JPH03203640A - Novel composite - Google Patents

Abstract

PURPOSE:To obtain a thin lightweight composite held in the long-time scattering preventing properties of glass and further having extremely high design effect by bonding a fluoroplastic layer (surface resin layer) and a glass layer through an adhesive layer. CONSTITUTION:As a fluoroplastic film, a film 1 composed of an ethylene/ tetrafluoroethylene copolymer is used and the surface coming contact with an adhesive layer or a colorant-containing resin layer of said film 1 is subjected to corona treatment. A colorant, an ultraviolet absorber, a light stabilizer, a defoaming agent and a curing agent are added to the fluorine-containing copolymer and, after sufficient stirring, solid printing is applied to the fluorine- containing copolymer 1 and dried to obtain a colorant-containing resin layer 2. An ultrasonic absorber and a light stabilizer are added to an acrylic resin adhesive to be dissolved therein and, thereafter, an isocyanate curing agent and a solvent are added to the resulting solution and, after stirring, the obtained composition is applied to release paper and dried to obtain an adhesive layer 3. Further, the adhesive layer 3 is laminated to the surface resin layer 1 having the colorantcontaining resin layer 2. The composite thus obtained is bonded to a glass layer 4.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel composite body, and more particularly, to a lightweight,
The present invention relates to a novel composite body that is thin, maintains glass shatterproof properties for a long period of time, and has an extremely high design quality.

[Prior Art] Various glass plates have been proposed that have a function of preventing glass from scattering when the glass plate is damaged. For example, a glass plate with a polyethylene terephthalate film or a polyethylene film glued to one side (surface), or a laminated glass plate with a three-layer structure mainly used in automobile windshields, etc. It mainly has a polybutylene terephthalate layer in the middle of the plate layers.

However, although glass plates with polyethylene terephthalate film or the like adhered to the glass surface have shatterproof properties at the initial stage of manufacture, their effectiveness rapidly declines over time, especially when used outdoors, making them impractical. It has been pointed out that this may become impossible to provide.

Furthermore, because of its structure, laminated glass sheets with a three-layer structure are heavy and thick, making it impossible to make them lighter and thinner, and furthermore, they have low productivity and are expensive. , could not be used for general purpose.

For example, there is a strong demand for lightweight and thin surface protection materials for solar cells, liquid crystals, EL, watches, etc., and in particular, solar cells, where the power generation part is mainly made of CdS
/ Cd Te, etc., and because of its toxicity, there has been a strong desire to develop a surface protective material that maintains its shatterproof properties for a long period of time.

[Problems to be Solved by the Invention] The purpose of the present invention is to solve the above-mentioned problems that the prior art had. The present invention provides a novel complex that has not been previously known.

[Means for Solving the Problems] The present invention has been made to solve the above-mentioned problems, and at least the fluorine-containing resin I'm (surface resin W!i) and the glass layer The object of the present invention is to provide a novel composite body characterized by being joined through.

The "fluorine-containing resin" used in the present invention may be any resin as long as it contains fluorine in the resin structural formula, and the fluorine content is not particularly limited. The content is 30% by weight or more, preferably 35% by weight or more, and more preferably 40% by weight or more. Examples of such fluororesins include ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and hexafluoropropylene-tetrafluoroethylene copolymer (FEP). ), perfluoroalkyl vinyl ether
Tetrafluoroethylene copolymer (PFA), polyhynylidene fluoride (PVDP), polyvinyl fluoride (PVF), vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene ( PCTFE), tetrafluoroethylene and/or monochlorotrifluoroethylene-hydroxyalkyl vinyl ether-alkyl vinyl ether copolymers, etc., and any of these can be used in the present invention, but among them, ETFE, F
EP and PFA are preferred, especially ETFE.

ETFE consists mainly of ethylene and tetrafluoroethylene (the molar ratio of ethylene/tetrafluoroethylene is generally 40/60 to 60/40), and if necessary, a small amount of ff1 (usually 10 mol% or less) is added to this. In the present invention, the molar ratio of ethylene/tetrafluoroethylene is 40/60 to 60/40, preferably 45,155 to 5.
5/45 and has the formula CH2-CH-CF
(Here, n is an integer from 2 to 10) n 2n
+1 perfluoroalkylvinyl monomer unit (
For example, CH-CH-C4H9 or CH2-CH-C
The content of units derived from 6H13 is 0.1 to 10
ETFE with a mole % of 96, preferably in the range of 0.3 to 5 mole %, is preferably used. This ETFE is known per se and can be produced, for example, by the method described in Japanese Patent Publication No. 59-50183, and is commercially available as "Teflon RCOP" from Asahi Glass Co., Ltd. It is also possible to use those commercially available under the trade names of "Neoflon ETFEJ" manufactured by Co., Ltd. and "Texel" manufactured by DuPont. Further, FEP is sold, for example, as "Neoflon FEPJ" manufactured by Daikin Industries, Ltd. or "Teflon FEPJ" manufactured by DuPont, and PFA is sold, for example, as "Neoflon PFAJ" manufactured by Daikin Industries, Ltd., or "Teflon PFAJ manufactured by DuPont. It is also possible to use those sold under the respective product names.

