JP2005144872A - Laminated plate, glazing material for window, and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated plate which has excellent abrasion resistance, scratch resistance, heat resistance, chemical resistance, and durability equivalent to those of inorganic glass, keeps various properties including lightweight and impact resistance equivalent to those of synthetic resins in a good balance, and has a satisfactory inorganic glass surface. <P>SOLUTION: The laminated plate in which an inorganic glass plate C (which is) 0.05-2 mm in thickness is adhered to at least one side of the surface of a molded plate made of a synthetic resin A of 1-30 mm thickness through a silane coupling agent condensate layer D and a layer of a synthetic resin B having a modulus of elasticity smaller than that of the synthetic resin A at 25°C and its production method are provided. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a laminate having improved wear resistance on the surface of a resin plate, and more specifically, wear resistance, transparency, surface smoothness, heat resistance, compared to wear resistant articles produced by conventional coating, Chemical resistance, durability, etc. are improved drastically, and glazing materials such as lightweight automobile windows, train and train railcar windows, and building windows, and flat panels such as LCD and PDP The present invention relates to a laminated plate that can be used for a display front plate and a light guide plate, and a manufacturing method thereof.

Optically transparent synthetic resin molded products manufactured from polymethyl methacrylate resin, polymethacrylimide resin, polycarbonate resin, polystyrene resin, polyolefin resin, etc. are not only lightweight and superior in impact resistance compared to glass products, In recent years, it has been used in various fields such as optical discs, home appliance parts, automotive plastic materials, and various film materials, taking advantage of various advantages such as good transparency and easy molding.
However, these synthetic resin molded products have insufficient wear resistance on the surface, so the surface is easily damaged by contact with other hard objects, friction, scratches, etc. Significantly reduce the commercial value. Therefore, there is a strong demand to improve the wear resistance and scratch resistance of the surface of the molded product.

On the other hand, inorganic glass plates have conventionally been used for automobile windows, railway vehicle windows, or building windows. Inorganic glass has a specific gravity approximately 2.5 times as high as that of the above synthetic resin, and has a weight and is inferior in impact resistance and easy to crack, but its wear resistance and scratch resistance, transparency, surface smoothness, Widely adopted because of its excellent heat resistance, chemical resistance and durability.
Attempts to replace inorganic glass with synthetic resin plates have been made for a long time to reduce the weight of automobile windows and railcar windows to lighten the vehicle body and increase energy efficiency, but there are drawbacks of synthetic resin molded products, especially wear resistance. As a means for improving the scratch resistance, heat resistance, chemical resistance, durability, etc., a hard coat film is generally formed mainly on the surface of a synthetic resin molded plate or an injection molded product. For example, a paint composed of a partially hydrolyzed condensate of a silane mixture mainly composed of alkyltrialkoxysilane and colloidal silica is applied to the surface of a molded article, and then this is heat-treated to form a crosslinked cured film, thereby providing abrasion resistance. A method for improving the property (for example, see Patent Document 1), an ultraviolet curable coating composed of colloidal silica, an alkoxysilane having a functional group of methacryloyloxy group or glycidyl group, and non-silyl acrylate, and then applied to the surface of the molded article. Have disclosed methods for obtaining a wear-resistant synthetic resin molded article (see, for example, Patent Document 2 and Patent Document 3), which both cure silicon-based coatings by heating or ultraviolet irradiation. Is formed.
However, the performance of the synthetic resin plate having a hard coat layer on the surface produced by the above-described coating method is far inferior to inorganic glass even though the film is formed from silica or silicate, In fact, it cannot be used for applications that require high wear resistance, scratch resistance, chemical resistance, and durability, such as automobile windows, railway vehicle windows, and building windows. In addition, the appearance of lightweight materials with the same performance as glass on the surface of flat panel display front plates and light guide plates such as LCDs, PDPs, and organic ELs, which have been growing rapidly in recent years, is desired.

  On the other hand, glass plate / ethylene vinyl acetate copolymer / polycarbonate film / ethylene vinyl acetate copolymer / glass plate laminate or glass plate / polyurethane / polycarbonate film / polyurethane / glass plate laminate frosted glass ( For example, Patent Document 4) has been proposed, but these laminates are for the purpose of controlling transparency and color tone of glass mainly composed of inorganic glass, and are equivalent to inorganic glass in terms of weight. Therefore, there is a problem that weight reduction cannot be achieved, and an ultra-thin sheet glass having a low mechanical strength of less than 2 mm cannot be used because it undergoes a hot roll pressure bonding process.

