JP2911153B2 - New complex - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a novel composite, and more particularly, to a novel composite which is lightweight, thin, retains glass shatterproof for a long period of time, and has extremely high design properties. It is about the body.

[Prior Art] Conventionally, various glass plates having a function of preventing scattering of glass when the glass plate is broken have been proposed. For example, a glass plate having a polyethylene terephthalate film or a polyethylene film adhered to one surface (surface) of a glass plate, a glass plate having a three-layer structure mainly used for a front laminated glass of an automobile, and two glass plates It has a polybutylene terephthalate layer mainly in the middle of the plate layer.

However, a glass plate in which the above-mentioned polyethylene terephthalate film or the like is adhered to the glass surface has an anti-scattering property at an early stage of the production, but when used outdoors, its action and effect is sharply reduced with time. It has been pointed out that this will not be possible.

In addition, a laminated glass plate having a three-layer structure has a large weight and a large plate thickness due to its structure, cannot be reduced in weight and thickness, and has poor productivity and is expensive. , Could not be used for general purposes.

For example, solar cells, liquid crystals, EL and surface protective materials such as EL, wristwatches, lightweight and thin ones are strongly desired, especially when the power generation unit is mainly CdS / CdTe in solar cells, Further, due to its toxicity, development of a surface protective material that maintains the anti-scattering property for a long time has been eagerly desired.

[Problems to be Solved by the Invention] An object of the present invention is to solve the above-mentioned problems of the prior art. And to provide a novel complex that has not been known hitherto.

[Means for Solving the Problems] The present invention has been made to solve the above-mentioned problems, and at least a fluorine-containing resin layer (surface resin layer) and a glass layer are interposed via an adhesive layer. The present invention provides a novel complex characterized by being joined together.

The `` fluorinated resin '' in the present invention may be any resin as long as it is a resin containing fluorine in the resin structural formula,
The fluorine content is not particularly limited, but is generally 30% by weight or more, preferably 35% by weight or more, and more preferably 40% by weight or more. Examples of such a fluorine-containing resin include ethylene-tetrafluoroethylene-based copolymer (ETFE), ethylene-chlorotrifluoroethylene-based copolymer (ECTFE), and hexafluoropropylene-tetrafluoroethylene-based copolymer (FET) ), Perfluoroalkyl vinyl ether-tetrafluoroethylene copolymer (PFA), polyvinylidene fluoride (PVD
F), polyvinyl fluoride (PVF), vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene (PCTFE),
Examples thereof include tetrafluoroethylene and / or monochlorotrifluoroethylene-hydroxyalkyl vinyl ether-alkyl vinyl ether-based copolymers, and any of these can be used in the present invention.
FE, FEP and PFA are preferred, and ETFE is particularly preferred.

The ETFE is mainly composed of ethylene and tetrafluoroethylene (the molar ratio of ethylene / tetrafluoroethylene is generally in the range of 40/60 to 60/40), and if necessary, a small amount (usually 10 mol% or less) of the third In the present invention, particularly, the content molar ratio of ethylene / tetrafluoroethylene is in the range of 40/60 to 60/40, preferably 45/55 to 55/45. And the formula CH ₂ = CH
-C _n F _{2n + 1} (where, n is an integer from 2 to 10) perfluoroalkyl vinyl monomer unit represented by _{(e.g., CH 2 = CH-C 4} H 9 or CH ₂ = CH-C ₆ content of 0.1 to 10 mol% of units) derived from H _13, preferably from 0.3 to 5
ETFE in the mole% range is preferably used. This ET
FE is known per se, for example, Japanese Patent Publication No. 59-5016
It can be manufactured by the method described in Japanese Patent Publication No. 3 and is available from Asahi Glass Co., Ltd. as "Aflon ^R COP"
Commercially available products under the trade names "Neoflon ETFE" manufactured by Daikin Industries, Ltd. and "Texel" manufactured by DuPont can also be used. Further, FEP is sold, for example, as "Neoflon FEP" manufactured by Daikin Industries, Ltd. and "Teflon FEP" manufactured by DuPont. PFA is, for example, "Neoflon PFA" manufactured by Daikin Industries, Ltd. It is also possible to use those sold under the trade name "Teflon PFA".

Further, the above fluorinated resins can be used alone or in combination of two or more.

The above-mentioned fluorine-containing resin can be formed into a film using the raw material as a raw material and bonded to the glass layer, but the film is formed according to a method known per se, for example, by an extrusion molding method, a calendar molding method, an inflation molding method, or the like. Can do it. At the time of film formation, a coloring agent (for example, titanium oxide, zinc white, calcium carbonate, precipitated silica, carbon black, chrome yellow, phthalocyanine blue, phthalocyanine green, etc.) can be added to the fluorine-containing resin as necessary. .

