WO2001038088A1

WO2001038088A1 - Multilayer structure

Info

Publication number: WO2001038088A1
Application number: PCT/JP2000/008212
Authority: WO
Inventors: Nobuhiro Watanabe; Mitsugu Nakae; Jiro Chiba
Original assignee: Idemitsu Petrochemical Co., Ltd.
Priority date: 1999-11-25
Filing date: 2000-11-21
Publication date: 2001-05-31
Also published as: JP4439782B2; TW581724B

Abstract

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

Description Multilayer structure Technical field

The present invention relates to a multilayer structure that can be used for window glasses of automobiles, aircraft, etc., windows of buildings, schools, shops, etc., show windows, roofs, etc., wherein a polycarbonate resin layer and a glass layer are integrated with an adhesive resin layer. The present invention relates to a multilayer structure having improved weather resistance. Background art

Inorganic glass has been used as windows, roofs, and transparent walls for cars, buildings, schools, shops, and so on. In recent years, there has been a demand for a lightweight material that can replace inorganic glass because of the demand for improved fuel efficiency of automobiles, the impact resistance of building windows, the weight reduction, and the ease of handling. In addition, in the case of window glass, ceiling glass for automobiles, public buildings, etc., an adhesive resin such as polybierbutyral is placed between two glass plates to prevent glass from scattering when the inorganic glass plate is broken. A laminated glass plate is used as a layer.

However, the specific gravity of glass is high even for inorganic glass sheets and laminated glass sheets, and it is necessary to reduce the thickness in order to reduce the weight. Due to the strength characteristics required for the intended use, the thinness of the glass sheet Naturalization has its own limitations. For this reason, it has recently been proposed to use light-weight polymethyl methacrylate or polycarbonate-based resin plates instead of inorganic glass plates, which have been used as windows and roofing materials for public buildings.

Polymethyl methacrylate is not always sufficient in terms of impact resistance, and polycarbonate-based resins have recently been receiving attention. However, polycarbonate-based resins do not have sufficient surface hardness and pulling hardness, resulting in surface damage. It is likely to occur and its field of use is limited. In order to improve the surface hardness and scratch resistance, improvements have been proposed by coating the surface of the polycarbonate resin plate with a hard resin such as a silicone resin, or by depositing a metal oxide such as silicon oxide. ing.

However, these polycarbonate-based resin sheets with a surface coating layer also have insufficient durability and have not yet been replaced with inorganic glass sheets. For this reason, multilayer boards have been proposed that combine the strengths of glass plates, such as hardness and abrasion resistance, and the transparency and strength of polycarbonate resins, and particularly excellent impact resistance. For example, a glass plate of about 1 to 2 mm is placed on one side of a polycarbonate resin plate of about 2 to 8 mm, for example, polybutyral, ethylene / butyl acetate copolymer, polyurethane, polycarbonate-organo. A multilayer structure (laminate) has been proposed that is laminated via an adhesive resin such as a siloxane (block) copolymer.

These multilayer structures exhibit significantly better resistance to impact and penetration as compared to the inorganic glass plate alone, and the thickness ratio between the inorganic glass plate and the polycarbonate-based resin changes. It has a major feature that allows the design of materials that balance physical properties and weight reduction.

The multilayer structure is based on the three-layer structure described above. However, depending on the long-time use and the place of use, stress cracks and fogging may occur due to differences in the basic physical properties of the glass plate and the polycarbonate resin. However, signs of detachment may be seen. In such a case, a symmetrical multi-layered structure in which a glass plate is further laminated on the polycarbonate-based resin layer side of the multi-layered structure via an adhesive resin layer may be employed. Further, various proposals have been made to provide another arbitrary resin layer, for example, a hard resin such as methyl methacrylate, an elastic resin layer, or the like, depending on the purpose.

These plate-like multilayer structures (laminates) having an inorganic glass plate Z and a polycarbonate resin plate as a basic configuration have excellent characteristics as described above. is there. However, most of these multilayer structures are mainly used outdoors, such as automobiles and building window materials. For this reason, in the multilayered structure, ultraviolet rays from the sun largely act, and the yellowing of the polycarbonate resin layer proceeds. As a result, coloring occurs over time, the appearance is deteriorated, and the field of use is greatly restricted by the decrease in transparency. For this reason, it is conceivable to add an ultraviolet absorber when molding the polycarbonate resin plate. However, in order to prevent yellowing, it is necessary to add a certain amount or more of an ultraviolet absorber, and the additive may cause coloring of the polycarbonate resin plate. In addition, polycarbonate resins have problems such as high melt viscosity, high molding temperature, easy sublimation of ultraviolet absorbers, and narrow selection of ultraviolet absorbers to be used.