US Pat. No. 4,006,271 Japanese National Patent Publication No.57-500984 US Pat. No. 4,438,462 JP-A-8-225346

  Therefore, the object of the present invention is to provide various abrasion resistance and scratch resistance, heat resistance, chemical resistance and durability comparable to those of inorganic glass, and various light weight and impact resistance equivalent to those of synthetic resins. An object of the present invention is to provide a laminate having an inorganic glass surface that maintains a balanced performance and is satisfactory.

  As a result of intensive studies on the above problems, the present inventors have conducted a silane coupling treatment on the surface of an inorganic glass plate C having a thickness of 0.05 to 2 mm, and then relaxed the different thermal expansion coefficients of the inorganic material and the organic material. A layer of synthetic resin B, which is a layer, is formed and polymerized after injecting a radically polymerizable composition (a) containing (meth) acrylate as a main component into a mold using at least one of the inorganic glass plates E Instead of solidifying or subjecting the surface of the inorganic glass plate C to silane coupling treatment, a radically polymerizable composition mainly composed of (meth) acrylate containing a silane coupling agent or a silane coupling agent condensate (d ′) By injecting the product (a ′) and then solidifying the polymer, the inorganic glass plate C is formed on the synthetic resin A at room temperature on one side or both sides of the synthetic resin A surface. Found that laminates having excellent abrasion resistance that is adhered through the layer of synthetic resin B having a smaller elastic modulus than sex ratio is obtained, and have completed the present invention.

That is, in the present invention, an inorganic glass plate C having a thickness of 0.05 to 2 mm is formed on one side or both sides of a surface of a molded plate made of a synthetic resin A having a thickness of 1 to 30 mm, and a layer D of a silane coupling agent condensate, The synthetic resin A is in a laminated plate bonded through a layer of a synthetic resin B having an elastic modulus smaller than the elastic modulus at 25 ° C.
Further, the present invention uses at least one sheet having the synthetic resin B side of the inorganic glass plate C in which one side of the inorganic glass plate C is subjected to silane coupling treatment and then a synthetic resin B layer is formed on the treated surface. Inorganic glass in which a radically polymerizable composition (a) containing (meth) acrylate as a main component is injected between cast molds and then polymerized and solidified, or a layer of synthetic resin B is formed on one side of an inorganic glass plate C Radical polymerization mainly composed of (meth) acrylate containing silane coupling agent or silane coupling agent condensate (d ′) between the molds using at least one sheet of the synthetic resin B side of the plate C When polymerizing and solidifying after injecting the adhesive composition (a ′), at least a part of the silane coupling agent or the silane coupling agent condensate (d ′) is a layer of the inorganic glass plate C and the synthetic resin B. Moves to the interface, in the manufacturing method of the laminate to form a layer of the silane coupling Zaichijimigo product (D).

Further, the present invention provides an inorganic glass plate C having a thickness of 0.05 to 2 mm on one side or both sides of a surface of a molded plate made of a synthetic resin A having a thickness of 2 to 20 mm, a layer D of a silane coupling agent condensate, It exists in the glazing material for windows which is adhere | attached through the layer of the synthetic resin B which has an elastic modulus smaller than the elastic modulus in 25 degreeC of the said synthetic resin A, and specific gravity is 2 or less.
Further, the present invention uses at least one sheet having the synthetic resin B side of the inorganic glass plate C in which one side of the inorganic glass plate C is subjected to silane coupling treatment and then a synthetic resin B layer is formed on the treated surface. Inorganic glass in which a radically polymerizable composition (a) containing (meth) acrylate as a main component is injected between cast molds and then polymerized and solidified, or a layer of synthetic resin B is formed on one side of an inorganic glass plate C Radical polymerization mainly composed of (meth) acrylate containing silane coupling agent or silane coupling agent condensate (d ′) between the molds using at least one sheet of the synthetic resin B side of the plate C When polymerizing and solidifying after injecting the adhesive composition (a ′), at least a part of the silane coupling agent or the silane coupling agent condensate (d ′) is a layer of the inorganic glass plate C and the synthetic resin B. Moves to the interface, in the manufacturing method of the window glazing material to form a layer (D) silane coupling Zaichijimigo thereof.

  In the present invention, “(meth) acrylate” means “acrylate and / or methacrylate”, and “(meth) acryloyloxy group” means “acryloyloxy group and / or methacryloyloxy group”.

  The laminate having the inorganic glass of the present invention on its surface is not only excellent in abrasion resistance, scratch resistance, transparency, surface smoothness, heat resistance, chemical resistance, durability, etc., but also in conventional inorganic glass plates. Compared to synthetic resin, it has the same lightness, impact resistance, and has an inorganic glass surface that maintains various performances in a balanced manner, so it can be used for automobile windows, railway vehicle windows, and building windows. It is particularly useful for applications such as glazing materials such as flat panel display front plates and light guide plates such as LCD and PDP.

