JP2013091201A - Acrylic resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acrylic resin laminate having excellent collision resistance, weather resistance, wear resistance, and heat resistance.SOLUTION: On the acrylic resin laminate, a methacrylic resin plate having a surface hardened layer on at least one surface, and ethylene/vinyl acetate copolymer resin sheet having an ethylene content of 55-90 mass% are laminated via the surface hardened layer.

Description

  The present invention relates to a resin laminate excellent in impact resistance using a methacrylic resin plate, and more particularly to a resin laminate excellent in impact resistance, weather resistance, abrasion resistance, and heat resistance.

  In recent years, environmental problems (reducing carbon dioxide emissions) have become a major problem in the automobile industry, and as the need for weight reduction increases, studies have been made to change the window material from glass to methacrylic resin plates or polycarbonate resins. ing. Similar investigations have been made to improve the impact resistance and safety of glass for building materials, and to reduce the weight of display window protection plates.

JP-A-7-112514 Special table 2009-541099 gazette

Attempts have been made to use a highly impact-resistant polycarbonate resin plate as a glazing material for vehicles, glass for building materials, and display window protection plates, but polycarbonate resin has low weather resistance and is easily scratched due to its soft surface. Have a problem. In order to solve this problem, various hard coat treatments have been studied, but the cost is very high and defects such as blisters are likely to occur, which is not practical. In addition, when polycarbonate resin is injection-molded, it is also impractical to use a very expensive injection compression molding machine that is likely to be distorted.
On the other hand, methacrylic resin plates have particularly good weather resistance and transparency among resin materials, and have basic performance as a window material. However, compared with a polycarbonate resin plate, a methacrylic resin plate is easily broken and inferior in impact resistance. As a study to improve impact resistance, studies have been made to increase impact resistance by laminating an interlayer film such as polyurethane and ethylene-vinyl acetate copolymer between methacrylic resin plates, but the performance was insufficient. (See Patent Documents 1 and 2)

In order to solve the problem that the impact resistance performance of the methacrylic resin plate is insufficient, the present invention has been made through extensive studies.
That is, in the present invention, a methacrylic resin plate having a surface hardened layer on at least one surface and an ethylene-vinyl acetate copolymer resin sheet having an ethylene content of 55 to 90% by mass are laminated via the surface hardened layer. It is the resin laminated body currently made.

  The laminate obtained by the present invention has improved adhesion between the methacrylic resin plate and the ethylene-vinyl acetate copolymer sheet and can have sufficient impact resistance. It is excellent in transparency and is suitable for a resin laminate for vehicle glazing material, a resin laminate for building glass, and a resin laminate for display window protection plate.

  The methacrylic resin plate is formed by using a known extrusion molding method, a radical polymerizable monomer mainly composed of methyl methacrylate, or a (co) polymer mixture in which a part of the radical polymerizable monomer is polymerized. It can be produced by a cast polymerization method in which it is cast and polymerized. A methacrylic resin produced by a cast polymerization method is preferred, and a methacrylic resin plate having a high softening temperature can be obtained by using the cast polymerization method.

  The methacrylic resin plate used in the present invention is a resin plate made of a (co) polymer of methyl methacrylate alone or 50 parts by mass or more of methyl methacrylate and another copolymerizable ethylenically unsaturated monomer.

  Examples of ethylenically unsaturated monomers copolymerizable with methyl methacrylate include monofunctional monomers such as methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and phenyl (meth). (Meth) acrylic acid esters such as acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate; unsaturation such as (meth) acrylic acid, maleic anhydride, and crotonic acid Acids: styrene, α-methylstyrene, (meth) acrylonitrile, phenylmaleimide, cyclohexylmaleimide and the like. Examples of the polyfunctional monomer include alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. And divinylbenzene. The methacrylic resin plate may contain glutaric anhydride units and glutarimide units. In addition, (meth) acryl means “acryl” and / or “methacryl”.

  A methacrylic resin plate having a surface hardened layer on one or both sides used in the present invention is obtained by applying a curable composition to the surface of a methacrylic resin plate not having a surface hardened layer, or such a methacrylic resin. A method obtained by immersing a plate in a curable composition and then curing with heat or ultraviolet light (UV), applying a curable composition to a mold and curing it with heat or UV, and then using the mold to methacrylic Examples thereof include a method obtained by cast polymerization of a resin plate. The latter method is more preferable because the surface of the mold is transferred so that defects such as blisters are less likely to occur.