Furthermore, the above-mentioned fluororesins can be used alone or in combination of two or more.

The above-mentioned fluororesin can be made into a film using the raw material and bonded to the glass layer, but the film can be formed by methods known per se, such as extrusion molding,
This can be carried out by a calendar method, an inflation molding method, or the like. When forming the film, colorants (e.g., titanium oxide, zinc white, calcium carbonate, precipitated silica, carbon black,
chrome yellow, phthalocyanine blue, phthalocyanine green, etc.).

The thickness of the fluororesin layer is not particularly limited, but within the shell it is 5 to 1000 microns, preferably 30 to 500 microns, and more preferably 50 to 200 microns.

There are no particular restrictions on the glass used for the "glass layer" in the present invention, but for example, "Material Encyclopedia, Complete Materials Encyclopedia Editorial Committee," published by Sangyo Kenkyukai Co., Ltd., February 5, 1980, ” pp. 410-427 and edited by Shizo Uesaka, 1972
Glass described in "Product Encyclopedia" published by Toyo Keizai Inc. on June 15, 2015, pages 783-796, etc., specifically,
a softening temperature of 500°C or higher, preferably 600"C or higher,
More preferably 700°C or higher, particularly preferably 800°C
℃ or above, and furthermore, in a solar cell, one surface of the glass plate is coated with Cd as a sunlight absorbing material for power supply.
When printing and firing a system film, such as a CdS film or a CdTe film, and sintering it, a glass containing a small amount of alkali components 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 them, borosilicate glass, barium borosilicate glass, and quartz glass are preferred, and barium borosilicate glass is particularly preferred.

The thickness of the above-mentioned glass layer is not particularly limited, but is generally 0.1 to 20 wrm, preferably 0.1 to 20 wrm.
5-15 am, more preferably 1-10+am.

Particularly preferably, it is 1.5 to 5 mm.

In the composite of the present invention, the fluorine-containing resin layer and the glass layer described above are bonded together via an adhesive, and the adhesive used for this is not particularly limited. Adhesives are preferably used, specifically, for example,
Examples include acrylic resins, fluorine resins, natural or synthetic rubber resins, urethane resins, vinyl resins, and silicone resins, among which acrylic resins and/or fluorine resins are preferred.

Examples of acrylic resins include ethyl acrylate,
n-propyl acrylate, n-butyl acrylate,
Isobutyl acrylate, n-hequinyl acrylate,
Acrylic acid ester resins such as 2-ethylhexyl acrylate, n-octyl acrylate, 2-methylbutyl acrylate, 2-hydroxyethyl acrylate, 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-hydroquine ethyl methacrylate, hydroxypropyl methacrylate It is a methacrylic acid ester resin such as. Further, there are copolymers made of the above-mentioned acrylic acid compounds, and copolymers made of the above-mentioned acrylic compounds and vinyl esters such as vinyl acetate and vinyl propionate, and styrene. As the acrylic compound forming these copolymers, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and acrylic acid are preferred, and ethyl acrylate and butyl acrylate are particularly preferred.

Examples of fluororesins include polyvinylidene fluoride resins, fluoroalkyl acrylate resins, fluorinated rubber resins, and vinylidene fluoride-tetrafluoroethylene resins.
Examples include hexafluoropropylene copolymer resins, tetrafluoroethylene and/or monochlorotrifluoroethylene-hydroxyalkyl vinyl ether-alkyl vinyl ether copolymer resins, among which vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer resins. , tetrafluoroethylene and/or monochlorotrifluoroethylene hydroquine alkyl vinyl ether-alkyl vinyl ether copolymer resins are preferred.

Examples of urethane resins include polyoxyalkylated diols or polyols, tackifiers with a softening point of 40" and 0 to 140°C, aliphatic or aromatic diisocyanates or polyisocyanates. Examples of vinyl resins include, for example. Examples include vinyl ether-based resins such as vinyl chloride-vinyl acetate copolymer, vinyl acetate polymer, polyvinyl butyral, and polyalkyl vinyl ether.Furthermore, silicone-based resins include rubbery polysiloxane, resinous polysiloxane, etc. can be given.

