JPH01135639A - Polyester laminate - Google Patents

Abstract

PURPOSE:To produce a coating polyester film laminate, excellent in resistances to scuffing, water and weather, by a method wherein liquid substance, having good adhering property, is applied on the surface of the base material of polyester film and is cured to form a first layer, then, another liquid substance, containing silicon resin, is applied on the first layer and is cured to form a second layer. CONSTITUTION:A polyester laminate consists of a first layer, formed by applying liquid substance, containing anionic group, acrylic resin and inorganic fine particles, on the surface of the base material of polyester film having the thickness of 10-500mum and curring it, and a second layer, formed on the outside surface of the first layer so as to come into contact with the same by applying another liquid substance, containing organic silance compound and especially containing inorganic particles having the grain size of 1-100nm and the partial hydrolyzate of silicon compound shown by a general formula (1), and curring it.

Description

Detailed Description of the Invention <Industrial Field of Application> The present invention involves coating the surface of a polyester fluff material, particularly a polyester film base material, with a liquid material having good adhesion to the polyester film base material by covering it with sand and curing it. 1 layer, and coated and cured a liquid material containing a silicon-based resin on the first layer to form a second layer. Scratch resistance, water resistance,
Coated polyester film fJi with excellent weather resistance! It is about things.

<Prior art> In general, biaxially stretched polyester films are widely used as transparent materials due to their excellent mechanical properties and transparency, but they have the disadvantage of poor scratch resistance and easy scratching on the surface. are doing. In order to improve these shortcomings,
Various methods of coating with thermosetting resin have been proposed.

For example, in Japanese Patent Publication No. 60-53703, a polyester resin is applied as an undercoat layer on a polyethylene terephthalate molded product, and on top of that a polyester resin containing mainly melamine groups (meth) is applied.
A scratch-resistant laminate is disclosed, which is formed by coating and curing a top coat containing a vinyl polymer made of acrylate. In addition, in Japanese Patent Publication No. 60-43303, a resin composition containing a vinylpyrrolidone-acrylic ester copolymer and a quaternary ammonium salt polymer was applied as an undercoat layer on a polyester polymer, and colloidal silica was applied thereon. Disclosed is an abrasion-resistant laminate obtained by coating and curing a top coat containing a hydrolyzate of an epoxy group-containing alkoxysilane as a main component.

<Problems to be Solved by the Invention> However, the above-mentioned polyester laminate cannot be said to have sufficient durability when used under severe conditions such as when used outdoors.

For example, after durability tests such as immersion in boiling water or accelerated weathering tests, there have been problems such as poor appearance, reduced scratch resistance, and reduced adhesion between the polyester film and the ffl film.

Means for Solving the Problems> The present inventors have developed a polyester-based polyester film that has been improved in such a manner that the deterioration of the resistance to shrinkage after such a durability test or the deterioration of the adhesion between the polyester film and the coating film has been improved. With the aim of providing a film article, as a result of intensive research, the first layer was applied by coating a polyester film with a specific organic polymer, and the first layer was coated with a composition containing a specific silicone resin and inorganic particles as main components. By coating and curing the second layer on the first layer, it is possible to improve the adhesion between the first layer and the polyester film after the durability test, and to improve the adhesion of the polyester resin laminate after the durability test. It has been found that appearance and scratch resistance can be improved. That is, the present invention has a thickness of 10-500 mm.
A first layer formed by applying a liquid material containing an anionic group-containing polyurethane resin, an acrylic resin, and inorganic fine particles to the surface of a μm polyester film base material and curing it; and the first layer. A liquid material containing an organic silane compound, especially the following components a and b a; inorganic particles b having a particle size of 11 to 100 nm;
) % Formula % (In the formula, R1 is an alkyl group of carbon rA1-6, an alkoxyalkyl group, an acetyl group, R2 is a hydrocarbon group having 1 to 6 carbon atoms, R3 is a hydrocarbon group, or an epoxy group (meth)acryloyl group , an organic group containing a vinyl group, an allyl group, a mercapto group, a halogen atom, an amino group, a ureido group, or an amide group, n is 2.3 or 4, m is 0 or 1
) This is a polyester laminate comprising a second layer formed by applying and curing a liquid material containing a partially hydrolyzed silicon compound shown in the following.