Hereinafter, preferred embodiments of the present invention will be described.
First, the structure of the laminated glass and the glazing material for windows having the abrasion resistance and scratch resistance of the inorganic glass of the present invention will be described with reference to the attached FIGS.
FIG. 1 is a cross-sectional view of a laminated sheet and a glazing material in which the wear resistance and scratch resistance of an inorganic glass C are imparted to both sides of a molded sheet made of synthetic resin A. In the figure, the outermost surface is an inorganic glass plate C, C having a thickness of 0.05 to 2 mm, and a layer D of a silane coupling agent condensate that firmly binds a molded plate made of inorganic glass C and synthetic resin A inside. , D, and a layer of synthetic resin B, B having a smaller elastic modulus at room temperature than that of synthetic resin A, and a molded plate of synthetic resin A which is a central plate substrate. .
FIG. 2 is a cross-sectional view of a laminated plate having a wear resistance and a scratch resistance of inorganic glass C and a glazing material on one side of a molded plate made of synthetic resin A. The opposite surface of the inorganic glass C may be a synthetic resin A or an inorganic or organic hard coat H by a coating method depending on the desired performance required for the laminate. Further, an inorganic film may be formed on the hard coat by inorganic CVD or vapor deposition. In this hard coat forming method, a hard coat layer may be formed in advance on one glass or stainless steel mold, and transferred to a plate when the synthetic resin A is polymerized and integrated.
Next, the synthetic resin A and the synthetic resin B component forming the synthetic resin plate or the synthetic resin layer used in the present invention will be described.

[About Synthetic Resin A]
As the synthetic resin A, acrylic resin, polycarbonate resin, polyester resin and the like are preferable. Among these, an acrylic resin having a (meth) acrylate unit as a main component is preferable, and is a crosslinked or non-crosslinked copolymer obtained by polymerizing a radical polymerizable composition (a) having methyl methacrylate as a main component. A cured product of a composition containing a polymerized acrylic polymer, other high molecular weight bodies, oligomers, various additives or plasticizers is particularly preferable. “Containing as a main component” means containing 50% by mass or more. The polymerization of the radically polymerizable composition (a) is performed in a mold constituted by the inorganic glass C and a gasket for preventing liquid leakage.
The thickness of the synthetic resin A layer after polymerization and solidification is preferably 1 to 30 mm, and is preferably 2 to 20 mm, more preferably 3 to 10 mm in consideration of use as a glazing material for in-vehicle windows.

In the radical polymerizable composition (a), a monomer having at least one (meth) acryloyloxy group or vinyl group in one molecule can be used, and an aliphatic, alicyclic or aromatic group can be used. Mono- or poly (meth) acrylates, aliphatic, alicyclic or aromatic urethane poly (meth) acrylates, epoxy poly (meth) acrylates, polyester poly (meth) acrylates and other oligomeric compounds, aliphatic, Alicyclic or aromatic mono, or polyvinyl compounds or vinyl ether compounds can be used.
Specific examples thereof include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, stearyl (meth) acrylate, acrylonitrile, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) ) Acrylate, polyethylene glycol mono (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl Mono (meth) acrylate compounds such as (meth) acrylate, adducts of phthalic anhydride and 2-hydroxyethyl (meth) acrylate; 1,4-butanediol di (meth) acrylate 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol (n = 2) -15) Di (meth) acrylate, polypropylene glycol (n = 2-15) di (meth) acrylate, polybutylene glycol (n = 2-15) di (meth) acrylate, 2,2-bis (4- (meta ) Acryloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, trimethylolpropane diacrylate, bis (2- (meth) acryloxyethyl) -hydroxyethyl-isocyanurate Di (meth) acrylate compounds such as trimethyl Propane propane tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, tris (2- (meth) acryloyloxypropyl) isocyanurate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, Bis (2- (meth) acryloyloxypropyl) -2-ethoxypropyl isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) ) Multifunctional (meth) acrylate compounds such as acrylate and dipentaerythritol hexa (meth) acrylate; bisphenol A diepoxy and (meth) acrylic acid Epoxy poly (meth) acrylates such as epoxy di (meth) acrylate reacted; urethane tri (meth) acrylate obtained by reacting 1,6-hexamethylene diisocyanate trimer with 2-hydroxyethyl (meth) acrylate, isophorone diisocyanate Di (meth) acrylate obtained by reacting 2-hydroxypropyl (meth) acrylate and urethane hexa (meth) acrylate obtained by reacting isophorone diisocyanate and pentaerythritol tri (meth) acrylate, dicyclomethane diisocyanate and 2-hydroxy Urethane di (meth) acrylate reacted with ethyl (meth) acrylate, urethanization reaction product of dicyclomethane diisocyanate and poly (n = 6-15) tetramethylene glycol 2 Urethane poly (meth) acrylates such as urethane di (meth) acrylate reacted with hydroxyethyl (meth) acrylate; polyester (meth) acrylate and trimethylol reacted with trimethylolethane, succinic acid and (meth) acrylic acid Polyester (poly) methacrylate such as polyester (meth) acrylate obtained by reacting propane with succinic acid, ethylene glycol, and (meth) acrylic acid, mono styrene, divinylbenzene, vinyl acetate, ethylene glycol divinyl ether, Or a polyvinyl compound or a vinyl ether compound can be mentioned.

