastic resins (b) and (c) are based on the thermoplastic resins (b) and (c), respectively. The total amount of the resin contained in the) is 0.005 to 2.0% by mass of the ultraviolet absorber.         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 based on all the resins contained in each of the thermoplastic resins (b) and (c). ) Each contains (meth) acrylic resin in an amount of 50% by mass or more.         The manufacturing method as described in claim 13 in which the weight average molecular weight of the (meth) acrylic resin contained in each of the thermoplastic resins (b) and (c) is 50,000 to 300,000.