TW581724B - Multilayer structure - Google Patents

Abstract

Disclosed is a multilayer structure having (A) a polycarbonate resin layer, (B) an adhesive resin layer and (C) a glass layer, wherein at least one of the glass layer and the adhesive resin layer comprises an ultraviolet ray-absorbing component, and preferably, the polycarbonate resin layer has terminal hydroxyl groups in an amount of 8 mole % or less of moles of the repeating unit of its polymer chain. The multilayer structure is lightweight and excellent in impact resistance and the like, and also is reduced in the yellowing and in the decrease of transparency in the case of being used outdoors for a long period of time.

Description

581724 A7

V. Description of the Invention (1) Technical Field Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The present invention relates to window glass, windows, display windows, roofs, etc. that can be used in automobiles, aircrafts, etc. Multi-layered structure; "Yangyue Zhi" is a multilayered structure in which the polycarbonate resin and glass layer are integrated by using an adhesive resin layer with improved weather resistance. Advanced technology Windows, roofs, and transparent wall materials for automobiles, buildings, schools, and shops have always been made of inorganic glass. However, in recent years, due to the increase in automobile fuel costs, the impact resistance, weight reduction, and accessibility of building window materials have demanded lightweight materials that replace inorganic glass. In addition, in order to prevent the scattering of inorganic glass plates when the window glass and sunroof glass of public buildings are damaged, there are two glass plates with an adhesive resin such as polyvinyl butyral as an intermediate layer. Use with laminated glass. However, the specific gravity of glass in inorganic glass plates and laminated glass plates is still high. It is necessary to reduce the thickness in order to reduce the weight. However, from the strength characteristics required for applications, the thinning of glass plates is limited. Therefore, recently, there have been proposals to replace inorganic glass plates with polymethyl methacrylate or polycarbonate resin plates with low specific gravity, and they have been used in windows or roofs of public buildings. Polymethyl methacrylate may not have sufficient impact resistance, and polycarbonate resins have recently attracted attention. However, the surface hardness and wiping hardness of polycarbonate-based resins are not sufficient, and they are prone to surface damage, and the use range is limited. In order to improve the surface hardness and scratch resistance, the surface of the polycarbonate resin plate is coated with a hard resin such as a silicone resin or vapor-deposited to

It --- * ---------- Order --------- line (Please read the precautions on the back before filling this page) This paper size applies to Chinese national standards (CNS) A4 specification (210 X 297 public reply) -4-581724 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (2) Proposals for improvement methods such as silicon oxide or metal oxides. However, the polycarbonate-based resin sheet having such a surface coating layer has insufficient durability, and has so far failed to replace the inorganic glass sheet. For this reason, there are proposals for a multilayer board which combines the hardness and scratch resistance of a glass plate with the transparency and strength of a polycarbonate-based resin, and particularly excellent impact resistance. For example, on the side of a polycarbonate resin sheet of about 2 to 8 mm, a glass sheet of about 1 to 2 mm is interposed with, for example, polyvinyl butyral, ethylene-vinyl acetate copolymer, polyurethane, poly It has been proposed to synthesize multilayer structures (laminates) of adhesive resin layers such as carbonate-organosiloxane (block) copolymers. These multilayer structures show significantly better resistance to impact or penetration than the individual materials of the inorganic glass plate. At the same time, by changing the thickness ratio of the inorganic glass plate and polycarbonate resin, physical properties and weight reduction can be designed. A balanced material is a major feature. In addition, the multilayer structure is based on the three-layer structure described above. For long-term use or because of the place of use, due to the difference in basic physical properties between the glass plate and the polycarbonate resin, stress cracks and fogging may be seen. , Peeling, etc. In this case, the polycarbonate resin layer of the multilayer structure may be laminated with a glass plate layer to form a symmetrical multilayer structure through an adhesive resin layer. Furthermore, according to the purpose, various other resin layers, such as hard resins such as polymethyl methacrylate, and elastic resin layers, have been proposed. These plate-like multilayer structures (laminates) having an inorganic glass plate / polycarbonate resin plate as a basic structure have excellent characteristics as described above. But this paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 male H ^ »r --------------- Order --------- line (please (Please read the notes on the back before filling out this page) 581724

