JPH06255050A - Transport resin laminated body - Google Patents

Abstract

PURPOSE:To provide good impact resistance, pollution resistance, and chemical stability in a laminated body comprising a plurality of layers by laminating a first layer consisting of crystalline fluorine having a melting point of a specific temperature or higher, a second layer consisting of flexible fluororesin, and a third layer consisting of methacrylic resin. CONSTITUTION:A first layer is made such that an acrylic polymer is blended in crystalline resin having a melting point of 130 deg.C or higher. A second layer is such that one or more of monomers containing one or more of fluorine-containing monomers and a monomer having at the same time double bond and peroxy group within its molecule are copolymerized for preparing a fluorine-contained elastic copolymer having a glass transition temperature being at most room temperature, and further flexible fluororesin graft-polymerized with a vinylidene fluoride monomer is blended with an acrylic polymer. A third layer consists of methacrylic resin. The first layer satisfies the surface rigidity and chemical resistance, and the second layer is made thicker than the first layer in order to impart shock resistance, and the third layer is arbitrarily set in accordance with the mechanical strength required, wherein each interstice between the first layer and second layer, and between the second layer and third layer is subjected to thermal fusion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resinous laminate having excellent durability, transparency and chemical resistance, which is used as a resin glass for automobiles, constructions, etc., or in the form of a film, a liquid crystal substrate or a solar cell substrate. It is used as a protective film.

[0002]

2. Description of the Related Art Methacrylic resin has high light transmittance, excellent weather resistance, and is beautiful, so it can be used as a safety window glass for automobile tail lamps, signboards, skylights, store roofs, carport roofs, schools, etc. It is used. In addition, the usage amount is increasing in optical devices such as optical fibers, Fresnel lenses, resin substrates for solar cells, and electronic devices such as magneto-optical disk materials. Methacrylic resin is known to have compatibility with vinylidene fluoride resin (hereinafter referred to as "PVDF"), and USP
No. 3253060 (1966), PVDF75-9
A polymer composition of 9% and 1 to 25% of polymethylmethacrylate (hereinafter referred to as "PMMA") has been proposed, while a laminated body composed of PVDF and PMMA is disclosed in Japanese Patent Application Laid-Open No. S5-5200.
1-55381, and laminated films are also commercially available. This film is used for the purpose of improving the stain resistance of vinyl chloride sheet by adhering it to a vinyl chloride resin sheet. By using PVDF laminated to prevent scratches on the surface, PMMA film is used alone. Improved chemical resistance is recognized.

[0003]

Methacrylic resins are often used outdoors because of their weather resistance and transparency, but there are increasing demands for improvements in chemical resistance, flame retardancy, impact resistance, and the like. ing. In terms of chemical resistance, in particular, acid resistance to prevent deterioration due to acid rain and organic solvent resistance to remove stains are required. Among these required characteristics, flame retardancy, chemical resistance, etc. are improved by laminating a hard fluororesin such as PVDF on the surface of methacrylic resin, but impact resistance is not improved by such laminating, In some cases, there was a problem that it decreased. The present invention provides a methacrylic resin laminate having such a fluororesin on its surface and having a good impact strength.

[0004]

The present inventors have examined the impact resistance of a laminate of a fluororesin and a methacrylic resin having good chemical resistance and flame retardancy, and as a result, have found that the two layers have an impact absorption capacity. It was found that the impact resistance was improved by laminating a flexible material having a certain property. Further, as a result of studying a combination which is excellent in weather resistance, transparency and adhesiveness, which is the original purpose, it was found that the use of a soft fluororesin meets the purpose, and the present invention has been completed.

The "soft fluororesin" referred to in the present invention means one or more monomers containing at least one or more fluorine-containing monomers, and monomers having a double bond and a peroxy group in the molecule at the same time. And the glass transition temperature (T
The first step is to produce a fluorine-containing elastic copolymer (granular polymer) in which g) is room temperature or lower, and in the second step, an aqueous emulsion or dispersion solution of the copolymer obtained in the first step. Among them, it is a resin characterized by graft-copolymerizing at least one monomer containing at least one fluorine-containing monomer, which gives a crystalline polymer having a melting point of 130 ° C. or higher. This soft fluororesin has a good impact absorbing ability derived from the elastic copolymer of the trunk polymer, and has the property that it can be heat-sealed with the fluororesin of the first layer due to the melt moldability of the graft-polymerized PVDF.