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

The thickness of the adhesive layer is not particularly limited, but - within the film is 5 to 500 μm, preferably 10 to 300 μm.
, more preferably 20 to 200μ. Furthermore, by adding particulate matter such as glass beads to the adhesive layer, the initial bonding strength between the fluororesin layer and the glass layer can be reduced, thereby facilitating the bonding process.

The particle size of the granules used here is 5 to 50 microns, preferably 20 to 30 microns. The thus bonded composite can be bonded more firmly by further crimping later.

Furthermore, various additives and colorants can be added to the adhesive to improve weather resistance, heat resistance, and adhesive strength. Examples of these additives and colorants include the following ultraviolet absorbers, antioxidants, light stabilizers, tackifiers, plasticizers, and pigments/dyes.

The ultraviolet absorber that can be incorporated into these adhesives can be appropriately selected from a wide range of types, taking into consideration the ultraviolet absorbing ability of the ultraviolet absorber and its compatibility with the adhesive used. Examples of usable ultraviolet absorbers include the following.

Hydroquinone series - hydroquinone, hydroquinone disalicylate salicylic acid series - phenyl salicylate, roseoctylphenyl salicylate benzophenone series - 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-〇-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-sulfone benzophenone, 2.2
°.

4.4°-Tetrahydroxybenzophenone, 2,2
゛-Hydroxy-4,4°-dimethoxy-5-sodium sulfobenzophenone, 4-dodecyloxy-2-
Hydroxybenzophenone, 2-hydroxy-5-
Chlorbenzophenonebenzotriazole-2-(2'-hydroxy-
5'-methylphenyl)benzotriazole, 2-(
2'-hydroxy-51-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'-hydroquine-
3°, 5-di-tert-butylphenyl)-5-chloro-benzotriazole, 2- (2'-hydroxy-5'
-methoxyphenyl)benzotriazole, 2-(2'
-Hydroxy-51-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-(2'-hydroxy-5'phenylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methquinphenyl)-5-methylbenzotriazole, 2- (2'hydroxy-5'
-methylphenyl)-5-carboxylic acid ester benzotriazole, 2-(2°-acetoxy-5'-methylphenyl)benzotriazole, 2- (2'-hydroxy-3°,5°-ditertiaryptylphenyl)-
5-chlorobenzotriazole.

Among 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; benzotriazole types include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroquine-5'-methylphenyl)-5,8-dichlorobenzotriazole ), 2-(2'-hydroxy-5'-tert-butylphenyl)hencytriazole,
2- (2'-hydroquine-3'-methyl-5'
-tert-butylphenyl)benzotriazole, 2-
(2'-Hydroquine-3°,5°-di-tert-butylphenyl)-5chloro-benzotriazole and 2-(
2'-hydroxy-5'-phenylphenyl)-5
-Chlorbenzotriazole, 2- (2'-Hydroquine-3°,5°-ditertiarybutylphenyl)-
5-chlorobenzotriazole, 2-(2'-hydroquine-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroquine-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'-Hydroquine-3'-(3", 4", 5"5
6”-tetrahydrophthalimidomethyl)-5′-methylphenyl)benzotriazole, 2-(2-hydroxy-3,5bis(α,α′-dimethylbenzyl)phenyl)=2-hydroxybenzotriazole, particularly suitable UV light In the absorbent, R and R2 are the same or different and each represent a lower and higher alkyl group, especially a branched lower alkyl group or an aryl group, especially a phenyl group; may have a functional group such as a hydroxyl group or an amino group, and X is a hydrogen atom or a halogen atom, particularly a chlorine atom.

The amount of the UV absorber mentioned above can vary widely depending on the type of UV absorber, the type of adhesive used, the thickness of the adhesive layer, etc. 1
00 parts by weight, 0.01 to 15 parts by weight, preferably 0
．． The amount is in the range of 1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight.

Furthermore, examples of light stabilizers include hindered amine compounds and nickel complex salt compounds, among which hindered amine compounds are preferred.

Examples of hindered amine compounds include bis(2
,2,6,B-tetramethyl-4-piperidyl)sebacatebis(1,2,2,6,if-pentamethyl-4piperidyl)sebacatedimethylsuccinate-1(2-hydroquinethyl)-4-hydroxy-2, 2,8,8-tetramethylpiperidine polycondensate, 1[2-+3- (3
,5-di-t-butyl-4-hydroxyphenyl)propionyloxy) -ethyl] -4-+3- (3,
5-di-tert-butyl-4-hydroxyphenyl)propionyloxy)2,2,8,6-titramethylpiperidine 2-(3,5-di-tert-butyl-4-hydroxydibenzyl)-2-n-butylmalone acid bis(1,2
,2,6,[i-pentamethyl-4-piperidyl) and poly[(6-(1,1,3,3-tetramethylbutyl)
Imino 1.3.5-triazine-24-diyl
+ (2,2,G,6tetramethyl-4-piperidyl)
imino)hexamethylene + (2,2,8,8-tetramethyl-4-piperidyl)imino)], among which dimethyl succinate-1-(2-hydroxyethyl)-4
- Hydrocy 2.2.8.8-tetramethylbiperazine polycondensate is preferred.