  These monomers may be used alone or in admixture of two or more. However, in the case of imparting excellent heat resistance and high rigidity to the laminate, It is preferable to use a compound having two or more (meth) acryloyl groups or vinyl groups and a compound having one (meth) acryloyl group or vinyl group in the molecule for reducing the viscosity at the time of casting. In order to shorten the template polymerization time, a copolymer of (meth) acrylate and a compound having one (meth) acryloyl group or vinyl group in the molecule is included in the total amount of the radical polymerizable composition (a). 1 to 30 parts by mass may be added, or the primary particles obtained by emulsion polymerization or the like may be added within a range where transparency of nano-order butadiene / styrene rubber fine particles and the like is not impaired. As the polymerization initiator, a known radical polymerization initiator such as benzoyl peroxide or azobisbutyronitrile is added in an amount of 0.005 to 1 part by mass with respect to 100 parts by mass of the total amount of the radical polymerizable composition (a) and dissolved. And then injecting into the mold, followed by polymerization by heating, or by adding an active energy ray-sensitive catalyst such as benzophenone to irradiate light energy, for example, active energy such as visible light, α, β and γ rays, and electron beams A method of irradiating a line by a known method can be used and is not particularly limited.

  In the radical polymerizable composition (a), if necessary, inorganic fine particles, organic fine particles, light diffusing agent, colorant, antioxidant, yellowing inhibitor, bluing agent, pigment, leveling agent, antifoaming Various additives such as an agent, a thickener, an anti-settling agent, an antistatic agent, an antifogging agent, an ultraviolet absorber, and a light stabilizer may be contained.

[About Synthetic Resin B]
As an example of the synthetic resin A, among the monomers used for the above-mentioned radical polymerizable composition (a), for example, methyl methacrylate having a modulus of elasticity of about 3 GPa and neopentyl glycol dimethacrylate are arbitrarily selected. Synthetic resin having a modulus of elasticity at 25 ° C. of 3 to 4 Gpa in a cross-linked copolymer obtained by combining at a ratio, or a low modulus of elasticity of less than 2 GPa at 25 ° C. of methyl methacrylate and a homopolymer after polymerization. Although it is a crosslinked copolymer obtained by combining monomers such as tetraethylene glycol (n = 4) diacrylate at about 8 to 2, a synthetic resin having an elastic modulus at 25 ° C. of 2 to 3 Gpa, and the like can be mentioned. If the synthetic resin B is a synthetic resin having an elastic modulus smaller than the elastic modulus at 25 ° C. of these synthetic resins A There. Specifically, the elastic modulus at 25 ° C. of the synthetic resin B is preferably less than 2 GPa, more preferably less than 1 GPa.

  Specific examples of the synthetic resin B include ethyl acrylate (EA) in which, for example, the homopolymer has an elastic modulus of less than 2 GPa among the monomers listed in the radical polymerizable composition (a) used for the synthetic resin A. Or a homopolymer such as isobutyl methacrylate, or a monomer in which such a homopolymer exhibits a low elastic modulus of less than 2 GPa and a monomer in which the homopolymer such as methyl methacrylate (MMA) exhibits 3 Gpa or more For example, a copolymer obtained by copolymerizing at a ratio of EA / MMA = 7/3 and having a lower elastic modulus at 25 ° C. than that of the synthetic resin A can be used. Since the synthetic resin B forms the synthetic resin layer B on the silane-treated glass plate by various coating methods, it is preferable to apply the non-crosslinked homopolymer or copolymer obtained by the above-described method in an organic solvent.