  The curable composition is not particularly limited as long as it can be cured by irradiation with active energy rays such as ultraviolet rays or heating, and among others, a (meth) acrylate compound having a (meth) acryloyl group is used. It is mentioned as a suitable thing. Among these, a photocurable composition is preferred, and the use of a polymerizable compound having a (meth) acryloyl group in the molecule and a photopolymerization initiator exhibits high curability when irradiated with active energy rays such as ultraviolet rays, and the curing rate. Is more preferable.

  The photopolymerization initiator is not particularly limited. For example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, acetoin, butyroin, toluoin, benzophenone, p-methoxybenzophenone, 2,2- Diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4′-bis (dimethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenyl Carbonyl compounds such as propan-1-one; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; 2,4,6-trimethylbenzoyldiphenylphosphine Kisaido include a benzo dichloride ethoxy phosphine oxide and the like. The photoinitiator mentioned above may be used individually by 1 type, and may use 2 or more types together.

  It is preferable that the addition amount of a photoinitiator is 0.1-10 mass parts with respect to 100 mass parts of polymeric compounds. The curability of a curable composition improves that it is 0.1 mass part or more. On the other hand, when the amount is 10 parts by mass or less, coloring of the hard coat film formed after curing tends not to occur.

  The content of the (meth) acrylate compound having a (meth) acryloyl group in the curable composition is 30 to 80 parts by mass of the (meth) acrylate compound having 3 or more (meth) acryloyl groups, (meth) The content of the (meth) acrylate compound having one or two acryloyl groups is preferably 20 to 70 parts by mass. If the content of the (meth) acrylate compound having 3 or more (meth) acryloyl groups is 80 parts by mass or less, the shrinkage rate when curing the curable composition is small, and cracks are unlikely to occur in the surface cured layer. Become. Moreover, it becomes difficult to produce a curvature in the laminated resin board which has this surface hardening layer. Further, the adhesion between the surface hardened layer and the methacrylic resin plate is improved. When the content of the (meth) acrylate compound having 3 or more (meth) acryloyl groups is 30 parts by mass or more, the scratch resistance of the surface-hardened layer becomes good.

Specific examples of the polymerizable compound are shown below.
As a (meth) acrylate compound having one or two acryloyl groups, methyl (meth) acrylate, 2-hydroxyl methacrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, (meth) acrylate compound having 3 or more acryloyl groups As trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaglycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Ritol tetra (meth) acrylate, glycerin tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri Examples include pentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, and tripentaerythritol hepta (meth) acrylate. Polyisocyanates obtained by trimerization (for example, trimethylolpropane toluylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, trimethylhexamethylene Diisocyanate and the like) and an acrylic monomer having active hydrogen (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate), N-methylol (meta ) Acrylamide, N-hydroxy (meth) acrylamide, 1,2,3-propanetriol-1,3-di (meth) a Acrylate, 3-acryloyloxy-2-hydroxypropyl (meth) acrylate, and the like, and urethane (meth) acrylate obtained by reacting 3 or more moles of acrylic monomer per mole of polyisocyanate, tris-hydroxyethyl isocyanuric acid diester Poly [(meth) acryloyloxyethylene] isocyanurate such as (meth) acrylate and tri (meth) acrylate, known epoxy polyacrylate, known urethane polyacrylate, malonic acid / trimethylolethane / (meth) acrylic acid, malon Acid / trimethylolpropane / (meth) acrylic acid, malonic acid / glycerin / (meth) acrylic acid, malonic acid / pentaerythritol / (meth) acrylic acid, succinic acid / trimethylolethane / (meth) acrylic acid, koha Acid / trimethylolpropane / (meth) acrylic acid, succinic acid / glycerin / (meth) acrylic acid, succinic acid / pentaerythritol / (meth) acrylic acid, adipic acid / trimethylolethane / (meth) acrylic acid, adipic acid / Trimethylolpropane / (meth) acrylic acid, adipic acid / glycerin / (meth) acrylic acid, adipic acid / pentaerythritol / (meth) acrylic acid, glutaric acid / trimethylolethane / (meth) acrylic acid, glutaric acid / Trimethylolpropane / (meth) acrylic acid, glutaric acid / glycerin / (meth) acrylic acid, glutaric acid / pentaerythritol / (meth) acrylic acid, sebacic acid / trimethylolethane / (meth) acrylic acid, sebacic acid / tri Methylolpropane / (meth) acrylic , Sebacic acid / glycerin / (meth) acrylic acid, sebacic acid / pentaerythritol / (meth) acrylic acid, fumaric acid / trimethylolethane / (meth) acrylic acid, fumaric acid / trimethylolpropane / (meth) acrylic acid, Fumaric acid / glycerin / (meth) acrylic acid, fumaric acid / pentaerythritol / (meth) acrylic acid, itaconic acid / trimethylolethane / (meth) acrylic acid, itaconic acid / trimethylolpropane / (meth) acrylic acid, itaconic Acid / glycerin / (meth) acrylic acid, itaconic acid / pentaerythritol / (meth) acrylic acid, maleic anhydride / trimethylolethane / (meth) acrylic acid, maleic anhydride / trimethylolpropane / (meth) acrylic acid, Maleic anhydride / glycerin / (meth) act Two or more (meth) acrylic acids, maleic anhydride / pentaerythritol / polyhydric alcohols such as (meth) acrylic acid, and polycarboxylic acids or anhydrides thereof and (meth) acrylic acid are used. ) An esterified product having an acryloyloxy group may be mentioned. The above-mentioned polymerizable compounds may be used alone or in combination of two or more.