The present invention provides a lightweight, multi-layer structure excellent in impact resistance and the like obtained by integrating a polycarbonate resin and a glass plate via an adhesive resin layer under the above-mentioned conditions, and for long-term outdoor use. Also in this case, an object is to provide a multilayer structure with less yellowing and lowering of transparency. Disclosure of the invention

In order to achieve the object of the present invention, the present inventors have intensively studied on the improvement of the weather resistance of a multilayer structure composed of a polycarbonate resin and glass. As a result, they have found that there is an excellent effect when a specific layer contains an ultraviolet absorbing component (agent), and thus completed the present invention.

That is, the present invention

(1) A multilayer structure comprising a polycarbonate resin layer (A), an adhesive resin layer (B), and a glass layer (C), wherein at least one of the glass layer and the adhesive resin layer contains an ultraviolet absorbing component. Structure.

(2) UV-absorbing components are applied to both the glass layer (A) and the adhesive resin layer (B). The multilayer structure according to (1), comprising:

(3) The multilayer structure according to (1) or (2), wherein the glass layer (A) is soda lime silica glass, and the ultraviolet absorbing component contained in the glass is cerium.

(4) The multilayer structure according to any one of (1) to (3), wherein the ultraviolet absorbing component contained in the adhesive resin layer (B) is a benzotriazole-based compound and / or a triazine-based compound.

(5) The adhesive resin layer (B) is made of ethylene-butyl acetate copolymer, polyvinyl acetate, ethylene- (meth) acrylate copolymer, polyurethane, polyester-polyurethane copolymer, poly-carbonate-one The multilayer structure according to any one of (1) to (4), comprising at least one layer of a resin selected from an organosiloxane copolymer and polybutylbutyral.

(6) The polycarbonate resin used in the polycarbonate resin layer (A) has an amount of terminal hydroxyl groups of 8 mol% or less per repeating unit of the polymer chain, as described in any of (1) to (5). Multi-layer structure.

(7) The multilayer according to any one of (1) to (6), wherein the adhesive resin layer (B) comprises two layers, of which the polycarbonate resin layer (A) side is a polycarbonate-polyorganosiloxane copolymer. Structure.

(8) A multilayer structure according to any one of (1) to (7), wherein a glass layer is formed on the polycarbonate resin layer (A) side via an adhesive resin layer. Description

FIG. 1 is a conceptual sectional view showing an example of the multilayer structure of the present invention.

In the figure, reference numeral 1 denotes a polycarbonate resin layer, reference numeral 2 denotes an adhesive resin layer, and reference numeral 3 denotes a glass layer. BEST MODE FOR CARRYING OUT THE INVENTION

The details will be described below.

I. Components constituting the multilayer structure of the present invention

(1) Polycarbonate 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 includes various types. Usually, an aromatic polycarbonate produced by reacting a divalent phenol with a carbonate precursor can be used. That is, a product prepared by reacting a divalent phenol with a carbonate precursor by a solution method or a melting method, that is, a reaction between a divalent phenol and phosgene, and a transesterification method between a divalent phenol and dipheninolecarbonate. Can be used.

A variety of divalent phenols can be mentioned, and in particular, 2,2-bis (4-hydroxyphenyl) prononone (bisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-Hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-1,3,5-dimethynolephene / re) Pro / Kun, 4,4,1-dihydroxydiphenyl, bis (4-hydroxyphenyleneole) ) Cycloanolecan, bis (4-hydroxypheno) oxide, bis (4-hydroxypheno) sulfide, bis (4-hydroxypheno) snorehon, bis (4-hydroxypheno) / Refoxide, Bis (4-hydroxyphenone) ethenole, Bis (4-hydroxyphene) ketone, etc. Substituents and the like.

Particularly preferred divalent phenols are bis (hydroxyphenyl) alkanes, particularly those containing bisphenol A as the main raw material. Examples of the carbonate precursor include carbonyl halide, carbonyl ester, and haloformate. Specific examples include phosgene, dihaloformate of divalent phenol, diphenyl carbonate, dimethyl carbonate, and diethyl carbonate. It is. In addition, as a divalent phenol, Droquinone, resorcin, catechol and the like. These divalent phenols may be used alone or in combination of two or more.