In order to increase the heat resistance of the synthetic resin B layer, a crosslinkable resin that has an elastic modulus at 25 ° C. lower than that of the synthetic resin A and does not melt even at high temperatures can be used depending on the application. As a specific example, among the monomers listed in the radical polymerizable composition (a), for example, a bifunctional tetraethylene glycol (n = 4) having an elastic modulus of a homopolymer of less than 2 GPa at 25 ° C. An example will be described in which diacrylate and cyclohexyl acrylate having a homopolymer elastic modulus at 25 ° C. of 3 GPa or more are selected. These two monomers are mixed in a ratio of 8 to 2, for example, and a composition obtained by adding a photosensitive radical polymerization initiator to this is applied to a silane-treated glass plate, and then irradiated with active energy rays. Thus, the synthetic resin layer B can be obtained by copolymerization. Synthetic resin B made of this copolymer exhibits an elastic modulus of 1 to 2 GPa at 25 ° C.
In addition, as the synthetic resin B, a two-component or one-component urethane resin, an epoxy resin, an unsaturated polyester resin, or the like that has a characteristic that the elastic modulus at 25 ° C. is smaller than that of the synthetic resin A can be used.

In forming the layer of the synthetic resin B, the synthetic resin B is previously dissolved in an organic solvent such as xylene and butyl acetate to form a coating solution having a solid content of 5 to 50% by mass, washed, and then subjected to silane coupling treatment. The surface of the glass plate C is applied by conventional methods such as brush coating, spray coating, dip coating, spin coating, roll coating, curtain coating, and the like, and if necessary, heated to dry the organic solvent contained therein.
The thickness of the synthetic resin B layer is preferably 0.05 to 5 mm, more preferably 0.1 to 1 mm.

[Inorganic glass plate C]
The inorganic glass plate C has a plate thickness of 2 mm or less. Such an inorganic glass plate C is commercially available, and the thinner the plate thickness, the better. When it exceeds 2 mm, the weight of the produced laminated board becomes heavy and is not preferable. Further, curved surfaces are required for glazing materials such as automobile windows. If the glass plate C is thick at the time of this heat bending process, it is difficult to process, it is easy to break, or the heating temperature required is not preferable. If the plate thickness is less than 0.05 mm, the inorganic glass plate C is cracked due to the polymerization shrinkage at the time of preparation or the heat-cooling cycle stress at the time of use of the laminated plate, and the impact resistance is inferior. A particularly preferable plate thickness of the inorganic flat glass C is 0.1 to 1.5 mm.

[Silane coupling treatment]
In order to firmly bond the inorganic glass plate C and the synthetic resin B layer, the surface of the inorganic glass plate C is preferably subjected to silane coupling treatment. The thickness of the layer D of the condensate of the silane coupling agent is preferably as small as possible, but is less than 10 μm, more preferably less than 1 μm, but the lower limit is the thickness of the monomolecular film layer in which the silane coupling agent is oriented, that is, about 0.001 μm. It is.
Specific examples of the silane coupling agent include, for example, 3- (meth) acryloyloxypropyltrimethoxysilane, 2- (meth) acryloyloxyethyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- Examples thereof include at least one silane compound selected from glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane and the like.
These silane compounds are dissolved in an organic solvent such as isopropanol, a hydrolysis catalyst such as water and hydrochloric acid is added, and the surface of the inorganic glass C washed with water and stirred while stirring at room temperature is brushed. It is applied by a conventional method such as spray coating, dip coating, spin coating, roll coating or curtain coating, and if necessary, it is heated to dry the organic solvent contained therein. As described above, instead of subjecting one surface of the inorganic glass plate C to silane coupling treatment, the above-mentioned silane coupling agent or silane coupling agent condensation is added to the radical polymerizable composition (a) mainly composed of (meth) acrylate. The radically polymerizable composition (a ′) to which the product (d ′) is added can also be used. When the radical polymerizable composition (a ′) is polymerized and solidified, at least a part of the silane coupling agent or the silane coupling agent condensate (d ′) is present at the interface between the inorganic glass plate C and the synthetic resin B layer. The inorganic glass plate C and the synthetic resin B layer are firmly bonded to each other by forming the layer (D) of the silane coupling agent condensate. The amount of the silane coupling agent or silane coupling agent condensate (d ′) added per 100 parts by mass of the radically polymerizable composition (a) based on (meth) acrylate is 0.001 to 5 parts by mass. It is preferable to be within the range.