  Various additives conventionally used can be added to the curable composition depending on the purpose. Examples of the additive include a surfactant, a leveling agent, a dye, a pigment, an antioxidant, an ultraviolet absorber, a stabilizer, a flame retardant, and a plasticizer. The addition amount of an additive can be suitably selected within the range in which the physical properties of the surface cured layer of the resulting cured film are not impaired.

  Examples of the methacrylic resin plate having a cured surface layer on one or both sides of the present invention obtained by the above method include “Acrylite MR” (trade name, manufactured by Mitsubishi Rayon Co., Ltd.). It is preferable to use it.

  The thickness of the methacrylic resin plate having a hardened surface layer on at least one surface used in the present invention can be appropriately selected according to the use, but usually 0.5 mm to 10 mm is used. The thickness of the surface cured layer of the methacrylic resin plate according to the present invention is generally in the range of 1 μm to 100 μm, preferably 5 μm to 30 μm.

  The ethylene-vinyl acetate copolymer resin sheet having an ethylene content of 55 to 90% by mass has good adhesion to the methacrylic resin plate of the present invention, and further has good transparency. If the ethylene content in the ethylene-vinyl acetate copolymer is 90% by mass or less, the adhesiveness between the methacrylic resin plate and the ethylene-vinyl acetate copolymer is improved, and the transparency of the ethylene-vinyl acetate copolymer resin sheet is improved. Property is improved. If the ethylene content in the ethylene-vinyl acetate copolymer is 55% by mass or more, the strength of the ethylene-vinyl acetate copolymer resin sheet increases. The more preferable lower limit of the ethylene content is 60% by mass, the more preferable upper limit is 80% by mass, the still more preferable lower limit is 65% by mass, and the still more preferable upper limit is 75% by mass. When the adhesion with the methacrylic resin plate is not good, when an object collides with the laminate and the laminate is broken, the fragments of the methacrylic resin plate are peeled off from the ethylene-vinyl acetate copolymer resin sheet and around the periphery. There is a risk of splashing. If the transparency of the ethylene-vinyl acetate copolymer resin sheet is not good, the transparency of the laminate is deteriorated. Therefore, when used as a window material, the visibility is deteriorated. Further, if the strength of the ethylene-vinyl acetate copolymer resin sheet itself is low, when an object collides with the laminate, it may be broken and scattered integrally with the methacrylic resin plate.

  Furthermore, these ethylene-vinyl acetate copolymers can be used in various kinds of ultraviolet absorbers, antioxidants, plasticizers, chain transfer agents, infrared absorbers, colorants, adhesive strength modifiers and the like generally used for the methacrylic resin plates. An additive may be contained. In order to further improve the adhesiveness to the methacrylic resin plate, the ethylene-vinyl acetate copolymer preferably contains an adhesive strength adjusting agent such as a silane coupling agent.

  The thickness of the ethylene-vinyl acetate copolymer resin sheet is preferably from 0.1 to 1 mm, more preferably from 0.2 to 0.5 mm.