The polycarbonate resin may have a branched structure. Examples of the branching agent include 1,1,1-tris (4-hydroxyphenyl) ethane and α, α, α "-tris (4-hydroxyphenyl). Nore) 1,3,5-triisopropylbenzene, phloroglysin, trimellitic acid, isatin bis (ο-tarezol), etc. In addition, phenol, ρ-t— Butylphenol, p-t-octinolephenol, p-cumylphenol, ρ-dodecylphenol and the like are used.

The polycarbonate resin used in the present invention may be a random copolymer having a polycarbonate portion and a polyorganosiloxane portion, a block copolymer, or a polycarbonate resin containing this copolymer. Further, it may be a polyester-polycarbonate resin obtained by performing polymerization of polycarbonate in the presence of a bifunctional carboxylic acid such as terephthalic acid or an ester precursor such as an ester-forming derivative thereof. Also, a mixture of various polycarbonate resins can be used. The polycarbonate resin used in the present invention has a viscosity average molecular weight of from 10,000 to 100,000, preferably from 15,0,0, from the viewpoint of mechanical strength and moldability. Those having a value of from 0 to 40, 000, especially those having a value of 20, 000 to 30, 0, 00 are suitable.

Furthermore, the amount of terminal hydroxyl group in the polycarbonate resin, the repeating units per 8 mol% of the polymer chains or less, preferably 6 mol% or less, rather still more preferably has those 4 mole ^_0/0 or less, in terms of weather resistance preferable.

The polycarbonate resin layer is usually compounded with additives such as an antioxidant and formed into a sheet by extrusion molding. In forming this sheet, a polycarbonate-organosiloxane copolymer was formed on the side to be the glass layer side. Any adhesive resin layer can be co-extruded to form a multilayer sheet with the adhesive resin. The thickness of the sheet is preferably l to 10 mm, and more preferably about 2 to 6 mm. The polycarbonate resin may also contain a light stabilizer and an ultraviolet absorber in an allowable range. Further, as a manufacturing method, injection molding, injection compression molding, or the like can be adopted.

(2) Glass layer

The glass used in the glass layer (C) used in the present invention is not particularly limited as long as it is an inorganic glass, and ordinary window glass is used. Such a glass sheet is prepared by mixing main raw materials such as silica sand, soda ash, limestone, and glass nitrate at a certain ratio, and then mixing glass waste (cullet) at an appropriate ratio. Magnesium oxide, calcium oxide, iron oxide, nickel oxide, cobalt oxide, titanium oxide, selenium, etc. are completely melted in a kiln in a temperature range of 1,500 to 1,600. The foundation is made. Next, there are glass molds obtained by the glass substrate, float, float method (molding on the surface of molten metal) and the like, and those obtained as polished glass by secondary processing.

(3) Adhesive resin layer

There is no particular limitation on the adhesive resin used for bonding the glass plate and the poly-carbonate resin sheet, and any resin that has been conventionally used is used. Adhesive resins include ethylene-butyl sulfate copolymer, polybutyl acetate, ethylene- (meth) acrylate copolymer, polyurethane, polyester-polyurethane copolymer, polycarbonate-polyorganosiloxane block copolymer. Examples thereof include polymers, random copolymers, and polybutyral.

Here, as the ethylene-butyl phosphate copolymer, those having a vinyl acetate component, preferably about 5 to 60% by mass are used. Also, poly power The toorganosiloxane copolymer preferably has a polyorganosiloxane content of 2 to 70% by mass, more preferably 20 to 60% by mass. That is, when the polysiloxane content is high, a soft or elastic resin is preferable. Examples of the polysiloxane include those in which a polysiloxane block unit is bonded to a main chain through a “silicon-oxygen-silicon” bond, and a polysiloxane block unit is bonded to a main chain through a “silicon-carbon” bond.

As a method for producing these polycarbonate-organosiloxane copolymers, a methylene chloride solution of a polycarbonate oligomer and a terminal phenol dimethyl siloxane or a dihydroxy compound having siloxane bonded to carbon are used in the presence of a triethylamine catalyst. If necessary, it can be produced by a known method by adding an aqueous solution of bisphenol A and reacting.