[Create laminate]
After the one side of the surface of the inorganic glass plate C is subjected to silane coupling treatment by the method described above, a layer of the synthetic resin B is formed. The treated inorganic glass plate C is used as a mold using at least one, preferably two, and a radical polymerizable composition (a) containing (meth) acrylate as a main component is injected between them. Polymerized and solidified by irradiation. At the time of pouring, the inorganic glass plate C is very thin and cannot withstand the liquid thickness depending on the thickness of the synthetic resin A, so that the thickness uniformity of the final laminated plate is lowered. Therefore, as shown in FIG. In order to hold it, it is preferable to perform polymerization by placing a mold plate P for holding the shape outside the inorganic glass plate C. When two inorganic glass plates C are used, a laminated plate having inorganic glass on both surfaces is obtained, and a mold plate P2 made of one inorganic glass plate C1 and a glass plate having a thickness of 5 mm or more as shown in FIG. By using the sheet, a resin plate having only one surface made of an inorganic glass plate can be obtained. As the mold plate P, a glass plate having a thickness of 5 mm or more, a wood plate, a plastic plate, a metal plate such as stainless steel having a thickness of 1 mm or more, or the like can be used.

The polymerization conditions for the radically polymerizable composition (a) may be appropriately selected depending on the composition, the amount of the polymerization initiator, and the like, but are usually 30 in an atmosphere of 80 to 150 ° C. using an infrared ray or hot air drying furnace. Hold for ~ 120 minutes to solidify by polymerization. In the case of an active energy ray, particularly when a high-pressure mercury lamp is used, the light energy of 360 nm conversion is irradiated at 10 J / cm ² or more from both sides or one side. These combinations may be performed.

  In order to produce the laminate of the present invention, the above method is preferable in terms of productivity. However, when other resin plates such as polycarbonate resin and polyester resin that cannot be produced by radical polymerization are used as the center layer A, These resin plates can be produced by placing them at the center of the mold and injecting the radical polymerizable composition (a) into the gaps and then curing.

Hereinafter, the present invention will be described in more detail with reference to examples.
In addition, evaluation in an Example and a comparative example was performed with the following method.
1. Appearance (1) Transparency Based on ASTM D-1003, the haze value was measured using a haze meter.
In addition, in the evaluation results in the table, in combination with the haze value, when the haze value having no optical problem is less than 1, ○, and when the haze value having an optical problem is 1 or more, × Is written.
2. Abrasion resistance (1) Taber abrasion test In accordance with ASTM D-1044, an abrasion test was conducted under conditions of an abrasion wheel CS-10F, a load of 500 g, and a rotation speed of 500 cycles. After abrasion, the sample was washed with a neutral detergent and the haze value was measured with a haze meter.
In addition, in the evaluation results in the table, in addition to the haze value of the haze value, the wear resistance is ○ when the haze increase value after wear with respect to before wear is less than 2 which is a practical level, and is put into practical use. Two or more, which are unbearable levels, are indicated by x.
(2) Steel Wool Test A # 000 steel wool (manufactured by Nippon Steel Wool Co., Ltd., Bonstar (registered trademark)) is mounted on a 1 cm ² circular pad, and this is applied to the surface of a sample held on a reciprocating abrasion tester table. The pad was worn and worn for 50 cycles under a load of 1,000 g. This sample was washed with a neutral detergent, and the haze value was measured with a haze meter.
In addition, in the evaluation results in the table, in addition to the haze value of the haze value, the wear resistance is h when the haze increase value after wear with respect to before wear is less than 0.5, which is a practical level, 0.5 or more, which is a level that cannot be practically used, is indicated by x.
3. Heat resistance The sample was left in a hot air dryer at 120 ° C. for 240 hours, and the appearance change was visually observed. The circles with no change are indicated by ◯, and those with changes such as warpage, yellowing, cracking of the glass, peeling from the layer of the synthetic resin B, and whitening are indicated by X.
4). Impact Resistance A sample was placed on a rubber sheet, 30 g of a steel ball was dropped from a height of 50 cm above it, and the presence or absence of cracking or peeling from the synthetic resin B layer was visually evaluated. Those that did not change are indicated by ◯, and those that have changed such as cracking or peeling from the layer of the synthetic resin B are indicated by ×.
5). The weight of the laminated plate The specific gravity (g / cm ³ ) at 25 ° C. of the A4 size laminated plate having a length of 297 mm, a width of 210 mm, and a thickness of 8 mm was measured. Those with 2 are marked with ◯, and those with more than 2 are marked with ×.
6). Thickness of the laminated plate Measure the thickness of the manufactured A4 size laminated plate. Thickness suitable as a glazing material for windows is indicated with ◎, less than 10mm is indicated by ◎, 10-20mm is indicated by ○, and more than 20mm is indicated by ×. ing.

[Adjustment of radical polymerizable composition (a1)]
A 2-liter, 3-necked flask equipped with a stirrer, thermometer and condenser was mixed with 1,000 g of methyl methacrylate (trade name: Acryester M, manufactured by Mitsubishi Rayon Co., Ltd.) and 0.2 g of azobisisobutyronitrile. And prepolymerized at 80 ° C. for 2 hours and cooled. A radical polymerizable composition (a1) was prepared by mixing and stirring 250 g of neopentyl glycol dimethacrylate (trade name: NK ester, Shin-Nakamura Chemical Co., Ltd.) and 0.5 g of azobisisobutyronitrile at room temperature. did. In addition, the elasticity modulus in 25 degreeC of the hardened | cured material of (a1) is 3.6 GPa.