The thickness of the fluorine-containing resin layer is not particularly limited, but generally, 5 to 1000μ, preferably 30
-500μ, more preferably 50-200μ.

The glass used for the “glass layer” in the present invention is not particularly limited. For example, “Glass Layer” edited by the Editorial Board of the Material Encyclopedia, published on February 5, 1984, published by the Industrial Research Institute, Inc. Pp. 413-425 and Ed.Nishizo Kamisaka, June 15, 1976
Japan, published by Toyo Keizai Shimpo, `` Product Encyclopedia '' pages 783-795, etc., specifically, the softening temperature is 500 ℃
Above, preferably 600 ° C. or higher, more preferably 700 ° C. or higher, particularly preferably 800 ° C. or higher, and further, in a solar cell, a Cd-based film as a solar power absorbing material for power supply on one surface of the glass plate, For example, in the case where a CdS film, a CdTe film, or the like is printed and fired and sintered, glass having a small alkali component in the glass composition is preferable. Examples of these glass types include soda ash glass, borosilicate glass, barium borosilicate glass, quartz glass and lead glass, among which borosilicate glass, barium borosilicate glass and quartz glass are preferred, and particularly barium borosilicate glass Is preferred.

The thickness of the glass layer is not particularly limited, but is generally 0.1 to 20 mm, preferably 0.5 to 15 mm,
It is more preferably 1 to 10 mm, particularly preferably 1.5 to 5 mm.

In the composite of the present invention, the above-mentioned fluororesin layer and the glass layer are bonded via an adhesive. The adhesive used for this is not particularly limited, but the organic polymer-based Adhesives are preferably used, specifically, for example, acrylic resins, fluorine resins, natural or synthetic rubber resins, urethane resins, vinyl resins and silicone resins, among which acrylic resins, and And / or fluororesins are preferred.

As the acrylic resin, for example, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, 2-methylbutyl acrylate, 2-hydroxyethyl acrylate, Acrylic ester resins such as cyanoacrylate and ethyl methacrylate,
Methyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, 2-methylbutyl methacrylate, 2-hydroxyethyl methacrylate A methacrylate resin such as acrylate and hydroxypropyl methacrylate. Further, there are copolymers composed of the above-mentioned acrylic compound and copolymers composed of the above-mentioned acrylic compound and vinyl esters such as vinyl acetate and vinyl propionate, and styrene. Acrylic compounds forming these copolymers include ethyl acrylate, butyl acrylate,
2-Ethylhexyl acrylate, 2hydroxyethyl acrylate and acrylic acid are preferred, and ethyl acrylate and butyl acrylate are particularly preferred.

Examples of the fluorine-based resin include a polyvinylidene fluoride-based resin, a fluoroalkyl acrylate-based resin, a fluororubber-based resin, a vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer-based resin, tetrafluoroethylene and / or monochlorotrifluoro. Ethylene-hydroxyalkyl vinyl ether-alkyl vinyl ether copolymer resins, etc., among which vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer resins, tetrafluoroethylene and / or monochlorotrifluoroethylene-hydroxyalkyl vinyl ether-alkyl Vinyl ether copolymer resins are preferred.

Examples of the urethane-based resin include polyoxyalkylated diols or polyols, tackifiers having a softening point of 40 ° C to 140 ° C, aliphatic or aromatic diisocyanates or polyisocyanates. As the vinyl resin, for example, vinyl chloride-vinyl acetate copolymer,
Examples of the resin include vinyl ether-based resins such as a vinyl acetate polymer, polyvinyl butyral, and polyalkyl vinyl ether. Further, examples of the silicone type include rubbery polysiloxane and resinous polysiloxane.

The adhesive described above can be used alone or as a copolymer of two or more of these and a mixture thereof.

The thickness of the adhesive layer is not particularly limited, but is generally 5 to 500 µm, preferably 10 to 300 µm, and more preferably 20 to 200 µm. Furthermore, by adding particulate matter such as glass beads to the adhesive layer, the initial bonding strength between the fluorine-containing resin layer and the glass layer can be reduced, so that the bonding step can be performed easily. The particle size of the granular material used here is 5 to 50 μ, preferably 20 μm.
3030μ. The composite joined in this manner can be joined more firmly later by further pressure bonding.

Further, various additives and coloring agents for improving weather resistance, heat resistance, and adhesive strength can be added to the adhesive. Examples of these additives and colorants include the following ultraviolet absorbers, antioxidants, light stabilizers, tackifiers, plasticizers, pigments and dyes, and the like.

The ultraviolet absorber that can be added to these adhesives can be appropriately selected from a wide variety of types in consideration of the ultraviolet absorbing ability of the ultraviolet absorber, compatibility with the adhesive used, and the like. Examples of usable ultraviolet absorbers include the following.