These adhesive resins may contain a resin chemically modified with unsaturated acids such as maleic anhydride and fumaric acid or ruponic acid or a derivative thereof, or a chemically modified resin. Further, a coupling agent such as 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyl ethoxysilane, or burtriethoxysilane may be included in order to improve the adhesion to the glass plate.

As the adhesive resin, a soft resin (having an elastic modulus of 1, OOOMPa or less) is preferable in terms of buffer adhesion between the glass plate and the polycarbonate resin. As this soft adhesive resin, polybutyral is often used as an adhesive intermediate layer for laminated inorganic glass. However, when this polyvinyl butyral is used as it is as the adhesive resin layer of the present invention, there is no problem with inorganic laminated glass, but there is a problem with lamination with a polycarbonate resin sheet.

This is because a plasticizer is blended in the polyvinyl butyral film, and the plasticizer migrates to the polycarbonate resin after lamination, and This causes whitening of the resin sheet and a decrease in transparency. In such a case, there is no need to worry about migration of a plasticizer between the polyvinyl butyral resin layer and the polycarbonate resin layer. For example, other adhesive resins such as polycarbonate-poly / polysiloxane copolymer and polyurethane Can be used. That is, the number of adhesive resin layers is two or more.

II. Multilayer structure of the present invention

Hereinafter, the multilayer structure of the present invention will be described based on its manufacturing method. FIG. 1 is a conceptual sectional view of the multilayer structure of the present invention. In FIG. 1, 1 is a polycarbonate resin layer, 2 is an adhesive resin layer, and 3 is a glass layer. As shown in FIG. 1 (1), the multilayer structure of the present invention basically comprises a polycarbonate resin layer (A) 1, a glass layer (C) 3, and an adhesive resin layer (B) 2. . The present invention is characterized in that at least one of the glass layer (C) and the adhesive resin layer (B), preferably both layers, contain an ultraviolet absorbing component (agent).

First, a glass plate is manufactured by melting soda ash, limestone, carbon, and sodium sulfate with silica sand as the main component, and adding a frit containing various components that become ultraviolet absorbing components, and usually a colored frit, to this melt. Is done. Specifically, soda lime silica glass can be exemplified. Here, as the ultraviolet ray absorbing component, one containing cerium can be exemplified without particular limitation as long as it reduces the transmittance of ultraviolet rays when it becomes a glass plate. The cerium component is produced by adding 1 to 2% by mass of oxidized cerium to a glass raw material. The component that absorbs ultraviolet light may be a compound that absorbs ultraviolet light in a complex manner, such as a titanium component and a coloring component.

Molten glass containing UV-absorbing components is made into sheet glass by the float method, casting method, down-draw method, or pulling method. If necessary, it is polished to make polished glass. The multilayer structure of the present application is, as a rule, a flat plate glass, but it is used for window glass for automobiles, roofing materials, and the like. In such a case, it is processed into a gentle curved surface. The thickness of the glass plate can be appropriately determined depending on the application, size, etc., but the multilayer structure of the present invention is intended to reduce the weight of the inorganic glass, is not very thick, and preferably has a thickness of 0.5 to 4 mm. Preferably, it is about 0.7 to 3 mm.

Next, the resin described above is used as the adhesive resin, and the ultraviolet absorbing component (agent) used for the adhesive resin is not particularly limited. Specifically, there are benzotriazole-based, triazine-based, benzoate-based, benzophenone-based and the like, and among them, benzotriazole-based and triazine-based are preferably used.

Benzotriazoles include 2- (3-t-butyl-1-5-methynole-1 2-hydroxyphenylene) -1-5-chloro-benzotriazo-1 / re, 2- (3,5-di-t-butynole) 1-Hydroxyphenyl) 1-5-Chlorobenzobenzoyl, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butylinole) 2-Hydroxypheninole) benzotriazole, 2- (2-hydroxy-5-t-octylphenyl) benzotriazonole, 2- (2-hydroxy-3,5-di-t-aminorefeninole) benzotriazole, 2,2,1-methylenebis [4- (1,1,3,3-tetramethylbutyl) -16-(:( 2H-benzatriazole-12-yl) pheno]], 2,2,2 -Methylenebis [6- [(2H-benzotriazole) One 2-I le) phenol]] and the like.

As triazines, there are 2,4-bis (2,1-hydroxyphenyl) -16-aryl-1,3,5-triazine type (see Japanese Patent Application Laid-Open No. Hei 8-239396). And the like.