Examples of the monomer used herein having a double bond and a peroxy bond at the same time include unsaturated peroxyesters such as t-butylperoxymethacrylate and t-butylperoxycrotonate, and t-butylperoxy. Unsaturated peroxycarbonates such as allyl carbonate and p-menthane peroxyallyl carbonate can be exemplified.

The composition of the fluorine-containing elastic copolymer is a binary copolymer of vinylidene fluoride (VDF) and hexafluoropropene (HFP), and a ternary copolymer of VDF, HFP and tetrafluoroethylene (TFE). Examples thereof include polymers and binary copolymers of VDF and chlorotrifluoroethylene (CTFE), but the composition thereof is not particularly limited.

On the other hand, examples of the fluorine-containing crystalline polymer having a melting point of 130 ° C. or higher include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, PVDF, a copolymer of VDF and TFE, VDF and H.
FP copolymer, VDF, HFP and TFE ternary copolymer, VDF and hexafluoroacetone copolymer, VD
Examples thereof include a copolymer of F and CTFE, a copolymer of TFE and ethylene, a copolymer of CTFE and ethylene, and a copolymer of TFE and fluorine-containing vinyl ether.

The first layer of the present invention is a crystalline fluororesin having a melting point of 130 ° C. or higher. For example, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, PVDF, a copolymer of VDF and TFE. , VD
F-HFP copolymer, VDF, HFP-TFE terpolymer, VDF-hexafluoroacetone copolymer, VDF-CTFE copolymer, TFE-ethylene copolymer, CTFE-ethylene copolymer Copolymer and TF
Examples thereof include copolymers of E and fluorine-containing vinyl ether, but those having a vinylidene fluoride structural unit are preferable, and PVDF or VDF described above is used.
Examples thereof include copolymers.

PVDF has a melting point of 165 to 170 ° C., has good melt moldability, has high rigidity and surface hardness among the fluororesins, and has excellent wear resistance. It is a resin. Further, a copolymer resin of VDF and another monomer as exemplified above may be used within a range that does not significantly lower the melting point. By copolymerization, the low temperature characteristics, impact resistance, surface hydrophilicity, etc. of PVDF can be modified. The molar ratio of the other monomer copolymerized with VDF is VDF: other monomer = 99: 1.
The range of 50 to 50 is desirable, and 99: 1 to 70:30.
Is more preferable. If the amount of other monomers is less than 1 mol%, the modification effect due to copolymerization is difficult to appear. If the amount of other monomers exceeds 50 mol%, the melting point will decrease and the melt viscosity will increase. The adhesion property is impaired and the surface hardness is reduced, which is not preferable as the first layer of the present invention.

Further, an acrylic polymer may be blended with the crystalline fluororesin having a melting point of 130 ° C. or more in the first layer in order to improve transparency or heat fusion property with the second layer. it can. The amount of the acrylic polymer blended with the crystalline fluororesin having a melting point of 130 ° C or higher is 130 ° C.
1 to 8 with respect to 100 parts by weight of the above crystalline fluororesin
0 parts by weight is desirable. If it is less than 1 part by weight, the modifying effect due to blending is unlikely to appear. If the blending amount exceeds 80 parts by weight, the chemical resistance of the first layer, which is the object of the present invention, will be lost.

When the first layer is a fluororesin containing vinylidene fluoride, the soft fluororesin used in the second layer of the present invention contains at least one monomer containing at least one fluorine-containing monomer, A fluorine-containing elastic copolymer (stem polymer) having a glass transition temperature of room temperature or lower is produced by copolymerizing a monomer having a double bond and a peroxy bond at the same time in the molecule, and 100 parts by weight of the stem polymer. On the other hand, a resin obtained by graft-polymerizing a vinylidene fluoride monomer in an amount of 20 to 80 parts by weight is preferable from the viewpoint of heat fusion property with the first layer. Here, if the amount of the vinylidene fluoride monomer graft-polymerized with respect to 100 parts by weight of the trunk polymer is less than 20 parts by weight, the melt viscosity of the soft fluororesin becomes high and PV
Good thermal welding with DF is not achieved. On the other hand, if it exceeds 80 parts by weight, the soft fluororesin produced becomes hard and the impact resistance of the originally intended laminate is lowered, which is not preferable.