Hydroquinone-based hydroquinone, hydroquinone disalicylate salicylic acid-based phenyl salicylate, paraoctylphenyl salicylate benzophenone-based 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy -4-methoxy-
2'-carboxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-benzoyloxybenzophenone, 2,2'-hydroxy-
4-methoxybenzophenone, 2-hydroxy-4-
Methoxy-5-sulfonebenzophenone, 2,2 ', 4,4'
-Tetrahydroxybenzophenone, 2,2'-hydroxy-4,4'-dimethoxy-5-sodium sulfobenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-5-chlorobenzophenone benzotriazole-2- ( 2'-hydroxy-
5'-methylphenyl) benzotriazole, 2-
(2'-hydroxy-5'-methylphenyl) -5
Carboxylic acid butyl ester benzotriazole, 2-
(2'-hydroxy-5'-methylphenyl) -5,6
-Dichlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5-ethylsulfonebenzotriazole, 2- (2'-hydroxy-5'-
Tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-amylphenyl) benzotriazole, 2-
(2'-hydroxy-3 ', 5'-dimethylphenyl)
Benzotriazole, 2- (2'-hydroxy-
3 ', 5'-dimethylphenyl) -5-methoxybenzotriazole, 2- (2'-methyl-4'-hydroxyphenyl) benzotriazole, 2- (2'-stearyloxy-3', 5'-dimethylphenyl ) -5-Methylbenzotriazole, 2- (2'-hydroxy-5-carboxylic acid phenyl) benzotriazole ethyl ester, 2- (2'-hydroxy-3'-methyl-5'-
Tert-butylphenyl) benzotriazole, 2- (2 '
-Hydroxy-3 ', 5'-di-tert-butylphenyl)-
5-chloro-benzotriazole, 2- (2'-hydroxy-5'-methoxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-phenylphenyl) -5-chlorobenzotriazole, 2- (2 '-Hydroxy-5'-cyclohexylphenyl) benzotriazole, 2- (2'-hydroxy-5-cyclohexylphenyl) benzotriazole, 2- (2'-hydroxy-5-cyclohexylphenyl) benzotriazole, 2- (2'- Hydroxy-4 ', 5'-dimethylphenyl) -5-carboxylic acid benzotriazole butyl ester, 2- (2'-hydroxy-3', 5'-
Dichlorophenyl) benzotriazole, 2- (2'-
Hydroxy-4 ', 5'-dichloro) benzotriazole, 2- (2'-hydroxy-3', 5'-dimethylphenyl) -5-ethylsulfonebenzotriazole,
-(2'-hydroxy-5'-phenylphenyl) benzotriazole, 2- (2'-hydroxy-5'-
Methoxyphenyl) -5-methylbenzotriazole,
2- (2'-hydroxy-5'-methylphenyl)-
5-carboxylic acid ester benzotriazole, 2-
(2'-acetoxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole.

Of these ultraviolet absorbers, benzophenone-based and benzotriazole-based ones are preferred, and among the benzophenone-based ones, 2,3'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy -4-
Methoxybenzophenone and 2,2 ', 4,4'-tetrahydroxybenzophenone; 2 for benzotriazole
-(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5,6-dichlorobenzotriazole, 2- (2'-hydroxy-5 '-Tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-methyl-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-
Di-tert-butylphenyl) -5-chloro-benzotriazole and 2- (2'-hydroxy-5'-phenylphenyl) -5-chlorobenzotriazole, 2- (2 '
-Hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl)
-5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-t
-Butylphenyl) benzotriazole, 2- (2'-
Hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- {2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl} benzotriazole, 2- {2-hydroxy-3,5-bis (α, α'-)
(Dimethylbenzyl) phenyl} -2-hydroxybenzotriazole, a particularly preferred UV absorber is of the formula In the formula, R ₁ and R ₂ are the same or different and each represent a lower and higher alkyl group, particularly a branched lower alkyl group or an aryl group, particularly a phenyl group, and further, a hydroxyl group, It may have a functional group such as an amino group, and X is a type represented by a hydrogen atom or a halogen atom, particularly a chlorine atom.

The amount of the ultraviolet absorber as described above can be varied widely depending on the type of the ultraviolet absorber, the type of the adhesive to be used, the thickness of the adhesive layer, and the like.
It is in the range of 0.01 to 15 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, per 100 parts by weight.

Further, examples of the light stabilizer include a hindered amine compound and a nickel complex salt compound, among which a hindered amine compound is preferable.