Examples of the polyester film having a thickness of 10 μm to 500 μrn used in the present invention include saturated polyester films such as biaxially oriented polyethylene terephthalate and polybutylene terephthalate.

The main components of the anionic group-containing polyurethane in the present invention are an isocyanate compound, a polyol, a crosslinking agent, and the like.

Examples of isocyanate compounds include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, propane diisocyanate-1,2, butane diisocyanate-1) ,2, pentane diisocyanate-1,2
, pentane diisocyanate-1,3, hexane diisocyanate-1,5, hexane diisocyanate-1)
,3,3-methyl-hexane diisocyanate-1,4
Aliphatic isocyanate and polyisocyanate compounds such as; 2,4-tolylene diisocyanate, 4,4'-
Diphenylmethane diisocyanate, 4,4'-diphenyl diisocyanate, 1. Aromatic isocyanates and polyisocyanates such as 5-naphthalene diisocyanate, xylene diisocyanate, metaxylene diisocyanate, and triphenylmethane triisocyanate; cycloaliphatic isocyanates such as isophorone diisocyanate and their polyisocyanates, etc. When used outdoors etc. When weather resistance is required, hexamethylene diisocyanate, isophorone diisocyanate, and derivatives or prepolymers thereof are particularly preferred.

Examples of polyols include polyethers such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxytetramethylene glycol; compounds with sulfonic acid groups consisting of metal salts such as sulfoisophthalic acid and sulfoterephthalic acid; terephthalic acid and isophthalic acid; Aromatic dicarboxylic acids such as acids; aliphatic dicarboxylic acids such as adipic acid and azelaic acid;
Ethylene glycol, 1.4 butanediol, diethylene glycol, triethylene glycol, L 4-
Cyclohexane dimetatool, P-xylene diol,
polyethylene glycol, polypropylene glycol,
Polyester resins synthesized from compounds having hydroxyl groups such as polytetramethylene glycol, aliphatic, alicyclic, and aromatic diols; polyesters such as polyethylene adipate, polyethylene-butylene adipate, and polycaprolactone; acrylic polyols, etc. Can be mentioned. The above-mentioned polyester resin is an important component in terms of adhesion with polyester films, and polyester is added to the constituent components of the anionic group-containing polyurethane, or added to the liquid material used to form the vCl layer. It is desirable to add it as a water-soluble or water-dispersible anionic group-containing polyester resin.

Examples of crosslinking agents include ethylene glycol, propylene glycol, butanediol, diethylene glycol, trimethylolpropane, hydrazine ethylene diamine,
Examples include diethylenetriamine and water. The anionic groups in the polyurethane resin include sulfonic acid groups, carboxylic acid groups, ammonium salts thereof, lithium,
They are metal salts such as sodium, potassium, magnesium, etc., and by bonding them to a polyol in advance, an anionic group-containing polyurethane resin can be obtained.

By mixing an acrylic resin having an anionic group into the liquid material used to form the first layer, hot water resistance and weather resistance are improved. The acrylic resin is preferably a water-based one, that is, one that is water-soluble, water-dispersible, or emulsion.

The above acrylic resins include (meth)acrylic acid,
Sodium (meth)acrylate1. Methyl (meth)acrylate, Ethyl (meth)acrylate, Propyl (meth)acrylate, Butyl (meth)acrylate, M2-ethylhexyl (meth)acrylate, Stearyl (meth)acrylate, Dicyclopentenyl (meth)acrylate , hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, butylene glycol mono(meth)acrylate, glycerol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, γ-(meth)acrylate ) Acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropylmethyljethoxysilane, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dibutylamino Ethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminopropyl (meth)acrylate, dibutylaminopropyl (meth)acrylate, (meth)acrylamide, methylol (meth)acrylamide, butoxymethyl (meth)acrylamide, etc. can be mentioned.