Further, a thermoplastic flexible resin other than the fluororesin,
For example, when soft vinyl chloride, thermoplastic urethane resin, ethylene-vinyl acetate copolymer resin, etc. are used as the second layer,
These are inferior in weather resistance to the soft fluororesin, and are generally difficult to adhere to the fluororesin of the first layer. For example, the fluororesin must be adhered after plasma or corona discharge treatment, Not industrially preferable.

The methacrylic resin in the present invention refers to a resin composed of a polymer of which 90 mol% or more is composed of methacrylic acid alkyl ester. The methacrylic acid alkyl ester preferably has an alkyl group having 1 to 12 carbon atoms.
There are four, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, etc.,
Of these, methyl methacrylate is preferable. Further, up to 10 mol% of the polymer constituents, other vinyl monomers copolymerizable with the methacrylic acid alkyl ester, such as acrylic acid, methacrylic acid, acrylic ester, styrene, acrylonitrile, vinyl acetate, α-methylstyrene It is also possible to add etc.

The acrylic polymer as used in the present invention is a polymer having a methacrylic acid alkyl ester and / or an acrylic acid alkyl ester as a main component, and preferably a methacrylic acid having an alkyl group having 1 to 4 carbon atoms. It is composed of a combination of an ester and an acrylic acid ester having an organic group having 1 to 8 carbon atoms, and the content of the methacrylic acid alkyl ester and / or the acrylic acid ester is 90 mol% or more. The methacrylic acid alkyl ester is, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate or the like. Examples of the acrylate ester having an organic group having 1 to 8 carbon atoms include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, and the like. It is also possible to add up to 10 mol% of the polymer constituents, other vinyl-based monomers copolymerizable with acrylic acid ester, such as acrylic acid, methacrylic acid, styrene, acrylonitrile, vinyl acetate, α-methylstyrene. It is possible.

The preferred thickness constitution of the laminate provided in the present invention is as follows: first layer: 1 to 500 μm, second layer: 5 μm to 2 mm,
Third layer: in the range of 5 μm to 50 mm. The first layer preferably has a thickness of 1 μm or more in order to satisfy the surface hardness and chemical resistance. On the other hand, when the thickness is 500 μm or more, there is no particular difference in the effect, so that it is not necessary to increase the thickness. Second
The layer is preferably thicker than the first layer in order to develop impact resistance. The third layer is arbitrarily determined according to the required mechanical strength, but when used as a film, it is preferably 5 μm to about 1 mm, which exhibits flexibility, and for applications requiring self-supporting property. It is preferably 0.1 to 50 mm.

In the present invention, the methacrylic resin may be a preformed molded body, or a method in which the methacrylic resin is heat-sealed simultaneously with molding. The shape of the molded body is not limited, but a film, a sheet, a plate, a tube, or a plate-shaped body processed into an arbitrary shape can be exemplified. Also,
The molding method is not limited, and examples thereof include cell casting method, continuous casting method, extrusion method, free press molding, and free blow molding.

It is possible to add an ultraviolet absorber to the first layer and the second layer of the present invention. Addition amount is 0.0
It is 1 to 10% by weight, and if it is 0.01% by weight or less, the ultraviolet absorbing effect is low, and if 10% by weight or more, it is economically meaningless. The ultraviolet absorber is not particularly limited, and it can be used as long as it is usually used in a mixture with plastics. Benzophenone compounds, benzotriazole compounds, benzylidene malonate compounds, silicate compounds, acrylonitrile compounds, other compounds Can be mentioned. These compounds are, for example, 2,4-dihydroxy-benzophenone and 2,2′-dihydroxy-
4,4'-dimethoxybenzophenone, 2-hydroxy-4-alkoxybenzophenone, 2-hydroxy-4
-N-heptoxybenzophenone, 4-dodecyloxy-
2-hydroxybenzophenone, 2- (2'-hydroxy-5-methylphenyl) benzotriazole, 2-
(3 ', 5'-di-t-butyl-2'-hydroxy)-
5-chlorobenzotriazole, 2- (3'-t-butyl-2'-hydroxy-5'-methylphenyl) -5-
Chlorobenzotriazole, dimethyl p-methoxybenzylidene malonate, phenyl silicate, 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate, ethyl-2-cyano-3,3'-diphenyl acrylate, phenyl salsylate, Examples thereof include nickel bisoctylphenyl sulfide, β-benzoyloxy-2′-hydroxy-calcone, and benzoylferrocene derivative.