As the hindered amine compound, for example, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate bis (1,2,2,6,6-pentamethyl-4-piperidyl)
Dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine sebacate succinate polycondensate, 1- [2- {3- (3,5-di-t-butyl) -4-hydroxyphenyl) propionyloxy}
-Ethyl] -4- {3- (3,5-di-tert-butyl-4
-Hydroxyphenyl) propionyloxy {-2,2,6,
6-tetramethylpiperidine bis (1,2,2,6,6-pentamethyl-4-piperidyl) 2- (3,5-di-t-butyl-4-hydroxydibenzyl) -2-n-butylmalonate
And poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-24-diyl} (2,2,6,6-
Tetramethyl-4-piperidyl) imino {hexamethylene} (2,2,6,6-tetramethyl-4-piperidyl) imino} and the like, among which dimethyl-1- (2-succinate)
Hydroxyethyl) -4-hydroxy-2,2,6,6-tetramertylpiperazine polycondensate is preferred.

The amount of the light stabilizer as described above can be varied widely depending on the type of the light stabilizer, the type of the adhesive to be used, the thickness of the adhesive layer, and the like. It is in the range of 0.01 to 15 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight per 100 parts by weight.

Further, in the present invention, by providing a resin containing a continuous and / or discontinuous colorant on at least one surface of the fluorine-containing resin layer, it is possible to enhance the design of the composite of the present invention. The resin used for this purpose is not particularly limited, but is generally, for example, vinylidene fluoride / tetrafluoroethylene-hexafluoropropylene copolymer resin or tetrafluoroethylene and / or monochlorotrifluoroethylene-hydroxy resin. Solvent-soluble fluorocarbon resins such as alkyl vinyl ether-alkyl vinyl ether copolymer resins, acrylic resins, and urethane resins are preferred.

As the coloring agent, any coloring agent can be used, but a coloring agent that can be used for a long time is preferable.
Published by ciety of Dyers and Colorists. Color
It can be selected from the coloring agents listed in Index 3rd Edition (1971) and Supplements (1975).

Colorant names shown here are the Color Index Gener
According to ic Name. For example, Y-1 is CI Pigment Yellow 1
O means yellow (Orange), R means red (Red),
V is purple (Violet), B is blue (Blue), G is green (Gr
een) and Br represent brown, Bk represents black, and W represents white.

The color of the colorant used in the present invention is yellow, red, purple,
Any color tone such as blue, green, brown, black, and white can be used. Illustrative examples of the yellow colorants below include azo-based and condensed polycyclic metal complex-based pigments. Examples of the azo type include insoluble monoazo pigments (Y-97, Y-116, Y-120, Y-151, Y-154), disazo pigments (Y-81, Y-83, Y-155), and condensed azo pigments. (Y-93, Y-94,
Y-95, Y-128) are preferred, and in the condensed polycyclic system, anthraquinone pigments (Y-24, Y-108, Y-147, Y-123, Y-99) and isoindolinone pigments (Y-109, Y- 110, Y-173), isoindoline pigment (Y-139), quinophthalone pigment (Y-138)
In the case of a metal complex salt, the same azomethine pigment (Y-11
7, Y-129) nickel nitroso pigment (Y-153) nickel azo pigment (G-10) is preferred. Further, in the inorganic system, iron oxide yellow (Y-42), titanium-antimony-nickel oxide (Y-53) and the like are preferable.

As orange pigments, azo pigments and condensed polycyclic pigments are particularly preferred, and as azo pigments, insoluble monoazo pigments (O-36, O-5, O-38, O-60, O-62) and diazo pigments are preferred. (O-34), condensed azo pigments (O-31) are preferred, and as the condensed polycyclic pigments, perylene pigments (O-43), anthraquinone pigments (O-40, O-51), isoindolinone pigments Pigments (O-42), quinacridone pigments (O-48, O-49)
Are preferred.

As red pigments, azo pigments, condensed polycyclic pigments, and inorganic pigments are particularly preferred. As azo pigments, insoluble monoazo pigments (R-2, R-6, R-7, R-9, R- 10, R−12, R−
14, R-112, R-146, R-147, R-170, R-171, R-175, R-18
5, R-187, R-188, R-208), azo lake pigment (R-5
2: 2, R-115, R-151, R-243), condensed azo pigments (R-14
4, R-166, R-214, R-220, R-221, R-242) and disazo pigments (R-38, R-37). Examples of condensed polycyclic pigments are anthraquinone pigments (R -168, R-177, R-216),
Thioindigo pigments (R-88), perinone pigments (R-88)
194), perylene pigments (R-123, R-149, R-178, R-17)
9, R-190, R-224), quinacridone pigments (V-19, R-1)
22, R-202, R-207, R-209, R-206), and as a new pigment, a diketopyrrolopyrrole-based pigment (Irgadine DPP Red BO manufactured by Ciba Geigy) is exemplified.
Bengala (red iron oxide R-10)
1), zinc / iron oxide (R-225) and the like.