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (3) Yes, most of these multi-layered structures are used in cars, windows of buildings, etc., and they are mainly oriented to the outside. For this reason, the multilayer structure is deeply affected by the ultraviolet rays from the sun, and the polycarbonate resin layer may turn yellow. As a result, discoloration occurs after the time has elapsed, and the appearance is deteriorated, and transparency is reduced, so that its use range is greatly restricted. For this purpose, there is also a case where a polycarbonate-based resin plate is molded with an ultraviolet absorbent. However, in order to prevent yellowing, it is necessary to add an ultraviolet absorbent to a considerable extent, and the polycarbonate resin sheet may be colored due to the additives. In addition, the polycarbonate resin has a high melt viscosity and a high molding temperature, and it is liable to cause sublimation of an ultraviolet absorber, etc., and the selection range of the combined ultraviolet absorber is narrow, which is lacking. The object of the present invention is to provide a multilayer structure with light weight and excellent impact resistance integrated with a polycarbonate resin and a glass plate interposed by an adhesive resin layer under the above-mentioned current conditions. Long-term use also has little yellowing or loss of transparency. DISCLOSURE OF THE INVENTION In order to achieve the object of the present invention, the present inventors have carefully studied the improvement of the weather resistance of a multilayer structure of polycarbonate resin and glass. As a result, it was found that when an ultraviolet absorbing component (agent) is added to a specific layer, an excellent effect is achieved, and the present invention has been completed. That is, the present invention relates to (1) a multilayer structure made of a polycarbonate-based resin layer (A), an adhesive resin layer (B), and a glass layer (C), which is connected to the glass layer or the adhesive layer. Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -6 ^ Γ Γ I ----- I ------ ^ «— — — — — — I— (Please read first (Notes on the back then fill out this page) 581724

5. Description of the invention (4) At least one of the resin layers is a multilayer structure containing an ultraviolet absorbing component. (Please read the precautions on the back before filling out this page.) (2) Both the glass layer (A) and the adhesive resin layer (b) contain the multilayer structure described in (1) of the ultraviolet absorbing component. (3) The glass layer (A) is a soda lime oxidized sand-based glass, and the ultraviolet absorbing component contained in the glass is a multilayer structure as described in (.1) or (2). (4) The multilayer structure according to any one of (1) to (3) of the benzotriazole-based compound and / or the triazine-based compound, the ultraviolet-absorbing component containing the adhesive resin layer (b). (5) The adhesive resin layer (B) is selected from the group consisting of ethylene-vinyl acetate copolymer, polyvinyl acetate, ethylene- (meth) acrylate copolymer, polyurethane, polyester-polyurethane copolymer, and polycarbonate- The multilayer structure according to any one of (1) to (4), which is an organosiloxane copolymer and at least one layer of a polyvinyl butyral resin. (6) The amount of the terminal hydroxyl groups of the polycarbonate used in the polycarbonate resin layer ('A) is any one of (1) to (5) below 8 mol% of the repeating unit of the polymer chain. The multilayer structure described. (7) The adhesive resin layer (B) printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has two layers, of which the polycarbonate-polyorganosiloxane copolymer is on the side near the polycarbonate resin layer (A). The multilayer structure according to any one of (1) to (6). (8) The multilayer structure according to any one of (1) to (7), wherein a glass layer is provided on the side of the polycarbonate resin layer (A) through an adhesive resin layer. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 581724