  The resin laminate of the present invention comprises a methacrylic resin plate and an ethylene-vinyl acetate copolymer resin sheet laminated via a surface hardened layer. A methacrylic resin plate may be further laminated via a surface hardened layer on the side where the resin plate is not laminated. Furthermore, in the resin laminate of the present invention, (n + 1) methacrylic resin plates and n ethylene-vinyl acetate copolymer resin sheets may be alternately laminated. However, n represents an integer of 1 or more.

  In particular, when used for vehicle glazing and building glass, a laminate of three or more layers having both surfaces being methacrylic resin plates and having an ethylene-vinyl acetate copolymer resin sheet as an inner layer is preferable. In this case, it is preferable to use 0.5 to 10 mm as the methacrylic resin plate and 0.1 to 5 mm as the ethylene-vinyl acetate copolymer resin sheet. In addition, although a methacrylic resin plate and an ethylene-vinyl acetate copolymer resin sheet are laminated via a hardened surface layer, glass, polycarbonate resin, or the like may be laminated on the ethylene-vinyl acetate copolymer resin sheet side. it can.

  In particular, when used as a display window protection plate, a laminate of two layers, a methacrylic resin plate and an ethylene-vinyl acetate copolymer resin sheet, is used and bonded to glass on the ethylene-vinyl acetate copolymer resin sheet side. A protective plate is preferable. In this case, it is preferable to use 0.5 to 1 mm as the methacrylic resin plate and 0.1 to 0.4 mm as the ethylene-vinyl acetate copolymer resin sheet.

  Although both surfaces of a laminated board depend on a use, it is preferable to have a surface hardening layer. In vehicle glazing, building glass, and display protection plate, if the exposed surface has a hardened surface layer, the surface is hard to be scratched and can have beauty. In this case, the methacrylic resin plate to be laminated is preferably a methacrylic resin plate having a surface hardened layer on both sides.

  As a method for obtaining the laminate of the present invention, for example, an adhesion method using a hot press or an autoclave can be mentioned. The adhesive method by hot press is to insert a pre-sheeted ethylene-vinyl acetate copolymer between methacrylic resin plates, temporarily fix it, and heat the superposed one to make an ethylene-vinyl acetate copolymer resin. The sheet is softened and further integrated by pressing with a press. The adhesion method by autoclave is to insert a pre-sheeted ethylene-vinyl acetate copolymer between methacrylic resin plates and temporarily fix it, and then seal the superposed one in a vacuum bag and reduce the pressure with a vacuum pump. It is integrated by applying pressure and heating in an autoclave.

  In order to make it easy to remove air bubbles that have entered between the laminates, a method in which the space between the press plates of the hot press can be evacuated, or an adhesion method by an autoclave using a vacuum bag is preferable. If the heating temperature is 80 ° C. or higher, the adhesion between the methacrylic resin plate and the ethylene-vinyl acetate copolymer resin sheet will be good, and if it is 150 ° C. or lower, the surface state of the methacrylic resin plate will be good. It is preferable to heat at 80 to 150 ° C. The heating time needs to be selected at least as long as the heat is sufficiently transmitted to the ethylene-vinyl acetate copolymer resin sheet through the methacrylic resin plate. When the thickness of the methacrylic resin plate is 2 mm, heating for 10 minutes or more is necessary. The pressure at the time of pressurization is usually 0.01 MPa to 1 MPa.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by an Example.
Evaluation and test methods used in Examples and Comparative Examples are shown below.
(1) Humidity resistance test After holding a test piece for 2 days in a constant temperature and humidity chamber set at 50 ° C. and 95%, a methacrylic resin plate and an ethylene-vinyl acetate copolymer resin sheet were not separated. “◯”, “X” indicates that the methacrylic resin plate and the ethylene-vinyl acetate copolymer resin sheet were partially separated.
(2) Adhesive strength test Tensile testing machine for the peeled ethylene-vinyl acetate copolymer resin sheet portion of the test piece from which a part of the end of the methacrylic resin plate and the ethylene-vinyl acetate copolymer resin sheet was peeled off. (Orientec Co., Ltd., trade name RTE-120) was fixed with a chuck, and the laminate body was fixed with another chuck. Then, the film (ethylene-vinyl acetate copolymer resin sheet portion) was pulled in the 180 ° direction at a speed of 100 mm / min, and the peel strength at that time was measured.
(3) Optical characteristic evaluation The total light transmittance and haze value were measured using a haze meter (trade name HM-150, manufactured by Murakami Color Research Laboratory) (based on JIS K 7361-1, 7136).
(4) Abrasion resistance test Load: 500 g, abrasion wheel: rubber ring having hardness of 72 ± 5 IRHD, rotation speed: 60 rpm, test number: Taber abrasion test (Toyo Seiki Seisakusho, Taber abrasion) The haze value before and after the test was measured in the same manner as (3) optical characteristics, and a numerical value represented by Δhaze (the haze value after the test−the haze value before the test) was obtained.
(5) Impact resistance test After the laminate was cut into 100 mm x 100 mm and held at 23 ° C or -20 ° C for 24 hours or more, it was attached to a jig for fixing the laminate with 4 cm across 2 cm, and 1.04 kg The steel ball was dropped freely so as to hit the center of the laminate from a height of 1 m or 0.5 m. Evaluation was made as “◯” when the broken pieces were not scattered and the steel balls were not penetrated, and “X” when the broken pieces were scattered or the steel balls were penetrated.