In addition, benzoate compounds include 2,4-di-butynolephen-2-^-3,5-di-t-butynole-4-hydroxybenzoate, hexadecinole-1,3,5-di-t-butyl-4-hydroxybenzoate And so on. Benzophenones include 2,4-dihydroxybenzophenone, 2-hydroxy-14-methoxybenzophenone, and 5,5-methylenebis (2-hydroxy-14-methoxybensophen). Can be mentioned. If necessary, a plurality of these ultraviolet absorbers can be used.

Proportion of these ultraviolet absorbers, the adhesive resin component, preferably 0.0 to 3 wt%, more preferably 0.0 5-2 mass ⁰ / o of about. If the amount of the ultraviolet absorber is less than 0.01% by mass, the weather resistance is not sufficient, and if the amount exceeds 3% by mass, the effect corresponding thereto cannot be expected to be improved. In the present invention, unlike the case where an ultraviolet absorber is added to a polycarbonate resin, the adhesive resin has a relatively low molding temperature, and has a feature that it can be selected from a wide range irrespective of heat resistance, sublimation and the like. In addition, since the thickness of the adhesive resin layer is thin, even if the amount of addition is relatively high, there is an additional effect such as not being expensive.

In the adhesive resin layer, a light stabilizer, a coloring agent, and the like can be added to the ultraviolet absorber, if necessary. Here, examples of the light stabilizer include a hindered amine light stabilizer and a phenylbenzoate light stabilizer. Specific examples of the hindered amine or phenyl / levenzoate light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) separate, succinic acid and N— (2-H Condensation product with 1,2,2,6,6-tetramethinole-4-hydroxypiperidine, tetrakis (2,2,6,6-tetramethyl-14-piperidyl), 1,2,3 1,4-butanetetracarboxylate, N, N, 1-bis (2,2,6,6-tetramethyl-14-piperidinole) polycondensate of hexamethylenediamine with 1,2-dibromoethane, bis (2,2,6,6-tetramethylpiperidyl) adipate, bis (2,2,6,6-tetramethylpiperidyl) fumarate, poly [[6- (1,1,3,3-tetramethylbutyl) imino 1,3,5-triazine-1 2,4- I le] [(2, 2, 6, 6-tetramethyl-one 4 Piberiji Le) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], dimethyl containing 4-hydroxy-1-2,2,6,6-tetramethyl-1-piperidineethanol Succinate polymer, 2,4-di-t-butyleninolate 3,5-di-t-butyl / ret 4-hydroxy benzoate, 4-octynolephenone 3,5-di-t-butynole 4 Examples include hydroxybenzoate and _n- hexadecyl-3,5-di-t-butyl-14-hydroxybenzoate. The compounding amount of these light stabilizers is also compounded according to the ultraviolet absorber.

The adhesive resin layer used in the present invention may be composed of an ethylene-vinyl acetate copolymer, a polyurethane, a polyvinyl acetate, an ethylene- (meth) acrylate copolymer, a polyester-polyurethane copolymer, a polycarbonate-polyorganosiloxane copolymer. A required amount of an ultraviolet absorber and a desired additive are blended with the unified product, holibutyral, and the like, and the mixture is formed into a film by means of a film or sheet forming means such as extrusion molding, calendar molding, and inflation molding. The thickness of the adhesive resin film is preferably in the range of about 0.2 to 2 mm, and more preferably in the range of about 0.2 to 0.8 mm.

In general, the multilayer structure of the present invention is obtained by inserting an adhesive resin sheet between a glass plate having the shape of a target multilayer structure and a polycarbonate resin sheet, and inserting it into a rubber pack or a vacuum device. After sufficient vacuum degassing, it is manufactured by transferring it to a heating device while it is in a degassed state, and heating it to the temperature at which the adhesive resin in the intermediate layer softens and bonds. In addition, as shown in FIG. 1 (2), the adhesive resin layer described above can be made into two layers as the adhesive resin layer. In addition, the surface of the polycarbonate-based resin layer may be coated with a known silicone resin or the like to improve the surface properties such as hardness and scratch resistance. In other words, in general use, the performance of the inner surface is slightly lower than that of the outer surface, so that it can be sufficiently used.