The amount of the light stabilizer mentioned above can vary widely depending on the type of light stabilizer, the type of adhesive used, the thickness of the adhesive layer, etc., but in general, 100IE
0.01 to 15 parts by weight per part, preferably 0.1 to I
C1m part is more preferably in the range of 0.5 to 8 parts by weight.

Furthermore, in the present invention, the design of the composite of the present invention can be improved by providing a resin containing a continuous and/or discontinuous coloring agent on at least one surface of the fluororesin layer. The resin used for this purpose is not particularly limited, but generally, for example, vinylidene fluoride/tetraoethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene and/or monochrome trifluoroethylene, etc. Preferred are solvent-soluble fluororesins such as hydroxyalkyl vinyl ether-alkyl vinyl ether copolymer resins, acrylic resins, or urethane resins.

Although any coloring agent can be used, a coloring agent that can be used for a long time is preferable, and specifically, -, The
5ociety or Dyers and Col
Published by ourists. Co1our Inde
x 3rd Edition (1971) and Supp
Colorants can be selected from those listed in Colorants (1975).

The coloring agent name shown here is Co1our Ind specified in the same book.
By exGeneric Name. For example, Y-1 means C,1,PigsentYellow I, O is yellow (Orange), R is red (Rerl),
V is purple (Violet), B is blue (1) luc),
G is green, B r is brown (I3rov
n), B k is black (Illack), W is white (
ν old Le) respectively.

The colorant used in the present invention can be of any color such as yellow, red, purple, blue, green, brown, black, and white. Specific examples of the yellow colorant include: Azo pigments and fused polycyclic complex pigments are preferred. Examples of azo pigments include insoluble monoazo pigments (
Y-97, Y-116゜Y-120, Y-151, Y-
154), disazo pigment (Y-81゜Y-88,Y-
155), fused azo (Y-93, Y-94, Y-95
, Y-128) are preferable, and anthraquinone pigments (Y-24, Y-108, Y-147, Y-1
23, Y-99) Isoindolinone pigment (Y-109,
Y-110, Y-173), isoindoline pigment (Y
-139) Quinophthalone pigment (Y-138) is preferred, and among metal complex salts, the same azomethine pigment (Y-117, Y-
129) Nickel nitroso pigment (Y-153) Nickel azo pigment (G-10) is preferred. Among inorganic compounds, iron oxide yellow (Y-42) and titanium-antimony-nickel oxide (Y-53) are preferred.

Particularly preferred are azo pigments and condensed polycyclic pigments, and examples of azo pigments include insoluble monoazo pigments (0
-36,O-5,0-38,0-[io,O-[i2
) Disazo pigment (0-34), condensed azo pigment (0-34)
31) are preferred as the condensed polycyclic pigments, such as perylene pigments (0-43), anthraquinone pigments (0-40,
0-51>, isoindolinone pigment (0-42),
Preferred examples include quinacridone pigments (0-48, 0-49).

As red pigments, azo pigments, condensed polycyclic pigments, and inorganic pigments are particularly preferable, and as azo pigments, insoluble monoazo pigments (R-2, R-6, R-7, R-9゜R- 1
0, R-12, R-14, R-112, I? -146,
R-147, R-170, R-171゜R-175, R
-185, R-187, R-188, R-208),
Azo lake pigment (R-52:2.R-115, R-1
51, R-243), condensed azo pigment (1?-144)
, R-186, R-214, R-220, R-221,
R-242), disazo pigment (R-38,) l-37
), and examples of condensed polycyclic pigments include anthraquinone pigments (R-168゜R-177, R-216), thioindigo pigments (R-88), and perinone pigments (R-1).
94), perylene pigments (R-123, R-149,
R-178, R-179, I? -190, l? -224
), quinacridone pigments (V-19, R-122, R
-202, R-207, R-209°R-208) are preferred, and newer pigments include diketopyrrolopyrrole pigments (Irgazine DPP Red B manufactured by Ciba Geigy).
O) is mentioned. Inorganic pigments include red iron oxide (red iron oxide R-101) and zinc/iron oxide (R-225).
etc.