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (5) [Simplified description of the surface] Figure 1 is a sectional view of an example of the multilayer structure of the present invention. In the figure, reference numeral 1 indicates a polycarbonate resin layer, reference numeral 2 indicates a non-adhesive resin layer, and reference numeral 3 indicates a glass layer. The MMZ m best implementation is described in detail below. I. Components constituting the multilayer structure of the present invention (1) Polycarbonate-based resin layer The polycarbonate-based resin (P C) constituting the main layer of the multilayer structure of the present invention is not particularly limited, and various types can be listed. In general, aromatic polycarbonates can be made by reacting a divalent phenol with a carbonate precursor. In other words, Cinyi shellfish and carbonate are used to drive the product, which is produced by solution method or melting method, that is, the reaction of divalent phenol and phosgene, and the transesterification method of divalent phenol and diphenyl carbonate. Anyone can use it. Divalent phenols can be exemplified by various types, and in particular, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxybenzene) ) 'Ethane' 2,2-bis (4-monohydroxy-3'5-dimethylphenyl) propane, 4,4'-dihydroxybiphenyl, bis (4-monohydroxyphenyl) cycloalkane, bis ( 4 · monohydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl), bis (4-hydroxyphenyl), bis (4-hydroxyphenyl) Ethers, bis (4-hydroxyphenyl) methanone, etc., or halogen substitutes thereof. The best divalent phenols are bis (hydroxyphenyl) alkanes, especially for the size of the double paper, which is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) -8-M -------- Order --------- line (please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 581724 Α7 Β7 V. Description of the invention (6) Phenol A as the main raw material . Further, the carbonate precursor may be a carbonyl halide, a carbon ester, or a haloformate, and specifically, may be phosgene, a dihaloformate of a divalent phenol, diphenyl carbonate, Dimethyl carbonate, diethyl carbonate, etc. Examples of the divalent phenol include hydroquinone, resorcinol, and catechol. These divalent phenols may be used alone or in combination of two or more. In addition, the polycarbonate resin may have a branching structure, and the branching agent is 1, 1, 1, 1- (4-hydroxyphenyl) ethane, α, α ', α "-1 (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, pyrogallol, trimellitic acid, isatin bis (o-cresol), etc. In addition, in order to adjust the molecular weight, phenol, p-tertiary butylphenol, p Tertiary octylphenol, p-isopropylphenylphenol, p-decylphenol, etc. The polycarbonate resin used in the present invention may also be a random resin having a polycarbonate portion and a polyorganosiloxane portion. Copolymers, block copolymers, or polycarbonate resins containing the copolymers, or may be polymerized in the presence of a bifunctional carboxylic acid such as terephthalic acid or an ester precursor thereof. Polyester-polycarbonate resin obtained by polymerizing carbonates. Mixtures of various polycarbonate resins can also be used. Polycarbonate resins suitable for the present invention have an average viscosity from the viewpoint of mechanical strength and moldability. The molecular weight is preferably between 10,000 and 100,000, more preferably between 15,000 and 40,000, and between 20,000 and 30,000. In addition, the amount of terminal hydroxyl groups in the polycarbonate resin plate is 8 mol% or less, preferably 6 mol% or less, and more preferably 4 mol% or less in repeating units of the polymer chain. From the viewpoint of weather resistance, the following are particularly preferred. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -9- Bu —r ----- packing ----- --- Order --------- (Please read the notes on the back before filling this page) 581724 A7

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (7) Generally, the polycarbonate resin layer is compounded with additives such as antioxidants and formed into a film by extrusion. In this film formation, an adhesive resin layer such as a polycarbonate-organosiloxane copolymer or the like can also be co-extruded on the side that becomes the glass layer to form a multilayer film with an adhesive resin. The film thickness is preferably 1 to 10 mm, and more preferably about 2 to 6 mm. In addition, the polycarbonate resin may contain a light stabilizer or an ultraviolet absorber within an allowable range. Also, the manufacturing method may be injection molding, injection compression molding, or the like. (2) glass layer