The transparent resin laminate of the present invention comprises a first layer and a second layer.
The second layer and the third layer are also characterized in that the layers are heat-sealed.
It is also possible to bond the layers by heat fusion, in which case each 3
The layers can be all heated once or sequentially. Further, the second layer and the third layer can be adhered by various adhesives, but considering weather resistance, the first layer-the second layer and the second layer-the third layer are also adhered by heat fusion. Preferably.

The optimum temperature for heat fusion varies depending on the composition of each layer and the component resin of each layer, but is usually 170 to 230 ° C.
It is preferable to carry out. Since it is necessary to carry out at a temperature above the temperature at which the soft fluororesin softens, it is preferable to carry out at 170 ° C. or above for both the first layer-second layer and the second layer-third layer, while considering the softening temperature of the methacrylic resin. Then, the temperature between the second layer and the third layer is preferably 230 ° C. or lower. Further, the heat fusion may be performed in a state where the respective layers are in close contact with each other, and it is not always necessary to pressurize, but it is usually performed in a non-pressurized state of 0 to 30 Kgf / cm ² or a pressurized state.

Various kinds of plastics can be mixed with the resin of each layer of the present invention within the range that the property does not deviate from the object of the present invention. In addition, each layer of the present invention may be mixed with an additive which is generally used for imparting various effects in the technical field of plastics. Additives include
For example, plasticizer, curing agent, lubricant, antioxidant, filler,
Reinforcing agents, reinforcing agents, antistatic agents, flame retardants, flame retardants, heat stabilizers, surface treatment agents and the like.

Hereinafter, the present invention will be described in more detail by showing Examples, Comparative Examples and Reference Examples, but it goes without saying that the present invention is not limited to the description of these Examples.

[0023]

【Example】

Example 1 (A) Manufacture of soft fluororesin Pure water 50 was added to a stainless steel autoclave having a capacity of 100 L.
Kg, 100 g of potassium persulfate, 150 g of ammonium perfluorooctanoate and 100 g of t-butylperoxyallyl carbonate were added, and after evacuation, 12.5 kg of vinylidene fluoride monomer and 7.55 kg of chlorotrifluoroethylene monomer were charged, and the mixture was stirred at 50 ° C.
The polymerization reaction was carried out at the temperature of 20 hours. The product was obtained in the form of white latex, which was salted out to obtain rubber-like particles. After washing with water and vacuum-drying, washing with n-hexane to remove unreacted t-butylperoxyallylcarbonate and vacuum-drying again, white powdery elastic copolymer 16K
g was obtained. The DSC curve of this elastic copolymer has an exothermic peak at 160 to 180 ° C. based on the decomposition of peroxy groups, and the active oxygen content of the elastic copolymer was determined to be 0.042% by the iodometric titration method. It was

In the next step, 12 kg of the elastic copolymer of white powder and 75 kg of Freon-R-113 were added to a stainless steel autoclave having a capacity of 100 L, and after evacuation, 6 kg of vinylidene fluoride monomer was charged, and the mixture was heated at 95 ° C. for 24 hours. Polymerization was carried out. The produced polymer was separated from the solvent and dried to obtain 16.6 Kg of white powder of soft fluororesin.
Calculated from the yield, this soft fluororesin was obtained by graft-polymerizing 38.3 parts by weight of vinylidene fluoride monomer to 100 parts by weight of the elastic fluorocopolymer.

(B) Production of soft fluororesin pellets The soft fluororesin obtained in (A) above was extruded at a temperature of 180 to 200 ° C. with an extruder (L / D: 22) having a diameter of 30 mm, and a diameter of 3 mm. The strand was cooled and then cut into pellets.