As the violet pigments, azo pigments, condensed polycyclic pigments, and inorganic pigments are particularly preferred.As the azo pigments, monoazo pigments (V-50), as condensed polycyclic pigments, perylene pigments (V-29), Anthraquinone pigment (V-31,
V-33), thioindigo pigment (V-38゜V-H
), quinacridone pigment (V-19), dioxazine pigment (V-23, V-37>, inorganic pigments include cobalt phosphate (V-14:l) ferrolite violet pigment (V-18), Examples include cobalt lithium vanadium phosphate pigment (V-47).

As the blue pigment, phthalocyanine pigments, condensed polycyclic pigments, and inorganic pigments are particularly preferred.As the phthalocyanine pigments, α-type copper phthalocyanine pigments (B-15:1
．． B-15:2) β-type copper phthalocyanine pigment CB-1
5:3. B-15:4), ε-type phthalonanine pigment (B-15:6), metal-free phthalocyanine pigment (B-
16), Indatron pigments (
B-[io, B-21, [3-22, ll-64), inorganic pigments include navy blue (B-27), ultramarine blue (B-29)
), cobalt-aluminum oxide pigment (B-21
1), cobalt chrome aluminum oxide pigment (B-3[i), etc.

As the green pigment, phthalocyanine pigments, condensed fast pigments, and inorganic pigments are particularly preferable, and as the phthalocyanine pigments, medium chlorinated copper phthalocyanine pigments (G-37
), highly chlorinated copper phthalocyanine pigment (G-7), high chloride brominated copper phthalocyanine pigment (G-36), and violanthrone green (G-4) as a condensed fast pigment.
7) As the inorganic pigment, chromium oxide pigment (G-
17), cobalt-titanium-nickel-zinc oxide pigment (G-19), cobalt titanium pigment (G-50)
) etc.

Particularly preferred brown pigments are azo pigments, condensed fast pigments, and inorganic pigments, and examples of azo pigments include monoazo pigments (l1r-25, Br-32), metal complex azo pigments (13r-5, 8r -2), condensed azo pigment (Br-2
3) Anthraquinone pigments (
[1r-28), perylene pigment (Br-26), iron oxide pigment (l1r-[i), iron-
Examples include chromium oxide pigment (l1r-29), zinc-iron oxide pigment (B'-31), and the like.

As black pigments, there are organic pigments and inorganic pigments that can be preferably used. Examples of organic pigments include aniline black (Bk-1) and perylene black (Bk).
-31), carbon black (Bk-31) as an inorganic pigment
31), carbon black (Bk-
7), bone black (Bk-9) iron black (Bk-11
), cobalt oxide pigment (Bk-13), and the like.

Inorganic pigments are particularly preferred as white pigments or extender (transparent) pigments, such as zinc white (T4), zinc sulfide (Door), titanium dioxide (V-6), calcium carbonate (
V-18), RiL'-(V-19), barium sulfate (W-21), alumina white (V-24),
Examples include silica (W-27), muscovite (W-20), and tank CW-213).

Other particularly preferred pigments include titanium dioxide-coated mica known as pearl pigments.

The particle size is preferably from 2 to 200 microns, more preferably from 4 to 150 microns, particularly preferably from 5 to 100 microns.

Further, from the viewpoint of weather resistance, the titanium oxide of the mJIW is preferably of rutile type. Furthermore, it may be colored with a coloring agent such as iron oxide, or it may exhibit an interference color, or it may be silver-like or milk-like.

Commercially available products include those manufactured by Merck, Iriodinmar, and Highlight.

The resin containing these colorants can be present continuously and/or discontinuously on at least one surface of the fluororesin layer, but "continuous" here means the entire surface or one surface of the fluororesin layer. "Discontinuous" refers to existing in a state that is not substantially continuous, such as point state, line state, character and symbol state, It is to be present in a mottled pattern, a gradation state, etc., and the proportion of the presence is not particularly limited, but - 1 to 80%, preferably 2 to 50%, more preferably 5 to 30% in the shell. It is. The method of making the resin containing a continuous and/or discontinuous coloring agent exist on at least one surface of the fluororesin layer is not particularly specified, but examples include a roll coating method, a spin cord method, a spray coating method, and a gladia printing method. , screen printing method, jet spray printing method, flexographic printing method, letterpress printing method, intaglio printing method, planographic printing method, thermal lamination method,
Examples include pressure lamination method, coextrusion method, and the like.

Furthermore, in addition to the colorant described above, an ultraviolet absorber, a light stabilizer, and the like can be added to the resin containing a colorant, if necessary. The type and amount of the ultraviolet absorber and light stabilizer to be added can be determined according to the type and amount of the ultraviolet absorber and light stabilizer added to the adhesive.

The new composite thus obtained is lightweight, thin, has a long-term glass shatterproof effect, and has an extremely high design quality, making it suitable for use in, for example, solar panels. Surface protection material Used for watch surface glass, window glass, glasses, sunglasses, vehicle window glass, bulletin board surface glass, window window glass, liquid crystal and EL display window glass, etc., making an extremely large contribution to the industry. It is.