Example 1
TAS (condensation mixture of succinic acid / trimethylolethane / acrylic acid molar ratio 1: 2: 4) (Osaka Organic Chemical Co., Ltd.) 35 parts by mass, C6DA (1,6-hexanediol diacrylate) (Osaka Organic Chemical Industry Co., Ltd.) 30 parts by mass, M305 (pentaerythritol triacrylate M-305) (manufactured by Toagosei Co., Ltd.), 10 parts by mass, M400 (dipentaerythritol hexaacrylate M-400) (Toagosei Co., Ltd.) )) And 25 parts by mass of DAROCUR TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) (manufactured by Ciba Japan Co., Ltd.) X 30 cm) and a biaxially stretched film (diamond) made of polyethylene terephthalate having a thickness of 20 μm thereon. Yl Inc.) arranged, ironing with JIS hardness of 40 ° rubber roll was set the thickness of the photocurable resin composition layer to 15 [mu] m. Thereafter, the PET film was peeled off and allowed to stand in an atmosphere of 18 ° C. for 10 minutes, and then the position of 30 cm under a high-pressure mercury lamp with an output of 120 W / cm ² was set to 2.5 m with the application surface of the photocurable resin composition facing up. Cured at a speed of 2 minutes per minute. The two SUS plates treated in this way are opposed to each other with a space (2.44 mm) so that the coated surface of the cured coating film is on the inside, and the periphery is sealed with a gasket made of soft polyvinyl chloride for casting polymerization. A cell was prepared. In this cell, 100 parts by mass of syrup composed of 20% by mass of a methyl methacrylate polymer (molecular weight (Mw) 240000) and 80% by mass of methyl methacrylate, and 0.22 parts by mass of t-hexylperoxypivalate as a polymerization initiator. A resin raw material consisting of the following was injected and polymerized in an 82 ° C. water bath for 30 minutes and then in a 130 ° C. air furnace for 30 minutes. After cooling, the SUS plate was peeled to obtain a methacrylic resin plate having a thickness of 2 mm having cured films on both surfaces.
Next, two methacrylic resin plates having a surface hardened layer on both sides and an ethylene-vinyl acetate copolymer resin sheet “S-LEC EN-UT 0.4 mm” (trade name, manufactured by Sekisui Chemical Co., Ltd., The methacrylic resin plate, S-LEC EN-UT, and methacrylic resin plate were laminated in order and temporarily fixed. Next, after enclosing in a vacuum bag and reducing the pressure with a vacuum pump, it is put in an autoclave and pressurized to 0.08 MPa. After 10 minutes, the temperature rise is started and the system is heated to 80 ° C. and heated after 47 minutes. After stopping, the laminated body was produced by cooling. Table 1 shows the evaluation results of the moisture resistance test.
Further, a methacrylic resin plate having a hardened surface on both sides and an ethylene-vinyl acetate copolymer resin sheet “S-LEC EN-UT 0.4 mm” (trade name, manufactured by Sekisui Chemical Co., Ltd., ethylene content 67 (Mass%) and a 250 μm thick PET film (trade name Lumirror S10 manufactured by Toray Industries, Inc.) are laminated in the order of a methacrylic resin plate, S-LEC EN-UT, and a PET film, and a laminate is produced in the same manner as above. Then, an adhesive strength test was conducted. The PET film was measured by being fixed to the same chuck integrally with the ethylene-vinyl acetate copolymer resin sheet. Table 1 shows the evaluation results of the adhesive strength.