The glass used in the glass layer (C) of the present invention is not limited as long as it is an inorganic glass, and ordinary glass plates for windows can be used. This type of glass plate is prepared by mixing the main raw materials such as silica sand, soda ash, limestone, and thenardite at a certain ratio, and mixing the glass chips (broken glass) with an appropriate ratio, and adding auxiliary materials such as alumina, magnesium oxide, and calcium oxide if necessary Oxygen, iron, nickel oxide, cobalt oxide, titanium oxide, selenium, etc. are completely melted in the kiln at 1,500 to 1,600 ° C, and the glass is converted into a homogeneous plain glass. Next, flat glass is prepared from the plain glass by a floating layer method (molded on the surface of a molten metal), etc., and then polished to obtain a polished plate glass. (3) Adhesive resin layer There are no particular restrictions on the adhesive resin 'used to bond glass plates and polycarbonate resin films, and resins used in the past can be used. Adhesive resins can be listed as ethylene-vinyl acetate copolymer, polyvinyl acetate, ethylene- (meth) acrylate copolymer, polyurethane, polyester-polyurethane copolymer, polycarbonate L ------- -Order --------- (Please read the notes on the back before filling in this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -10- Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives 581724 A7 — B7 V. Description of the Invention (8)-Polyorganosiloxane block copolymer, random copolymer, polyvinyl butyral, etc. Here, the ethylene-vinyl acetate copolymer is preferably one having a vinyl acetate content of 5 to 60% by mass. The content of the polyorganosiloxane in the polycarbonate-organosiloxane copolymer is preferably 2 to 70% by mass, and more preferably 20 to 60% by mass. That is, those having a high polysiloxane content and being soft in quality are preferred as the elastic resin. The polysiloxane block unit of polysiloxane can be arbitrarily a "silicon-oxygen-silicon" bond as an intermediary main chain bonder 'or a "silicon-carbon" bond as an intermediary main chain bonder. These polycarbonate-organosiloxane copolymers may be prepared by combining a dichloromethane solution of a polycarbonate-based polymer with dimethylsiloxane, etc. at the end of phenol, or a combination of silicone and carbon. A known method of reacting a dihydroxy compound in the presence of a triethylamine catalyst by adding an alkaline aqueous solution of bisphenol A as necessary. These adhesive resins may be unsaturated carboxylic acids such as maleic anhydride, fumaric acid, or the like, or their derivatives may be chemically modified resins, or they may contain chemically modified resins. Furthermore, in order to improve the adhesion to the glass plate, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, vinyltriethoxysilane, etc. can also be added. Its couplant. The adhesive resin is preferably a soft (elasticity of 1,000 MPa or less) resin, and is preferable from the viewpoint of buffer adhesion between a glass plate and a polycarbonate resin. As such a soft adhesive resin, there is polyvinyl butyral which is an adhesive intermediate layer which is well used for bonding of inorganic glass. However, if the polyvinyl butyral is used as the adhesive resin layer of the present invention, the order is made in --------, -------------- --- (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -TT- Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 581724 A7 __ B7 V. Description of the invention (9) There is no problem in the bonding and fixing of inorganic glass, but there will be problems in the lamination of polycarbonate resin plates. This is a plasticizer mixed with polyvinyl butyral film. The plasticizer will migrate to polycarbonate resin after lamination, which will cause the whitening and transparency of the polycarbonate resin board to decrease. At this time, a polyvinyl butyral resin-free layer and a polymer can be used. For the migration of plasticizers between carbonate resin layers, for example, other adhesive resins such as polycarbonate-polyorganosiloxane copolymers, polyurethanes, etc. That is, the adhesive resin layer is made into two or more layers. II · Multilayer structure of the present invention Hereinafter, the multilayer structure of the present invention will be described step by step based on its manufacturing method. Figure 1 The schematic cross-sectional view of the multilayer structure of the present invention. In the first figure, the '1 series polycarbonate resin plate, the 2 series adhesive resin layer, and the 3 series glass layer. The multilayer structure of the present invention is shown in FIG. 1 (1 As shown in Figure), it basically consists of a polycarbonate resin layer (A) 1, a glass layer (C) 3, and an adhesive resin layer (B) 2. Among them, the glass layer (C) and the adhesive resin layer (B) At least one, and preferably, both of them contain ultraviolet absorbing components (agents), which is a feature of the present invention. First, the glass plate system, for example, uses silica sand as the main component, and soda ash , Limestone, carbon, and thenardite are melted, and a glass frit containing various components as an ultraviolet absorbing component is added to the melt, and is usually a colored glass frit. Specifically, soda lime silica glass can be used as an example. Here 'As a UV absorbing component, it is only necessary to be a person who can reduce the transmission of UV rays after forming a glass plate without special restrictions, and can include 钸 as an example. 钸 Composition This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -12- Bu ------------- Order --------- (Please read the notes on the back before filling out this page) 581724 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs For benzotriazoles, 2- (3-tert-butyl-5, methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2-3,5-tert-butyl —2 —Hydroxyphenyl) 5-chlorobenzotriazole, 2- (5-methyl-1—2-phenylphenyl) benzotriazole, 2- (3,5—primary and secondary butyl A 2-hydroxyphenyl) benzotrid,