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited only to the Examples.

Example A (Preparation of composite) 1) Preparation of surface resin layer ■Composite 1 to 5 and 7 to 15: Using the commercially available films shown in Table 2, the adhesive layer or colorant-containing resin layer was The contacting surfaces were subjected to corona treatment so that the "wetness" was within the range of 45 to 54 by a method based on JIS K-6768.

O complex demon 6: For 100 parts by weight of the fluorine-containing copolymer shown in Table 2, ■ (Asahi Glass Co., Ltd., "Lumiflon J"), anthraquinone yellow pigment shown in Table 7, ■ (Variogen L, manufactured by BASF)
-1560) and 0.5 parts by weight of the ultraviolet absorber 2-12'-hydroquine-3'-(3'
4'5'6'-tetrahydrophthalimidomethyl)-5'-methylphenyl)benzotriazole 1.53 Tfm parts, 2-12hydroxy-3,5-bis(α,α'-dimethylbenzyl)phenyl)-2-hydroxy Benzotriazole, 1.51! Part H1, table -
5. The light stabilizer shown in ■, dimethyl succinate-1-(2
-Hydroxy)-4-hydroxy-2,2,6,6-titramethylviper r, p, m, and was subjected to a dispersion treatment for 10 minutes. Add 30 parts by weight of xylene and 8 parts by weight of a hardening agent (Coronate HLJ manufactured by Nippon Polyurethane), and cast it onto a PET film using a coater. After drying at 120°C for 10 minutes, peel it off from the PET film to determine the layer thickness. A 50 μm colorant-containing resin layer and surface resin layer was obtained.

2) Preparation of glass layer For the glass layer, the following existing glass plate was used.

3) Preparation of adhesive layer ■Composite seeds 1, 4, and 10 to 15: Add the ultraviolet absorber and photostabilizer shown in Tables 1, 33) and 4) to the acrylic resin adhesive shown in Table 3 and ■. After adding and dissolving the agent, add 1.5 parts by weight of isoneanate curing agent (Coronate L, manufactured by Nippon Polyurethane), and 25 parts by weight of solvent (toluene).
After adding parts by weight and stirring, release paper (0Kc-110 manufactured by Tamako Kako)
PsG) using a bar coater and dried at 100° C. for 5 minutes to obtain an adhesive layer with a layer thickness of 40 μm. Furthermore, it was bonded to a surface resin layer having a colorant-containing resin layer at a temperature of 5 kg/cj.

O 狽 combination N11L2. 6 and 8-9: the above complex NI
Table 3 instead of the acrylic resin grafting agent used in ILL
, An adhesive layer was prepared in the same manner as in Composite N[Ll except that the acrylic resin adhesive shown in (1) was used.

■Composite Hiroshi 3 and 5: Add the ultraviolet absorber and light stabilizer shown in Tables 1, 3, 3) and 4) to 100 polymerized parts of the fluorine-containing copolymer shown in Table 3 and ■. Further, 30 parts by weight of a material (xylene) was added, and after dissolving the mixture, it was coated on the surface resin layer shown in Table 1 and dried at 80 DEG C. for 30 minutes to obtain an adhesive layer with a layer thickness of 40 .mu.m.

G-combination N11L7: 100 parts by weight of the fluorine-containing copolymer shown in Table 3, Add the coloring agent-containing resins shown in Tables 1 and 4, apply these compositions to the surface resin layer shown in Table 1 by adding 30 parts by weight of xylene using a colloid mill (newly manufactured by Nippon Seiki Co., Ltd.). It was dried at 80° C. for 30 minutes to obtain a colorant-containing resin layer/adhesive layer of layer #40μ.

4) Preparation of colorant-containing resin layer ■Composite Ko 1-5.10-13 and 15: For 100 parts by weight of the fluorine-containing copolymer shown in Table-6 and ■,
4. Colorants, ultraviolet absorbers and light stabilizers shown in 2) to 4), and antifoaming agents (manufactured by Toshi Silicone, 5C5540)
) 0.02 parts by weight, carpitol acetate 20 parts by weight, curing agent (Coronate HL manufactured by Nippon Polyurethane) af
fifi part was added and after thorough stirring, a 180 ml resin layer was obtained on the surface resin layer shown in Table 1.