The multilayer structure of the present invention basically comprises a polycarbonate resin layer (A), an adhesive resin layer (B), and a glass layer (C). However, in order to stabilize and improve the performance of the multilayer structure, as shown in FIGS. 1 (3) and (4), the adhesive resin layer (Β ′) 22 In some cases, it is preferable to integrate 1, 2, 2 and 2 and the glass layer (C,) 33 to form a symmetrical structure around the polycarbonate resin layer. In this case, the thickness of each layer can be appropriately changed. Further, the adhesive resin layer (′) and the glass layer (C ′) do not necessarily require the ultraviolet ray absorbing component, which is an essential component in the present invention. This is because the multilayer structure of the present invention is used in most cases facing the sun, and the deterioration of the polycarbonate-based resin layer usually occurs only from one side. The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited thereto.

[Examples 1 to 7, Comparative Examples 1 to 6, Reference Examples 1 and 2]

Laminate using the materials shown below to achieve the layer composition and layer thickness shown in Tables 1 to 3, and after deaeration under vacuum, apply to the adhesive layer in the range of 100 to 180. After setting the bonding temperature conditions, heating and holding, and slowly cooling, a multilayer structure was obtained. In Comparative Example 5, the thickness was changed as shown in the footnote of Table 2.

The weather resistance of the obtained multilayer structure was measured using a sunshine weather meter (test conditions: 63, rainfall conditions, 480 hours), and ΥI before and after the test was changed to JISK 705. It measured according to. Table 1, Table 2, and Table 3 show the measurement results along with the areal density of the multilayer structure.

① Polycarbonate resin (A) sheet

• PC 1: Bisphenol A polycarbonate resin with a viscosity average molecular weight of 22, 000. The amount of terminal hydroxyl groups is mol% per repeating unit of the polymer chain. • PC 2: Bisphenol 7-polycarbonate resin with a viscosity average molecular weight of 22,000. The amount of terminal hydroxyl groups is 6 mol% per repeating unit of the polymer chain.

• PC 3: Bisphenol A polycarbonate resin with a viscosity average molecular weight of 22,000. The amount of terminal hydroxyl groups is 10 mol% per repeating unit of the polymer chain.

• PC4: Bisphenol A polycarbonate resin with a viscosity average molecular weight of 22,000. The amount of terminal hydroxyl groups is 14 mol ⁰ / o per repeating unit of the polymer chain.

The amount of terminal hydroxyl groups was adjusted according to the method described in JP-A-1-74231, and 1.3 ppm based on the terminal structure (pt-butylphenyl) and the hydroxyl terminal were determined using iH-NMR. Calculated from the peak area of 6.7 ppm based on

②Glass plate

UV-absorbing glass plate (glass U) and glass plate without UV-absorbing (glass) obtained by adding 1.5% by mass of cerium oxide and titanium oxide to basic soda lime silica glass material

③ Adhesive resin

(1) EVA: ethylene vinyl acetate copolymer having a vinyl acetate content of 40 mass ⁰ / o

(2) EVA1: Ethyl acetate butyl copolymer with a butyl acetate content of 40 mass ⁰ / o, benzotriazole UV absorber: Tinuvin 329 [2-2, monohydroxy-5'-t-octylphenol (Benzotriazole) (Ciba Specialty 'Chemicals') 1.0 mass ⁰ / o content

(3) EVA 2: ethylene醉酸Bulle copolymer of acetate Bulle content of 40 wt%, triazine-based UV absorber: T inuvin 1 577 (manufactured by Chipa Su Bae Shariti Chemicals) 1.0 weight ^_0/0 containing Table i

Example Example 2 Example 3 Example 4 Example 5 Example 5 Example 6 Example

Material thickness

Ga EE m m

La VV

Waste glass exhibition glass U glass U glass U glass U glass U glass glass

AA

Structure Adhesion exhibition 0 U21.4 V A 1 E V A S P C 1 E V A 1 V A E V A 1 V A 2

Scratch hole 0.4 S P C S P C S P C S P C S P C

Purple

p cm P C 1 P C 1 P C 1 P C Z P C Z P C Z P C Z

Adhesion / s C 0.4 Suction S / C S P C S P C S P C S P C

Adhesive layer 0.4 SP C 1 E V A E V A E V A V A V Glass glass Glass Glass Glass Glass glass

Multilayer thickness (mm) 3. 4 3. 8 4. 8 5. 6 5. 6 5. 6 5. 6

Areal density (kg Zm ^z ) 5.3 8.39.