(C) Production of soft fluororesin film 30 mm of the soft fluororesin pellet obtained in (B) above
190-210 with a caliber extruder (L / D: 22)
The film was extruded at a temperature of ° C to form a film having a thickness of 300 µm and a width of 200 mm.

(D) Film formation of PVDF PVDF pellets (grade name: SOLEF1008) manufactured by SOLVEY Co., Ltd. as PVDF are extrusion-molded at the temperature of 200 to 230 ° C. in the same equipment as the above (C) to obtain a thickness of 5
A film having a width of 0 μm and a width of 200 mm was formed.

(E) Manufacture of first layer-second layer laminate A soft fluororesin film prepared in the above (C) and (D)
A laminate with the PVDF film molded in 1. was manufactured. 5
A PVDF film with a thickness of 0 μm, a width of 150 mm and a length of 150 mm is placed in the center of a 1 mm thick, 200 mm square stainless steel plate, and a PTFE film with a thickness of 0.1 mm is attached to a 50 × 150 mm portion on one side of the film to prevent welding. After placing
A 300 μm thick soft fluororesin film having the same dimensions was stacked, and a 1 mm thick, 200 mm square stainless steel flat plate was placed.

The sheet sandwiched between the stainless steel plates is 20
Put it in a compression molding machine heated to 0 ° C, heat it for the first 10 minutes without applying pressure, transfer it to a water-cooled compression molding machine, press it at a pressure of 10 Kgf / cm ² for 3 minutes, and cool it. A two-layer laminate (350 μm thick) was obtained.

(F) Production of three-layer laminate 350 μm thick, 150 mm wide, 15 produced in (E) above
Attach a 2-layer laminate with a length of 0 mm so that the PVDF surface is in contact.
Place it in the center of a 0 mm square stainless steel plate and place a 0.1 mm thick PTFE film on the 50 x 150 mm part on one side of the film that was not adhered in (E) in order to prevent welding, and then A commercially available PMMA plate (methacrylic resin plate manufactured by Mitsubishi Rayon, product name: Acrylite) having a thickness of 2 mm, a width of 150 mm, and a length of 150 mm was stacked, and a 1 mm thick, 200 mm square stainless steel flat plate was placed thereon.

The sheet sandwiched between the stainless steel plates is 18
Put it in a compression molding machine heated to 0 ° C, heat it for the first 10 minutes without applying pressure, transfer it to a water-cooled compression molding machine, press it at a pressure of 10 Kgf / cm ² for 3 minutes, and cool it. A three-layer laminate (2.35 mm thick) was obtained.

(G) Evaluation of Adhesiveness of Laminated Body The sheet of the three-layered laminate produced in (F) above has the unwelded portion in the longitudinal direction, and the boundary between the welded portion and the unwelded portion is in the center. A test piece having a width of 25 mm and a length of 100 mm is cut out so that the adhesive strength between the layers is 18 at 23 ° C. in accordance with JIS K6854 [Adhesive peel strength test method].
The 0 degree peel strength was measured. For the strength, the maximum value of the tensile load curve in the peel test was taken, and the results are shown in Table 1.

(H) Measurement of Transparency of Three-Layer Laminated Body In order to evaluate the transparency of the three-layered laminated body produced in the above (F), a haze meter (Tokyo Denshoku Co., Ltd.) of an integrating sphere method specified in JIS K6718. Co., Ltd. TC-H (III)
The total light transmittance was measured using DP). The results are shown in Table 1.

(I) Measurement of chemical resistance of the surface of the three-layer laminate A 70% sulfuric acid was dropped in spots on the first layer of the three-layer laminate produced in the above (F) using a dropper. After being left at room temperature for 24 hours, the surface was observed after washing with water. The results are shown in Table 1.

(J) Measurement of Surface Hardness of Three-Layer Laminate (Scratch Resistance) With the first layer of the three-layer laminate produced in (F) above,
The pencil scratching value was measured by the hand scratching method specified in JIS K5400, and the results are shown in Table 1.

(K) Measurement of Impact Resistance of Three-Layer Laminated Body It was carried out by using a DuPont type impact deformation tester specified in JIS K5400. The first layer of the three-layer laminate manufactured in (F) (a test piece of 70 × 150 mm was cut out from the heat-sealed portion) was fixed on a horizontal metal pedestal with the first layer facing upward. A shooting die having a radius of 6.35 mm was placed in contact with the top surface of the laminate. A weight having a mass of 500 g was dropped from a predetermined height from the upper part of the shooting die, and the presence or absence of breakage of the laminate was observed. The degree of impact resistance is represented by the maximum height at which the laminate does not break. The results are shown in Table 1.