O complex demon 6: For 100 parts by weight of the fluorine-containing copolymer shown in Table 6, In addition, a colloid mill (Newly manufactured by Nippon Seiki Seisakusho "Milmix MM-IJ") is used.
The treatment was carried out for 110 minutes. 30,111 parts of xylene and curing agent (Coronate HLJ manufactured by Nippon Polyurethane)
8 μm part was added and cast onto a PET film using a bar coater at 120°C.
Nearn'31 r SC-554D J) 0
．． 02ffiffi part was added and kneaded by passing it through a three-roll mill (rN R-84J manufactured by Noritake Co., Ltd.) four times. 30 parts by weight of cyclohexanone was added to the mixture and a pattern of Table 8 and ■ was formed on the surface resin layer of Table 1 using a 225 mesh screen.

The layer thickness of the colored layer-containing resin layer after drying at 80°C for 30 minutes is 5
It was μ.

■Composite N11L9: Part of the acrylic copolymer 407rJQ shown in Table 6, ■ was mixed with 20 parts by weight of cyclohexanone and an aromatic hydrocarbon solvent (
Colorants, ultraviolet absorbers, light stabilizers and antifoaming agents (manufactured by Toshinricorn) dissolved in Showa Shell Sekiyu's "Solbet'?i'>40 parts by weight and shown in Table 1, 4, 2) to 4) SC
-554D J ) 0.02 part by weight was added, and the mixture was kneaded by passing it through a three-roll mill (rNR-84J manufactured by Noritake Co., Ltd.) four times. Furthermore, 20 parts by weight of cyclohexanone was added, and the patterns shown in Table 8 and (2) were formed on the surface resin layer shown in Table 1 using a 180 mesh screen. 80℃, 3
The layer thickness of the colorant-containing resin layer after drying for 0 minutes was 10 μm.

■Composite N1114: For 100 parts by weight of the fluorine-containing copolymer shown in Table 6, Agent (Toshi Silicone r S C
-5540J) Add 0.02 parts by weight and make three-mouth HLJ
8 parts by weight was added and the pattern shown in Table 8 was printed using a screen with a surface resin layer of Egami 180 mm shown in Table 1. After drying at 80° C. for 30 minutes, a colorant-containing resin layer having a layer thickness of 10 μm was obtained.

5) Lamination of the surface resin layer and the glass layer, ■ Composite body 1, 2, 4. 6 and 8 to 15: Adhesion with release paper to the surface resin layer having the colorant-containing resin layer prepared in 4) above. The agent layers were pasted together at room temperature with a pressure of about 5 kg, and the front
1 complex? Jcil, 2°4.6 and 8-'15 were prepared.

O Composite Hiro 3, 5 and 7: The surface resin layer having the colorant-containing resin layer and adhesive layer prepared in the previous section 4) was combined with the glass layer at 150°C for about 5K.
Applying a pressure of g/cJ for 10 seconds
．． 5 and 7 were prepared.

O Composite Ko 16: Asahi Glass laminated glass "Lamisafe UVJ" approximately 75cm
A piece cut into 15C1+m was used. The structure is as shown in the attached drawing number 5, and the layer thickness is 3.8+em.
It was manufactured by heating and bonding two sheets of soda ash glass with a 0.4 inch thick adhesive layer sandwiched between them. The adhesive layer consists of polyvinyl butyral with the addition of UV absorbers.

Example B (Evaluation of composites) The weight, thickness, light transmittance and its sustainability, glass shatterproof property and its sustainability, designability and its sustainability were evaluated for the composites N11L1 to 16 prepared in Example A. The results were evaluated and a comprehensive evaluation was made regarding practicality, and the results are shown in Table 9.

Next, the evaluation items and their criteria will be explained.

(2) Weight: A composite measuring 75 mm x 150 mm was weighed using a digital top-pan electronic balance, and the weight was further converted to the weight per 10 cm area in duram units.

Judgment criteria Abbreviation: 100
sr＊shiho ・・・・・・・・・ 0.1
00g or more but less than 150g ・・・・・・・・・ Δ・1
50g or more ・・・・・・・・・×■
The thickness was measured three times with a caliper, and the average value was calculated to one decimal place.

Judgment criteria: 3.0 less than 1 peng
・・・ ・・・ ・・・
0.3.0 or more but less than 5.0
・・・ Δ65.0mm or more ・・・・・・
...×■ A light-receiving part with an integrating sphere was set on a light transmittance spectrophotometer (rUV-365J manufactured by Shimadzu Corporation), and the total light transmittance of the composite was measured at wavelengths of 500 to 800 mm. The transmittance at a wavelength of 650 - was read from the chart, and this was taken as the light transmittance of the composite.

Judgment criteria: 80% or more ・・・・・・・・・ 0
・Less than 80% 70% or more ・・・・・・・・・ Δ
・Less than 70% ・・・・・・・・・ ×
■Glass shatterproofness Place the composite on a horizontal floor with the surface resin layer facing up (excluding composite N116), and
When the steel ball No. g was dropped into the center of the composite, the state of damage to the glass layer, the scattering properties of the glass, the state of the surface resin layer, etc. were visually observed.