V. Description of the invention (W is based on the addition of 1 to 2 to the glass raw material. The ultraviolet absorbing component can also be titanium to absorb ultraviolet light. The glass containing light absorbing component is melted, pulled down, and pulled up to make a glass light glass plate. .The multilayer junction glass of this application is used, and the window glass for automobile can also be used for gentle curved surface processing. The glass is appropriately determined. For the purpose of the multilayer quantification of the present invention, it should not be too thick. About 3 millimeters is more preferred. Second, the adhesive resin can have the above-mentioned ultraviolet absorbing components (agents) without triazole, triazine, and benzotriazole, and triazine. It can be produced by dysprosium oxide. It can be divided into different colors and other components to make glass. It can be produced by floating layer method or die-casting method. It can also be honed into a paraboloid if necessary. In the case of roofing materials, etc., the thickness of the board can be based on the structure of the application and size. It is preferably 5 to 4 millimeters in weight due to the inorganic glass. Resin is the only material used for this adhesive resin. Specifically, With benzo and benzophenone Etc. in which mono (2-hydroxy-5 tertiary octylphenyl) benzotriazole '(2-hydroxy_3,5-tertiary pentylphenyl) benzotriazole'2, 2,1 Methylenebis (4--1,1,3,3-tetramethylbutyl) -6 [[(2H-benzoxazol-2-yl) phenyl]), 2,2,1-methylene Double [6_ 〔^ paper size applies to China National Standard (CNS) A4 specifications (210 X 297 public love --- r ---.--------- order ---------- --- line (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 581724 Α_ _7 Β7 V. Description of the invention (11) (2 pyrene, benzotriazole-1 2-1 ) Phenyl]] etc. For triazines, 2,4-bis (2,1-hydroxyphenyl) -6-aryl-1,3,5-triazine type (Japanese Patent Laid-Open No. 8-239368) Gazette), etc. For those who are benzoate, 2,4-tert-butylphenyl-3'5-tert-tert-butyl-4 4-hydroxybenzoate, hexadecyl-3, 5 1,2 tertiary butyl-4 monohydroxybenzoate, etc. For benzophenone series, 2,4-dihydroxydiphenyl Ketones, 2-hydroxy-4 4-methoxybenzophenone, 5,5'-methylenebis (2-hydroxy-4 -methoxybenzophenone), etc. These UV absorbers are used when necessary A plurality of them can also be used. The blending ratio of these ultraviolet absorbers is preferably from 0.01 to 3% by mass of the adhesive resin component, and more preferably from about 0.05 to 2% by mass. The blending amount of the ultraviolet absorber If it is less than 0.1% by mass, the weather resistance will be insufficient, and if it exceeds 3% by mass, the relative improvement of the effect cannot be expected. In addition, the present invention is different from adding a UV absorber to a polycarbonate resin and adhering it. The resin has a relatively low molding temperature, and can be selected from a wide range irrespective of heat resistance, sublimation properties, and the like. In addition, since the thickness of the adhesive resin layer is low, even if the amount of addition is high, there is an additional effect that the cost is not increased. In addition, a light stabilizer, a coloring agent, etc. may be blended with the ultraviolet absorber to the adhesive resin layer if necessary. Here, the light stabilizers include hindered amine light stabilizers, phenyl benzoate light stabilizers, and the like. Specific examples of the hindered amine-based or phenylbenzoate-based light stabilizers include double (2, 2, 6, 6-four paper sizes applicable to China National Standard (CNS) A4 (210 X 297 mm) L- ------- Order --------- Line (Please read the precautions on the back before filling this page) 581724