As violet pigments, azo pigments and condensed polycyclic pigment inorganic pigments are particularly preferred, as azo pigments are monoazo pigments (V-50), as condensed polycyclic pigments are perylene pigments (V-29), Anthraquinone pigments (V-31, V-33),
Thioindigo pigments (V-38, V-36), quinacridone pigments (V-19), dioxazine pigments (V-23, V-3)
7) As an inorganic pigment, a cobalt phosphate pigment (V-14:
1) Ferrolite violet pigment (V-18), cobalt lithium vanadium phosphate pigment (V-4)
7) and the like.

As the blue pigment, a phthalocyanine pigment, a polycondensation polycondensation pigment, and an inorganic pigment are particularly preferred. As the phthalocyanine pigment, an α-type copper phthalocyanine pigment (B-15: 1, B
-15: 2) β-type copper phthalocyanine pigment (B-15: 3, B-15:
4), ε-type phthalocyanine pigments (B-15: 6), metal-free phthalocyanine pigments (B-16), and indatron pigments (B-60, B-21, B-22, B −64),
As the inorganic pigment, navy blue (B-27), ultramarine blue (B-29),
Cobalt-aluminum oxide pigment (B-28), cobalt-chromium-aluminum oxide pigment (B-36), and the like.

As the green pigment, a phthalocyanine pigment, a condensed polycyclic pigment, and an inorganic pigment are particularly preferable. As the phthalocyanine pigment, a medium chlorinated copper phthalocyanine pigment (G-3
7), highly chlorinated copper phthalocyanine pigments (G-7), highly chlorobrominated copper phthalocyanine pigments (G-36), and condensed polycyclic pigments such as biolanthrone green (G-47);
Examples of the inorganic pigment include a chromium oxide pigment (G-17) and a cobalt-titanium-nickel-zinc oxide pigment (G-1).
9) and cobalt-titanium pigments (G-50).

As the brown pigment, an azo pigment, a polycondensed polycondensation pigment, or an inorganic pigment is particularly preferable. As the azo pigment, a monoazo pigment (Br-25, Br-32) metal complex salt azo pigment (Br-5, B
r-2), a condensed azo pigment (Br-23), an anthraquinone pigment (Br-28), a perylene pigment (Br-26) as a polycondensed pigment, and an iron oxide pigment as an inorganic pigment ( Br
-6), iron-chromium oxide pigment (Br-29), zinc-iron oxide pigment (Br-31) and the like.

As black pigments, there are pigments which can be preferably used for organic pigments and inorganic pigments, respectively. Examples of organic pigments include aniline black (Bk-1) and perylene black (Bk-3).
1) As an inorganic pigment, carbon black (Bk-3
1) Carbon black (Bk-
7), bone black (Bk-9), iron black (Bk-11), and cobalt oxide pigment (Bk-13).

As the white pigment or the extender (transparent) pigment, an inorganic pigment is particularly preferable. For example, zinc white (W-4), zinc sulfide (W-7), titanium dioxide (W-6), calcium carbonate (W-18) ), Clay (W-19), barium sulfate (W
-21), alumina white (W-24), silica (W-2)
7), muscovite (W-20), tank (W-26) and the like.

Other particularly preferred pigments include titanium dioxide-coated mica known as pearl pigments, and the particle size is 2 to 2.
It is preferably 200 μm, more preferably 4 to 150 μm.
μ, especially 5-100 μ, is preferred. In addition, from the viewpoint of weather resistance, the titanium oxide of the coating layer is preferably a rutile type. Further, they may be colored with a coloring agent such as iron oxide or the like, may show an interference color, or may have a silver tone or a milk tone.

Commercial products include Merck, Irio Zinmar, and highlights.

The resin containing these colorants can be continuously and / or discontinuously present on at least one surface of the fluororesin layer. The term “continuous” as used herein means the entire surface or a part of the fluororesin layer. The term “discontinuous” refers to a state that exists in a state that is not substantially continuously present, such as a point state, a line state, a character and symbol state, and a spot. It is to be present in a pattern state, a gradation state, and the like, and the ratio to be present is not particularly limited, but is generally 1 to 80%, preferably 2%.
-50%, more preferably 5-30%. The method for causing a resin containing a continuous and / or discontinuous colorant to be present on at least one surface of the fluorine-containing resin layer is not particularly limited, and examples thereof include a roll coating method, a spin coating method, a spray coating method, and a gravure printing method. , Screen printing, jet spray printing, flexographic printing, letterpress printing, intaglio printing, lithographic printing, heat lamination, pressure lamination, coextrusion and the like.