Weather resistance evaluation (Y I)

Initial 1.0 1 .3 1 .2 1 .2 1 .2 1 .2

After the weathering test 1. 9 2. 1 1. 6 1. 8 2. 2 2.0

*: Contains agent

： Contains agent ¾ 有

Table 2

Comparative example Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Material thickness

m m

m Glass layer Crow Glass Glass Glass Glass structure Adhesive waste 0.4 P V B V A S P C V A P V B Adhesive waste mouth 0.4 S P C S P C

PC layer PC 3 PC C PM PC DOO PC 4

Adhesive layer C 0.4 S P C S P C

0.4 P V B V A E V A

Glass layer Glass Glass Glass Glass multilayer thickness (mm) 5. 6 5. 6 3 , 4 4, 8 4. 8 surface density ^{(kg / m 2) 9. 0} 9. 0 5. 3 7. 8 1 0. 9 Weather resistance evaluation (YI)

Initial 1 1 1 1 1 1 1 1 3 1 2 After weathering test 9.28.

* Comparative Example 5 Glass = 2 mm, PVB = 0.8 mm

No. 3 Material Thickness

m m

m Glass layer 7 Lath U is “Lath U ゥ” La Assembly 0.4 H V A E. V A P V B Splicing * Scrap hole 0.4 S p C

P C layer P C 3 P c 3 P C t

Adhesive layer C 0.4 5 C

Contact layer 0.4 E A

Glass chips are la

Multiple thickness (mm) 3. 4 5 ".

Area density (kg / m ² ). 39.0 Weather resistance evaluation (YI)

Five

0 1- 2 ί '2 After weathering test. 0 0 7- G 3

From the results in Tables 1 and 2, the multilayer structure of the present invention has a smaller areal density and is lighter than the laminated glass of Comparative Example 5. It is also clear that the weather resistance is significantly better than the comparative example. Further, from Reference Examples 1 and 2 and Comparative Example 6, it is found that the amount of terminal hydroxyl groups in the polycarbonate resin is preferably 8 mol% or less per repeating unit of the polymer chain, from the viewpoint of weather resistance. Industrial applications

The outer surface of the multilayer structure (laminate) of the present invention is formed of inorganic glass. As a result, it has the same hardness and scratch resistance as inorganic glass, and has excellent performance due to its light weight and combined impact resistance with polycarbonate resin. Furthermore, the polycarbonate resin sheet is not substantially blended with an ultraviolet absorber, and the polycarbonate resin sheet is yellowed and the transparency is reduced, resulting in a multilayer structure having extremely excellent weather resistance. Therefore, in combination with the impact resistance of the polycarbonate resin, it can contribute to the weight reduction of automobiles such as automobile door glass and sunroof glass. In addition, it will be possible to expand its use as windows for buildings, schools, etc., shop windows, and roofing materials.

Claims

The scope of the claims

1. A multilayer structure comprising a polycarbonate resin layer (A), an adhesive resin layer (B) and a glass layer (C), wherein at least one of the glass layer and the adhesive resin layer contains an ultraviolet absorbing component. body.

2. The multilayer structure according to claim 1, wherein both the glass layer (A) and the adhesive resin layer (B) contain an ultraviolet absorbing component.

3. The multilayer structure according to claim 1, wherein the glass layer (A) is a soda-lime-silica glass, and the ultraviolet absorbing component contained in the glass is cerium.

4. The multilayer structure according to any one of claims 1 to 3, wherein the ultraviolet absorbing component contained in the adhesive resin layer (B) is a benzotriazole-based compound and / or a triazine-based compound.

5. The adhesive resin layer (B) is made of ethylene-butyl acetate copolymer, polyvinyl acetate, ethylene- (meth) acrylate copolymer, polyurethane, polyester-polyurethane copolymer, polycarbonate-organosiloxane. The multilayer structure according to any one of claims 1 to 4, comprising at least one layer of a resin selected from a polymer and polyvinyl butyral.

6. The multilayer structure according to any one of claims 1 to 5, wherein the amount of terminal hydroxyl groups of the polycarbonate resin used in the polycarbonate resin layer (A) is 8 mol% or less per repeating unit of the polymer chain.

7. The multilayer according to any one of claims 1 to 6, wherein the adhesive resin layer (B) comprises two layers, of which the polycarbonate resin layer (A) side is a polycarbonate-polyorganosiloxane copolymer layer. Structure.

8. The multilayer structure according to any one of claims 1 to 7, further comprising a glass layer formed on the polycarbonate resin layer (Α) side via an adhesive resin layer.