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (θ methyl.-4 monopiperidinyl) sebacate, succinic acid and ν-(2-hydroxypropyl) -2, 2, 6, Condensate of 6-tetramethyl-1, 4-hydroxypiperidine, (2, 2, 6, 6, 6-tetramethyl-1, 4-njd amidinyl), 1,2,3'4-butanetetracarboxylic acid ester, Polycondensation product of N, N, —bis (2,2,6'6-tetramethyl-4 piperidinyl) hexamethylenediamine and 1,2-dibromoethyl bromide, bis (2, 2,6,6-tetramethylpiperidinyl) adipate, bis (2,2,6, .6-tetramethylpiperidinyl) fumarate, poly [[6 — (1,1 , 3,3-tetramethylbutyl) fluorenimino-1,3,5-triazine-2,4-diyl] [(2,2 '6' 6 -tetramethyl-4 4-piperidine Amidinyl) imino] hexamethylene [(2'2'6,6-tetramethyl-1,4-piperidinyl) imine]], containing 4-hydroxy-2,2,2, Θ, 6- Tetramethyl-1, piperidine ethanol dimethyl succinate polymer, 2,4,2 tertiary butylphenyl-3,5-di 4-butyl-4-hydroxybenzoate, 4-octylphenyl-3,5-di-tertiary-butyl-4-hydroxybenzoate, n-hexadecyl-3,5-tertiary-butyl -4-hydroxybenzoate and the like. The blending amount of these light stabilizers is also blended in accordance with the above-mentioned ultraviolet absorber. The adhesive resin layer used in the present invention is based on ethylene-vinyl acetate copolymer, polyurethane, polyvinyl acetate, ethylene- (meth) acrylate copolymer, polyester-polyurethane copolymer, polycarbonate-poly Organosiloxane copolymer, polyvinyl butyral, etc., combined with the necessary amount of ultraviolet absorber, and the desired additives are formed by extrusion molding, roll molding, blown film molding and other film or sheet molding methods Membrane. The thickness of the adhesive resin film is preferably from 0. 1 to 2 mm, and from about 0.2 to 0. 8 mm. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -15 -IT I -II I-- · 1111111 ^ ----- I --- (Please read the notes on the back before filling this page) 581724 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 __B7_ V. Description of the invention (Θ is better.) The multilayer structure of the present invention is generally interposed between a glass plate and a polycarbonate resin plate having the shape of the multilayer structure of interest, and is inserted into a rubber bag or a vacuum device through an adhesive resin film. After vacuum degassing, it is moved to the heating device in the degassed state, and is manufactured by heating until the intermediate layer adhesive resin is softened to the adhesion temperature. The adhesive resin layer can be shown in Figure 1 (2) The above-mentioned adhesive resin layer is made of two layers. On the surface of the polycarbonate-based resin layer, a silicone resin can also be known to improve the surface properties such as hardness and scratch resistance. Handling, that is, the nature of the inner side relative to the outer side in general use It is also slightly durable enough to be sufficiently durable. In addition, the multilayer structure of the present invention is basically composed of a polycarbonate resin layer (A), an adhesive resin layer (B), and a glass layer (C). The stability and improvement of the performance of the multilayer structure may be configured as shown in Fig. 1 (3), and the resin layer (B ') 2 2-1 will be adhered to the polycarbonate resin layer (A) 1 side. 2 2-2, glass layer (C ') 3 3 is integrated, and it is better to focus on the polycarbonate resin layer. At this time, the thickness of each layer can be changed appropriately. Also, the adhesive resin layer (B ') and glass layer (C') are essential components in the present invention, but not ultraviolet absorbing components. This is because the multilayer structure of the present invention is almost always used when facing the sun. Degradation usually occurs only on one side. The following examples and comparative examples are used to describe the present invention in more detail, but the present invention is not intended to limit it. --- r --------------- --Order- ------- (Please read the notes on the back before filling out this page) This paper size applies Chinese national standards CNS) A4 specifications (210 X 297 mm) -16- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 581724 A7 __B7 V. Description of the invention (14 [Examples 1 to 7, Comparative Examples 1 to 6, Reference Example 1, 2] In order to form the layer structures and layer thicknesses shown in Tables 1 to 3, the following materials are used for polymerization and vacuum degassing, and then the bonding temperature is set in the range of 1000 to 180 ° C with the adhesive layer. The conditions are such that after heating, the multi-layer structure is slowly cooled. In Comparative Example 5, the thickness is changed as shown in the footnote of Table 2. The weather resistance of the obtained multi-layer structure is based on the Sun Shine Weather Meter [test conditions: 6 3 t :, rain conditions 480 hours] for the weather resistance test, and before and after the test I is based on j IS κ 7 1 0 5 Determination. The measurement results are shown in Table 1, Table 2 and Table 3 together with the areal density of the multilayer structure. ①Polycarbonate resin (A) board • PC1: Bisphenol A polycarbonate resin with a viscosity average molecular weight of 22,000. The amount of terminal hydroxyl groups is 4 mol% relative to the repeating unit of the polymer chain. • PC2: Bisphenol A polycarbonate resin 'terminal hydroxyl group with a viscosity average molecular weight of 22,000 is 6 mol% relative to the repeating unit of the polymer chain. • PC3: Bisphenol A polycarbonate resin 'terminal hydroxyl content with a viscosity average molecular weight of 22,000 is 10 mole% relative to the repeating unit of the polymerized chain. • PC4: Bisphenol A polycarbonate with a viscosity average molecular weight of 22,000. This paper is sized for China National Standard (CNS) A4 (210 X 297 mm) -17- --- ^ --- ^ ----- --------- Order --------- line (please read the notes on the back before filling out this page) 581724 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (1) For ester resins, the amount of terminal hydroxyl groups is 14% by mole relative to the repeating unit of the polymer chain. The amount of terminal hydroxyl groups is determined by the method described in Japanese Patent Application Laid-Open No. 1 _ 7 4 2 3 For the adjustment, 1 Η 1 n MR was used to calculate the peak area based on the terminal structure (p-tert-butylphenyl) of 1 · 3 ppm and the hydroxyl terminal based on the peak area of 6 · 7 ppm. ② The glass plate was made of thorium oxide and titanium oxide. Adding 1.5% by mass to basic soda-lime-silica-based glass raw materials, ultraviolet-absorbing glass plates (glass U) and non-ultraviolet-absorbing glass plates (glass) are obtained. ③ Adhesive resin (1) EVA: Ethylene vinyl acetate copolymer with 40% by mass of vinyl acetate (2) EVA1: 40% by mass of vinyl acetate % Ethylene vinyl acetate copolymer contains 1.0% by mass of a benzotriazole-based ultraviolet absorber: Tinuvin 329 [2-2, monohydroxy-5 '-tertiary octylphenol] benzotriazole] (steam (3) EVA2: ethylene vinyl acetate copolymer with a vinyl acetate content of 40% by mass and a triazine-based ultraviolet absorber containing 1.0% by mass: Tlnuvin 1 5 77 (Chembat Chemical (4) PVB ·· Polyvinyl butyral The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -------- ^ ------ --- (Please read the notes on the back before filling this page) 581724 A7 B7 V. Description of the invention (， VA3Dds · sd · lulcis · zvs · 0 0 9 “° 6