In addition to the colorant, the resin containing a colorant further includes
An ultraviolet absorber, a light stabilizer and the like can be added as needed. The type and amount of the ultraviolet absorber and the light stabilizer to be added can be determined according to the type and amount of the ultraviolet absorber and the light stabilizer to be added to the adhesive.

The novel composite obtained in this manner is lightweight and thin, and has a long-lasting effect of preventing glass from scattering, and further has extremely high design properties. Protective material Used for watch face glass, window glass, glasses, sunglasses, vehicle window glass, bulletin board surface glass, show window glass, liquid crystal and EL display window glass, etc. It is.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples.

Example A (Preparation of Composite) 1) Preparation of Surface Resin Layer i Composite Nos. 1-3 and 5-11: Using commercially available films shown in Table 2, an adhesive layer or a colorant-containing resin layer The surface in contact with was subjected to corona treatment so that "wetting" by a method based on JIS K-6768 was within the range of 45 to 54.

ii Complex No. 4: Fluorine-containing copolymer shown in Table 2 (manufactured by Asahi Glass,
100 parts by weight of “Lumiflon”) and an anthraquinone-based yellow pigment (Paliogen L-1 manufactured by BAS F) shown in Table 7
560) in an amount of 0.5 part by weight, and the ultraviolet absorber 2- {2'-hydroxy-3 '-(3 ", 4", 5 ", 6" shown in Table 4 and Table 4
-Tetrahydrophthalimidomethyl) -5'-methylphenyl} benzotriazole 1.5 parts by weight, 2- {2-hydroxy-3,5-bis (α, α'-dimethylbenzyl)
Phenyl｝ -2-hydroxybenzotriazole, 1.5
Parts by weight, the light stabilizer shown in Table 5, dimethyl-1- (2-hydroxy) -4-hydroxy-2,2,6,6-dimethylsuccinate
Add 1.5 parts by weight of 6-tetramethylpiperidine polycondensate,
Colloid mill (Nippon Seiki Seisakusho "Mill Mix MM-
1)), dispersion treatment was performed at 10,000 rpm for 10 minutes. 30 parts by weight of xylene and 8 parts by weight of a curing agent ("Coronate HL" made by Nippon Polyurethane) were added, cast on a PET film with a bar coater, dried at 120 ° C. for 10 minutes, and then peeled off from the PET film to give a layer thickness of 50 μm. A colorant-containing resin layer and a surface resin layer were obtained.

2) Preparation of glass layer The existing glass plate shown below was used for the glass layer.

3) Preparation of Adhesive Layer i-Composite Nos. 1, 3 and 6 to 12: The acrylic resin adhesive shown in Table 3 and the ultraviolet absorbents shown in Tables 1, 3, 3) and 4) After adding a light stabilizer and dissolving, add 1.5 parts by weight of an isocyanate-based curing agent (Coronate L, manufactured by Nippon Polyurethane) and 25 parts by weight of a solvent (toluene). After drying at 100 ° C. for 5 minutes, an adhesive layer having a layer thickness of 40 μ was obtained. Further, it was bonded to a surface resin layer having a colorant-containing resin layer at a normal temperature at a pressure of 5 kg / cm ² .

ii Composite Nos. 2, 4 and 5: Composite Nos. 1 and 2 except that the acrylic resin adhesive shown in Table 3 was used instead of the acrylic resin adhesive used in Composite No. 1 above. Similarly, an adhesive layer was prepared.

4) Preparation of Colorant-Containing Resin Layer i-Composite Nos. 1 to 3, 6 to 9 and 11: Based on 100 polymer parts of the fluorinated copolymer shown in Table 6, Tables 1, 4, and 2) To 4), a coloring agent, an ultraviolet absorber and a light stabilizer, and an antifoaming agent (manufactured by Toray Silicone, SC55
40) 0.02 parts by weight, 20 parts by weight of carbitol acetate, 8 parts by weight of a curing agent (Coronate HL made by Nippon Polyurethane) were added, and after sufficient stirring, solid printing was performed on the surface resin layer shown in Table 1 using a 180-mesh screen. did. After drying at 80 ° C. for 60 minutes, a colorant-containing resin layer having a thickness of 10 μm was obtained.

ii Complex No. 4: v Colorants, UV absorbers and light stabilizers shown in Tables 1, 4, 2) to 4) based on 100 parts by weight of the fluorinated copolymer shown in Table 6. Was added and the mixture was subjected to a treatment at 10,000 rpm for 10 minutes in a colloid mill (“Mill Mix MM-1” manufactured by Nippon Seiki Seisaku-sho, Ltd.). Add 30 parts by weight of xylene and 8 parts by weight of a curing agent ("Coronate HL" manufactured by Nippon Polyurethane), cast on a PET film using a bar coater, and dry at 120 ° C for 10 minutes.
A surface resin layer and a colorant-containing resin layer having a thickness of 50 μm were peeled off from the PET film.