Example 2
Two methacrylic resin plates each having a hardened surface layer prepared in the same manner as in Example 1 and an ethylene-vinyl acetate copolymer resin sheet “S-LEC EN-UT 0.4 mm” (trade name, Sekisui A methacrylic resin plate, S-LEC EN-UT, and a methacrylic resin plate were laminated in order and temporarily fixed. Using a hot press "NIC200 Laminating Press" (trade name, manufactured by Nissei Plastic Industry Co., Ltd.) that can evacuate the inside of the press plate, after preheating at 100 ° C for 15 minutes, hold at 100 ° C for another 5 minutes. Then, after pressing at 1 MPa, the laminate was produced by cooling and subjected to optical property evaluation, abrasion resistance test, and impact resistance test. The evaluation results are shown in Table 2.

Comparative Example 1
Two types of laminates were produced in the same manner as in Example 1 except that a methacrylic resin plate having no surface hardened layer was produced, and a moisture resistance test and an adhesive strength test were performed. The evaluation results are shown in Table 1.

Comparative Example 2
A methacrylic resin plate having a hardened surface layer disposed only on one side was prepared, and the same procedure as in Example 2 was performed except that the surface having no hardened layer was disposed so as to be laminated via an ethylene-vinyl acetate copolymer resin sheet. A laminate was produced and subjected to optical property evaluation, abrasion resistance test, and impact resistance test. The evaluation results are shown in Table 2.

Comparative Example 3
A methacrylic resin plate having a hardened surface on both sides was prepared in the same manner as in Example 1 except that the thickness of the methacrylic resin plate was 4 mm. The obtained methacrylic resin plate having a hardened surface on both sides was subjected to optical property evaluation, abrasion resistance test, and impact resistance test. The evaluation results are shown in Table 2.

Comparative Example 4
A methacrylic resin plate having no surface hardened layer was produced in the same manner as in Example 1 except that the thickness of the methacrylic resin plate was 4 mm and no surface hardened layer was formed. The obtained methacrylic resin plate not having a hardened surface layer was subjected to optical property evaluation, abrasion resistance test, and impact resistance test. The evaluation results are shown in Table 2.

Comparative Example 5
Two methacrylic resin plates having a hardened surface on both sides produced in the same manner as in Example 1 were directly stacked without an ethylene-vinyl acetate copolymer resin sheet interposed therebetween to evaluate optical characteristics and wear resistance. An abrasion test and an impact resistance test were performed. The evaluation results are shown in Table 2.

Evaluation About each laminated body produced above, it evaluated according to said evaluation and a test method. The results are summarized in Tables 1 and 2.

As is clear from Example 1 described above, when the surface-hardened layer is in contact with the ethylene-vinyl acetate copolymer resin sheet, the adhesive force is very high, and thus the moisture resistance and impact resistance are remarkably excellent.
The laminate obtained from Example 2 is excellent in impact resistance, abrasion resistance, and transparency, and is suitable for a resin laminate for vehicle glazing materials, a resin laminate for building material glass, and a resin laminate for display window protection plates. It was a thing.
As mentioned above, Example 1 or 2 was excellent as a resin laminated body for vehicle glazing materials, a resin laminated body for building material glass, and a resin laminated body for display window protection plates.

  The resin laminate according to the present invention can be widely applied as a resin laminate for vehicle glazing materials, a resin laminate for building material glass, a resin laminate for display window protection plates, and the like.

Claims (7)

  A resin laminate in which a methacrylic resin plate having a surface hardened layer on at least one surface and an ethylene-vinyl acetate copolymer resin sheet having an ethylene content of 55 to 90% by mass are laminated via the surface hardened layer. body.   The surface hardened layer has 30 to 80 parts by weight of (meth) acrylate compound units having 3 or more (meth) acryloyl groups, and (meth) acrylate compound units 20 to 70 having 1 or 2 (meth) acryloyl groups. The resin laminate according to claim 1, comprising a mass part.   The resin laminated body of Claim 1 which has a surface hardening layer on both surfaces of the said methacrylic resin board.   2. The resin laminate according to claim 1, wherein (n + 1) methacrylic resin plates and n ethylene-vinyl acetate copolymer resin sheets are alternately laminated (where n represents an integer of 1 or more). body.   The resin laminate according to claim 1, which is used for a vehicle glazing material.   The resin laminate according to claim 1, which is for building glass.   The resin laminate according to claim 1, which is used for a display window protection plate.