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This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) -TST 581724 A7 B7 V. Description of the invention (17) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 镒 ΛΛ PQ > 1 1 1 1 〇〇inch 0 \ 〇r— < Csl τ—Η 〇〇 < Ηinch If sea < > ω 1 inch u 1 < > m If 趦 〇〇inch〇〇r- csi τ— ((N1 σ \ cn U CU cn 1 inch U Ph 1 1 1 inch cn m un cn r—Η \ 〇〇〇CN1 ± Λ Warp < > ω u CU 00 inch u Ph u Oh < > ω If Pengο 〇 \ ”< r 1 < CNl f —Η 4J jf Peng OQ > 〇 < u Cu 00 cn U Dh U Qh cn PQ > IS Pengin ο 〇 \ iiv 1 Η CO r ^ · Warm W% < inch ο inch o CO inch o inch o Η 来 / ^ v 米 vt MoΗ-t Ηm ¥ n, fi, If Ε- t #, _ Pass U cx K, _ 卜 _ _ 朗 _鹄 W side R _ 馨 采 _00 · 0 = 3 Λ d, mwcxlH 鹄 peng: LOf ^ 镒 ugly * -------------------- Order --- ------ * 5 ^ ·-(Please read the precautions on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -ZΌ-581724 A # 17 V. Description of the invention (Class 1 Table 3, Reference Example 1 Reference Example 2 Comparative Example 6 Layer Material Thickness mm Millimeter Weight Glass 婀 1 Glass U Glass D U Glass and then armor 0,4 EVA1 EVA1 PVB connection »layer B 0,4-SPC SPC PC layer 2 PC3 PC3 PC1 followed by layer C 0,4-SPC SPC followed by layer 0,4 EVA PVB glass layer 1 — 'thickness of glass glass multilayer ( Mm) 3,4 5,6 5,6 Area density (kg / m2) 5,3 9,0 9,0 Weatherability evaluation (YI) Initial 1-0 1,2 1,2 After weathering test 6.0 5, 0 7,3 (Please read the * on the back before filling out this page. ”Printed by Table 1 and Table 2 from the results of Table 1 and Table 2 of the Ministry of Economic Affairs% 1 Property Agent X Clearance Cooperatives. The laminated glass of Comparative Example 5 has a small surface density and light weight. Also, the weather resistance is significantly better than that of Comparative Example. Furthermore, it can be seen from Reference Examples 1, 2 and Comparative Example 6 that polycarbonate __ resin The amount of the terminal hydroxyl group is 8 mol% or less relative to the repeating unit of the polymer bond, and the weather resistance is good. Industrial use: Moderate ruled paper 10 (21 grid Μ Ｍ 581724 A7 B7 V. Description of the invention (19) Because the multilayer structure (layered body) of the present invention is formed of inorganic glass, it has the same properties as inorganic glass. Glass has comparable hardness and abrasion resistance, and it is excellent in performance due to its light weight and impact resistance due to the polycarbonate resin. In addition, the polycarbonate resin has virtually no UV absorber and can be obtained. Polycarbonate resin sheet reduces yellowing and ensures transparency, and is a multilayer structure with significantly better weather resistance. Therefore, combined with the polycarbonate resin's impact resistance, it can contribute to automotive door glass and sunroof Lightweight of glass and other cars. It can also be extended to windows of buildings, schools, etc. ^ shop windows, roof materials, etc. ---? ------------- ---- Order --------- line (please read the notes on the back before filling this page) Printed on the paper by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employees' Cooperatives, this paper applies the Chinese National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