[Preparation of Coating Solution (b1) for Synthetic Resin B]
A 1-liter three-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 40 g of polyisobutyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: BR-101) and 760 g of n-butyl acetate. By mixing and stirring for a time, a coating solution (b1) of synthetic resin B was prepared. In addition, the elasticity modulus in 25 degreeC of (b1) is 1.5 GPa.

[Preparation of Silane Coupling Agent (d1)]
To a 0.5 liter Erlenmeyer flask, 20 g of 3-methacryloyloxypropyltrimethoxysilane (trade name: TSL-8370, manufactured by Toshiba Silicon Corporation) (hereinafter abbreviated as TSL-8370) and 380 g of isopropanol were mixed. A silane coupling agent (d1) was prepared by aging overnight at room temperature.

[Example 1]
An inorganic glass plate C (manufactured by Nippon Sheet Glass, ultra-thin plate glass, trade name: UFF 0.3 mm thickness, width 210 mm, length 297 mm) was thoroughly washed with detergent and water, poured into isopropanol and dried at room temperature. A silane coupling agent (d1) was applied to one side of the inorganic glass plate C by flow coating, and then heated at 100 ° C. for 30 minutes for polycondensation to form a silane coupling agent condensate layer D. In addition, the thickness of D layer is about 0.1 micrometer.
After cooling, a coating solution (b1) of synthetic resin B was further applied by flow coating on the silane-treated surface of the silane-treated inorganic glass plate C, and then heated at 80 ° C. for 30 minutes to dry the solvent. When the thickness of the synthetic resin B layer was measured with a non-contact film thickness meter, it was about 100 μm.
As shown in FIG. 3, two inorganic glass plates C on which a synthetic resin B layer subjected to silane coupling treatment is formed are combined through a vinyl chloride tube-like gasket (not shown). Two mold glass plates (mold plates) P having 210 mm length and 297 mm length were combined from the outside to form a mold and fixed with clips.
The radical polymerizable composition (a1) is poured into the mold from the gap of the gasket, and the surroundings are pressed with a clip so that the synthetic resin layer A has a thickness of 6.6 mm so that the content (a1) does not leak. After being immersed in a hot water bath at 1 ° C. for 1 hour for polymerization, it was further polymerized for 1 hour in a 120 ° C. hot air dryer.
After the polymerization, the clip was removed, and a laminated plate having an inorganic glass plate C and a thickness of about 7 mm was obtained. The evaluation results of the performance of the obtained laminate are shown in Table 1. The thicknesses of the synthetic resin A layer and the synthetic resin B layer are shown in Table 1 with numbers in parentheses (unit: mm).

[Examples 2 to 8]
The combinations shown in Table 1 were used in the same manner as in Example 1. However, in Example 7, the glass plate C was only one side, a laminated plate was prepared, and evaluated in the same manner as in Example 1. The performance evaluation results are shown in Table 1.
[Example 9]
In Example 1, a layer of the synthetic resin B is formed on the surface of the inorganic glass plate C without silane coupling treatment, and instead of the radical polymerizable composition (a1), 100 g of the radical polymerizable composition (a1) A laminate was prepared in the same manner as in Example 1 except that 1 g of 3 methacryloyloxypropyltrimethoxysilane was mixed and stirred at room temperature, and a radical polymerizable composition (a1 ′) was used. Evaluation was performed in the same manner. The performance evaluation results are shown in Table 1.

[Comparative Example 1]
Only the inorganic glass plate C having a thickness of 8 mm was evaluated in the same manner as in Example 1. The performance evaluation results are shown in Table 1.
[Comparative Example 2]
A silane coupling treatment was not performed, a synthetic resin B layer was not formed, and a laminated plate was formed in the same manner as in Example 1 using two glass plates having a thickness of 6 mm, a width of 210 mm, and a length of 297 mm for shape retention. The synthetic resin A plate was peeled off from the glass plate after forming, and the synthetic resin A plate was evaluated in the same manner as in Example 1. The performance evaluation results are shown in Table 1.
[Comparative Examples 3 to 6]
Laminates were prepared in the same manner as in Example 1 with the combinations shown in Table 1, and evaluated in the same manner as in Example 1. The performance evaluation results are shown in Table 1.
[Comparative Example 7]
Table 1 except that polymethyl methacrylate (b2: BR-83, manufactured by Mitsubishi Rayon Co., Ltd., elastic modulus at room temperature is 3.2 GPa) was used instead of the synthetic resin (b1: BR-101) of Example 1. A laminate was prepared in the same manner as in Example 1 with the combination shown in FIG. The performance evaluation results are shown in Table 1.
[Comparative Example 8]
A laminate was prepared in the same manner as in Example 1 except that the layer of the synthetic resin B was formed on the surface of the inorganic glass plate C without performing silane coupling treatment in Example 1, and as in Example 1. evaluated. The performance evaluation results are shown in Table 1.
[Reference Example 1]
Evaluation was performed in the same manner as in Example 1 using a double-sided hard coat treated plate (methacrylic resin plate, trade name: Acrylite MR, manufactured by Mitsubishi Rayon Co., Ltd.). The performance evaluation results are shown in Table 1.