1' Criteria - The glass does not break or even if it breaks, the integrity of the composite is not impaired, no glass scattering is observed, and there is no damage such as tears or cracks on the surface resin layer. There wasn't.・・・・・・○・Glass was broken and a portion of the glass was scattered from the composite, but no damage such as tears or cracks was observed on the surface resin layer.・・・・・・Δ・
The glass was broken and there was significant glass scattering, and the surface resin layer was broken and the damage was severe, including cracks. ...×■Design W-0-M test The appearance of the composite after 1500 hours and 3000 hours was compared with the original piece and visually observed.

Judgment criteria: Almost no change was observed compared to the original piece.・・・・・・O・
Slight discoloration, whitening, and other abnormalities were observed compared to the original piece. ....Δ: Abnormalities such as significant discoloration, whitening, or peeling were observed compared to the original piece.・・・・・・X■W
-0-M test sunshine weather meter (manufactured by Suga Test Instruments, WEL
The operating conditions of the i! Set the composite of t75mm x 150mm so that the surface resin layer is on the light source side, and
After testing for 3,000 hours, it was taken out and examined for light transmittance, glass shatter resistance, and design.

■Warm water immersion test Pour 50℃ distilled water into a 2D beaker and soak 75cm x 15cm.
The 0-1 composite was immersed and placed in a constant temperature bath at 50°C for 200 hours. After taking it out and leaving it at room temperature for 1 hour, the glass shatter prevention property was examined.

■Comprehensive evaluation Based on the evaluation items and criteria described above, the practicality of each composite was comprehensively evaluated.

The criteria and practicality are fully recognized.・・・・・・・・・
◎・Practical is recognized.・・・・・・・・・
○・Practicality is not recognized.・・・・・・・・・
・×

[Brief explanation of drawings]

1 to 5 schematically show the respective structures of composites No. 1 to 16 used in Examples 1 to 9 and Comparative Examples 1 to 7. Figure 1 shows composite seeds 1°9-13 and 15.
FIG. 2 shows complex bases 2 to 5.8 and 14,
FIG. 3 shows the structure of the complex seed 7, FIG. 4 shows the structure of the complex seed 6, and FIG. 5 shows the structure of the complex N[L16. 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 that serves as both a colorant-containing resin layer and an adhesive layer. and 6 indicate layers that serve as both a fluorine-containing resin layer and an adhesive-containing resin, respectively.

Claims (1)

[Scope of Claims] 1. A novel composite material characterized in that at least a fluorine-containing resin layer and a glass layer are bonded via an adhesive layer. 2. The novel composite according to claim 1, wherein the fluorine-containing resin has a fluorine content of 30% by weight or more. 3. The fluororesin is an ethylene-tetrafluoroethylene copolymer, an ethylene-chlorotrifluoroethylene copolymer, a hexafluoropropylene-tetrafluoroethylene copolymer, or a perfluoroalkyl vinyl ether-tetrafluoroethylene copolymer. Copolymers, polyvinylidene fluoride and polyvinyl fluoride, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymers, polychlorotrifluoroethylene, tetrafluoroethylene and/or monochlorotrifluoroethylene-hydroxyalkyl vinyl ether-alkyl The novel composite according to claim 1, which is a resin selected from vinyl ether copolymers. 4. The novel composite according to claim 1, wherein the fluororesin is an ethylene-tetrafluoroethylene copolymer. 5. The novel composite according to claim 1, wherein the glass has a softening temperature of 500°C or higher. 6. The novel composite according to claim 1, wherein the glass is barium borosilicate glass. 7. The novel composite according to claim 1, wherein the composition of the adhesive is mainly an acrylic resin and/or a fluororesin. 8. The novel composite according to claim 1, wherein a resin containing a continuous and/or discontinuous coloring agent is present on at least one surface of the fluororesin layer. 9. The novel composite according to claim 1, wherein the adhesive layer contains an ultraviolet absorber and/or a light stabilizer. 10. The novel composite according to claim 9, wherein the ultraviolet absorber is a benzotriazole compound. 11. The novel composite according to claim 9, wherein the light stabilizer is a hindered amine compound. 12. The resin containing the colorant is a fluororesin,
9. The novel composite according to claim 8, which contains an ultraviolet absorber and/or a light stabilizer. 13. Novel composite 1 according to any one of claims 1 to 13, wherein the composite is a surface protection material for a solar cell.
4. The novel composite according to claim 13, wherein the power source of the solar cell is mainly Cd-based. 15. The novel composite according to any one of claims 1 to 14, wherein the composite has a light transmittance of at least 60% at a wavelength of 650 nm.