581724 夂 、 Patent Application No. 89124956 Chinese Patent Application Amendment Chinese Patent Application Amendment January 14, 1993 Amendment 1. A multilayer structure characterized by a polycarbonate resin layer (A) and an adhesive resin layer (B) At least one of the glass layer or the adhesive resin layer formed by the glass layer (C) contains an ultraviolet absorbing component. 2. If the multilayer structure of item χ of the scope of patent application, where the glass layer (A) and the adhesive resin layer. (B) both contain ultraviolet absorbing components 3. If the scope of the application of the patent scope of item χ or 2 A multilayer structure, in which the glass layer (A) is a soda lime silica glass, and the ultraviolet absorbing component contained in the glass is a sister. 4. The multilayer structure according to item 1 of the patent application scope, wherein the ultraviolet absorbing component contained in the adhesive resin layer (B) is a benzotriazole-based compound and / or a triazine-based compound. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5 · If the multilayer structure of the first patent application scope is applied, the adhesive layer. The resin layer (B) is selected from ethylene-vinyl acetate copolymer, polyvinyl acetate, ethylene At least one layer of mono (meth) acrylate copolymer, polyurethane, polyester-polyurethane copolymer, polycarbonate-organosiloxane copolymer, and polyvinyl butyral resin. 6. The multilayer structure according to item 1 of the scope of patent application, wherein the amount of terminal hydroxyl groups of the polycarbonate resin used for the polycarbonate resin layer (A) is 8 mol% or less relative to the repeating unit of the polymer chain. This paper size is applicable to Chinese National Standard (CNS) A4 specification (2) 0 × 297 mm. 581724 ABCD 6. Application scope of patent 7. For the multilayer structure of the first scope of patent application, the adhesive resin layer (B) consists of The two-layer structure includes a polycarbonate-based resin layer (A) and a polycarbonate-polyorganosiloxane copolymer layer. 8. The multilayer structure according to item 1 of the scope of patent application, wherein the polycarbonate resin layer (A) is further provided with a glass resin layer through an adhesive resin layer. _ · Ι Pack II (Please read the notes on the back of the ministry before filling out this page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is printed in accordance with Chinese National Standards (CNS) Α4 specifications (2) 0 × 297 mm -2-