[0037]

[Table 1]

Example 2 When the film of the soft fluororesin was molded in (C) of Example 1, the acrylic polymer was used as a loam and
20 parts by weight of pellets of methyl methacrylate / butyl methacrylate copolymer resin (trade name: Paraloid B-66) manufactured by Haas Co. were mixed with 100 parts by weight of soft fluororesin pellets to form a film. In addition, in (D) of Example 1, 20 parts by weight of PMMA resin (trade name: Acrypet MD) pellets manufactured by Mitsubishi Rayon Co., Ltd. was used as an acrylic polymer when a PVDF film was molded.
A film was formed by mixing 100 parts by weight of VDF pellets. Operations (F) to (K) were performed in the same manner as in Example 1 except for the above-mentioned two points, and the results are shown in Table 1.

Comparative Example 1 Measurements from (H) to (K) of Example 1 were performed on a single plate of a 2 mm thick sheet of methacrylic resin used for the third layer in (F) of Example 1. The results are shown in Table 1, and it is clear that the impact resistance and the chemical resistance are particularly poor as compared with the examples.

Comparative Example 2 A film having a thickness of 350 μm was produced when the PVDF film was molded in (D) of Example 1. Using this film, a two-layer laminate of PVDF and PMMA was produced in the same manner as in the operation shown in (F) of Example 1, and about this laminate from (H) to (K) of Example 1. Was measured. The results are shown in Table 1, and it is clear that the impact resistance is particularly poor as compared with the examples.

Comparative Example 3 A film having a thickness of 350 μm was produced when the soft fluororesin film was molded in (C) of Example 1.
Using this film, a two-layer laminate of a soft fluororesin and PMMA was produced in the same manner as the operation shown in (F) of Example 1, and the laminate was prepared from (H) to (K ) Was measured. The results are shown in Table 1,
It is apparent that the surface hardness is particularly inferior as compared with the examples.

[0042]

EFFECTS OF THE INVENTION The transparent resin laminate of the present invention enables strong adhesion by using a soft fluororesin as a constituent component of the second layer, and as a result, as compared with PMMA alone, as shown in the examples. Despite the fact that the total light transmittance and the degree of scratches on the surface are almost unchanged, it is clear that the chemical stability by 70% sulfuric acid, and particularly the impact resistance, is significantly improved.

Therefore, the transparent resin laminate of the present invention has a remarkable effect that it can be widely applied as a PMMA resin having impact resistance, stain resistance and chemical stability when used outdoors.

Claims (6)

[Claims] 1. A laminate comprising at least three layers, comprising:
A transparent resin laminate characterized in that the three layers are formed by laminating a first layer made of a crystalline fluororesin having a melting point of 130 ° C. or higher, a second layer made of a soft fluororesin and a third layer made of a methacrylic resin. body. 2. The transparent resin laminate according to claim 1, wherein the first layer is a blend resin containing a crystalline fluororesin having a melting point of 130 ° C. or higher and an acrylic polymer. 3. The transparent resin laminate according to claim 1, wherein the second layer is a blend resin containing a soft fluororesin and an acrylic polymer. 4. The transparent resin laminate according to claim 1, wherein the crystalline fluororesin having a melting point of 130 ° C. or higher is a fluororesin containing at least a vinylidene fluoride structural unit. 5. A soft fluororesin obtained by copolymerizing at least one monomer containing at least one fluorine-containing monomer with a monomer having a double bond and a peroxy bond at the same time in the molecule. A fluorine-containing elastic copolymer (trunk polymer) having a glass transition temperature of room temperature or lower is produced, and 2 parts of vinylidene fluoride monomer is added to 100 parts by weight of the trunk polymer.
The transparent resin laminate according to claims 1 to 4, which is obtained by graft polymerization in an amount of 0 to 80 parts by weight. 6. The transparent resin laminate according to claim 1, wherein at least the first layer and the second layer are heat-sealed.