iv Complex No. 5: 40 parts by weight of the acrylic copolymer shown in Table 6 were dissolved in 20 parts by weight of cyclohexanone and 40 parts by weight of an aromatic hydrocarbon-based solvent (“Solvesso 100” manufactured by Showa Shell Sekiyu Sekiyu Sekiyu KK). −
0.02 parts by weight of a coloring agent, an ultraviolet absorber, a light stabilizer and an antifoaming agent (“SC-5540” manufactured by Toray Silicone) shown in 1,4,2) to 4) are added, and a three-roll mill (“NR- manufactured by Noritake”) is added. 84 ") four times. Further, 20 parts by weight of cyclohexanone was added, and the patterns shown in Table 8 were formed on the surface resin layer shown in Table 1 using a 180-mesh screen. 80
The layer thickness of the colorant-containing resin layer after drying at 30 ° C. for 30 minutes was 10 μm.

vComposite No. 10: 100 parts by weight of the fluorinated copolymer shown in Table-6, coloring agents and ultraviolet absorbers shown in Tables 1, 4, 2) to 4),
Light stabilizer and defoamer (“SC-5540” manufactured by Toray Silicone)
Add 0.02 parts by weight to a three-roll mill (NR-8
4 ") four times. In addition, carbitol acetate 20 parts by weight hardener (Nippon Polyurethane "Coronate
HL "(8 parts by weight) was added, and the patterns shown in Table 8 were printed on the surface resin layer shown in Table 1 using a 180-mesh screen. After drying at 80 ° C. for 30 minutes, a colorant-containing resin layer having a layer thickness of 10 μ was obtained.

5) Lamination of surface resin layer and glass layer, i-composites Nos. 1-4 and 5-11: adhesive layer with release paper on surface resin layer having colorant-containing resin layer prepared in 4) above Were bonded together at normal temperature with a pressure of about 5 kg / cm ² . Next, the release paper was peeled off and the adhesive layer was combined on one side of the glass layer and bonded at room temperature with a pressure of about 5 kg / cm ² ,
Complex Nos. 1-4 and 5-11 of Table 1 were prepared.

iii Composite No.12: Asahi Glass laminated glass “Lamisafe UV” approx. 75 mm x 15
The one cut to 0 mm was used. The structure is as shown in the attached drawing No. 5, and it is manufactured by heating and attaching two sheets of soda ash glass having a layer thickness of 3.8 mm and an adhesive layer having a layer thickness of 0.4 mm. The adhesive layer is made of potavinyl butyral to which an ultraviolet absorber has been added.

Example B (Evaluation of Composite) For Composite Nos. 1 to 16 prepared in Example A, weight, thickness, light transmittance and its persistence, glass scattering prevention and its persistence, and design and its persistence The performance was evaluated, and the overall applicability was evaluated. The results are shown in Table-9.

 Next, the evaluation items and their determination criteria will be described.

A composite having a weight of 75 mm × 150 mm was weighed with a digital precision electronic balance and converted to a weight per 10 cm ² area in grams.

Judgment standard Abbreviation ・ Less than 100 g ・ ・ ・ ・ ・ ・ ○ ・ 100 g or more and less than 150 g ・ ・ ・ ・ ・ ・ ・ ・ ・ △ ・ 150 g or more ・ ・ ・ ×× Thickness The thickness was measured three times with calipers, and the average value was calculated to the first decimal place.

Judgment criteria ・ Less than 3.0mm ……… ○ ・ 3.0mm or more and less than 5.0mm ……… △ ・ 5.0mm or more ……… × Light transmittance Spectrophotometer (“UV-365” manufactured by Shimadzu Corporation) Set the part and measure the total light transmittance of the complex at a wavelength of 500 nm to 800 nm, and the wavelength 650 n from the obtained chart
The transmittance at m was read and this was defined as the light transmittance of the composite.

Judgment criteria ・ 80% or more ……… ○ ・ Less than 80% 70% or more ……… △ ・ Less than 70% …… × × Glass scattering prevention (Except for composite No.16), and visually observe the broken state of glass layer, scattering of glass, state of surface resin layer, etc. when 225 g of steel ball is dropped from the height of 1 m to the center of the composite. did.

Judgment Criteria The glass was not broken, or even if broken, the integrity of the composite was not impaired, the glass was not scattered at all, and no damage such as breakage or tearing was observed on the surface resin layer.