  When the laminated board of the present invention is applied to windows of automobiles, railway vehicles, and buildings, the effect is great.

It is a cross-sectional schematic diagram of the laminated board glazing material which has the abrasion resistance and abrasion resistance of inorganic glass on both sides of a synthetic resin board. It is a cross-sectional schematic diagram of the laminated board glazing material which has the abrasion resistance and abrasion resistance of inorganic glass on the one side of a synthetic resin board. It is sectional drawing of the casting_mold | template which provided the casting_mold | template board in the outer side of inorganic glass for shape maintenance of a casting_mold | template. It is sectional drawing of the casting_mold | template which used one sheet | seat of the inorganic glass plate and the type | mold glass of thickness 5mm or more.

Explanation of symbols

A Synthetic resin plate B Synthetic resin layer C Inorganic glass D Layer of silane coupling agent condensate H Hard coat layer P Mold plate

Claims (7)

  An inorganic glass plate C having a thickness of 0.05 to 2 mm is formed on one side or both sides of the surface of a molded plate made of a synthetic resin A having a thickness of 1 to 30 mm, a layer D of a silane coupling agent condensate, and 25 of the synthetic resin A. A laminated board bonded through a layer of synthetic resin B having an elastic modulus smaller than the elastic modulus at ° C.   The laminated plate according to claim 1, wherein the molded plate made of the synthetic resin A is made of a polymer having a (meth) acrylate unit as a main component.   After one side of the inorganic glass plate C is subjected to silane coupling treatment, between the molds using at least one sheet having the synthetic resin B side of the inorganic glass plate C on which the synthetic resin B layer is formed on the treated surface. The manufacturing method of the laminated board of Claim 1 or 2 made to superpose | polymerize and solidify after inject | pouring the radically polymerizable composition (a) which has (meth) acrylate as a main component.   Condensation of silane coupling agent or silane coupling agent between the molds using at least one sheet of the inorganic glass plate C with the synthetic resin B side inside, in which the layer of the synthetic resin B is formed on one side of the inorganic glass plate C A silane coupling agent or a silane coupling agent condensate (d ′) is obtained when the radically polymerizable composition (a ′) containing a product (d ′) as a main component is injected and then solidified by polymerization. The manufacturing method of the laminated board of Claim 1 or 2 which transfers to the interface of the layer of the inorganic glass plate C and the synthetic resin B, and forms the layer (D) of a silane coupling agent condensate.   An inorganic glass plate C having a thickness of 0.05 to 2 mm is formed on one side or both sides of a surface of a molded plate made of a synthetic resin A having a thickness of 2 to 20 mm, and the layer D of the silane coupling agent condensate and the synthetic resin A at 25 ° C. A glazing material for windows which is bonded through a layer of synthetic resin B having an elastic modulus smaller than the elastic modulus and has a specific gravity of 2 or less.   After one side of the inorganic glass plate C is subjected to silane coupling treatment, between the molds using at least one sheet having the synthetic resin B side of the inorganic glass plate C on which the synthetic resin B layer is formed on the treated surface. The method for producing a glazing material for windows according to claim 5, wherein the radically polymerizable composition (a) containing (meth) acrylate as a main component is injected and then solidified by polymerization. Condensation of silane coupling agent or silane coupling agent between the molds using at least one sheet of the inorganic glass plate C with the synthetic resin B side inside, in which the layer of the synthetic resin B is formed on one side of the inorganic glass plate C A silane coupling agent or a silane coupling agent condensate (d ′) is obtained when the radically polymerizable composition (a ′) containing a product (d ′) as a main component is injected and then solidified by polymerization. 6. The method for producing a glazing material for windows according to claim 5, wherein at least a part of is transferred to an interface between the inorganic glass plate C and the synthetic resin B layer to form a silane coupling agent condensate layer (D).

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