··· O · Although the glass was broken, part of the glass was scattered from the composite, but no damage such as tearing or tearing was observed on the surface resin layer. …… △ ・ The glass was broken and the scattering of glass was remarkable, and the surface resin layer was severely damaged by tearing and tearing. ... × Designability After 1500 hours and 3000 hours after the WOM test, the appearance of the composite was compared with the original piece and visually observed.

Judgment criteria-Little change was observed compared to the original piece. ··· O · Slight abnormalities such as fading and whitening were observed compared to the original pieces. …… △ ・ Notable abnormalities such as fading, whitening or peeling were observed compared to the original pieces. …… × W-O-M test Sunshine weather meter (Suga Test Machine, WEL
-SUN-HC) operating conditions were set at 120 minutes cycle (18 minutes rainfall), black panel temperature (63 ± 3) ° C, and about 75 minutes.
The composite of mm × 150 mm was set so that the surface resin layer was on the light source side, and after 1500 hours and 3000 hours of test, the composite was taken out and examined for light transmittance, glass scattering prevention, and design.

Hot water immersion test Distilled water at 50 ° C. was placed in a 2 liter beaker, and a 75 mm × 150 mm composite was immersed in the constant temperature layer at 50 ° C. for 200 hours. After taking out and leaving at room temperature for 1 hour, the glass scattering prevention property was examined.

Comprehensive Evaluation The practicality of each composite was comprehensively determined based on the evaluation items and criteria described above.

Judgment criteria-Practicality is sufficiently recognized. ……… ◎

[Brief description of the drawings]

FIGS. 1 to 5 schematically show the respective structures of composite Nos. 1 to 12 used in Examples 1 to 5 and Comparative Examples 1 to 7. FIG. 1 shows complex Nos. 1, 5-9 and 11, and FIG.
The figure shows Complex Nos. 2, 3 and 10, and FIG. 4 shows Complex No. 4.
FIG. 5 shows the structure of the composite No. 12. Here, 1 is a surface resin layer such as a fluorine-containing resin layer, 2 is a colorant-containing resin layer, 3 is an adhesive layer, 4 is a glass layer, and 5 is a layer serving as both a colorant-containing resin layer and an adhesive layer. Numerals 6 and 6 denote a layer which also serves as a fluorine-containing resin layer and a colorant-containing resin.

Continuation of the front page (56) References JP-A-62-23751 (JP, A) JP-A-58-120535 (JP, A) JP-A-61-241331 (JP, A) JP-A-62-216275 (JP) , A) JP-A-2-123771 (JP, A) JP-A-1-244669 (JP, A) JP-A-67-1538 (JP, U) (58) Fields investigated (Int. Cl. ⁶ , DB Name) B32B 1/00-35/00 H01L 31/04

Claims (10)

(57) [Claims] Claims: 1. At least a fluorine-containing resin layer and a layer thickness of 1 to 10 mm
In a composite in which a borosilicate glass layer or a barium borosilicate glass layer is bonded via an adhesive layer,
The adhesive is an adhesive made of an acrylic resin containing an ultraviolet absorber and / or a light stabilizer, and the power supply unit is mainly
A composite, which is a surface protection material for Cd-based solar cells. 2. The fluorine-containing resin has a fluorine content of 30% by weight.
The composite according to claim 1, which is as described above. 3. The fluorine-containing resin is an ethylene-tetrafluoroethylene-based copolymer, an ethylene-chlorotrifluoroethylene-based copolymer, a hexafluoropropylene-tetrafluoroethylene-based copolymer, or a perfluoroalkyl vinyl ether-tetrafluoroethylene copolymer. Fluoroethylene-based copolymer, polyvinylidene fluoride and polyvinyl fluoride, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene-based copolymer, polychlorotrifluoroethylene, tetrafluoroethylene and / or monochlorotrifluoroethylene-hydroxyalkyl The composite according to claim 1, which is a resin selected from a vinyl ether-alkyl vinyl ether copolymer. 4. The composite according to claim 1, wherein said fluorine-containing resin is an ethylene-tetrafluoroethylene-based copolymer or a polyvinylidene fluoride-based copolymer. 5. The composite according to claim 1, wherein said glass has a softening temperature of 700 ° C. or higher. 6. The composite according to claim 1, wherein said ultraviolet absorber is a benzotriazole compound. 7. The composite according to claim 1, wherein said light stabilizer is a hindered amine compound. 8. The composite according to claim 1, wherein a resin containing a continuous and / or discontinuous colorant is present on at least one surface of said fluorine-containing resin layer. 9. The composite according to claim 8, wherein the resin containing the colorant is a fluorine-containing resin and contains an ultraviolet absorber and / or a light stabilizer. 10. The composite according to claim 1, wherein the composite has a light transmittance at a wavelength of 650 nm of at least 70%.