By mixing inorganic fine particles into the liquid material used to form the first layer, film winding performance on the production line (blocking property of the first layer), durability tests (e.g. water resistance, The adhesion between the first layer and v, 20 layer after solvent resistance, heat resistance, weather resistance tests) and the physical properties of the first layer (changes in film strength and elongation due to temperature difference, etc.) Well kept.

Inorganic fine particles include silica, silica sol, alumina,
Alumina sol, titania, titania sol, zirconia,
Zirconia sol, antimony, antimony sol, kaolin, talc, calcium carbonate, barium salt, molybdenum sulfide, carbon black, etc., preferably with a particle size of 11-1
00 nm, but silica particles are preferable from an optical viewpoint such as transparency of the film.

In addition to the above-mentioned components, a solvent and various additives are added as desired to form a liquid product.

As the solvent, water or a mixture of water and an organic solvent is used. Organic solvents include alcohols such as methanol, ethanol, isopropanol, isobutanol, and diacetone alcohol; cellosolves such as methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether; A solvent having good compatibility with water such as calpitol is used.

Examples of additives include flow control agents, ultraviolet absorbers, antioxidants, curing catalysts, crosslinking agents, and the like. Examples of flow control agents include commercially available fluorine-based surfactants, block copolymers of alkylene oxide and dimethylsiloxane, and O-5% by weight in the liquid used to form the first waste. More preferably 0.0
Add 01-1% by weight.

As the ultraviolet absorber, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,4-dihydroxybenzophenone,
Benzophenones such as 2,2'-dihydroxy-4-methoxybenzophenone; 2- (2''-hydroxy-
5'-methylphenyl)benzotriazole, 2-(2
'-Hydroxy-5'-t-butylphenyl)benzotriazole, Q ++ (2+-hydroxy-5'-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butyl phenyl)benzotriazole, 2-(2'-hydroxy-di-t
-Butylphenyl>-Benzotriazoles such as 5-chlorobenzotriazole: ethyl-2-cyano-3,3
Examples include cyanoacrylates such as '-diphenylacrylate. These may be used alone or in combination of two or more, and 0-
200 weights are used.

As an antioxidant, 2.6-tert-butyl-
P-cresol, 2 or 3-tert-butyl-4-
Methoxyphenol, stearyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis-(4-methyl-6-
tert-butylphenol), 4,4'-thiobis-
(3-methyl-6-tert-butylphenol), 4
．． 4'-butylidene-bis-(3-methyl-6-ter
t-butylphenol), 1. 1. 3-Tris-(
2-Methyl-4-hydroquine-5-tert-butylphenyl)butane, 1,3.5-)dimethyl-2,4,6
-) lis(3,5-di-tert-butyl-4-hydroxyhensyl)benzene, tetrakis-[methylene-3
-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate comethane, dilaurylthiodipropionate, similystylthiodipropionate, triphenylphosphite, diphenylisodecylphosphite, phenyl Diisodecyl phosphite, 4
,4'-butylidene-bis-(3-methyl-6-ter
t-butylphenyl-di-tridecyl) phosphite,
Examples include tris(nonylphenyl) phosphite, which may be used alone or in combination of two or more, and the weight of the total polymer contained in the liquid used to form the first layer is 100. 0-60 for part
Parts by weight, preferably 0-30 parts by weight, are used.

Examples of the curing catalyst include inorganic acids such as hydrochloric acid and sulfuric acid; ammonium salts such as ammonium chloride, ammonium nitrate, ammonium thiocyanate, and ammonium perchlorate; amines such as dimethylaminopropylamine and diethylaminopropylamine; dibutyltin laurate, etc. Examples include organic tin compounds, and the appropriate amount thereof is generally 0.001 to 10% by weight based on the solid content of the resin.

Adhesion between the polyester film and the second layer, the second
The initial layer of and? In order to improve the appearance and scratch resistance after the IA weather test, the weight ratio of the anionic group-containing polyurethane and acrylic resin contained in the liquid used to form the first layer should be set to 1. :9-3:1 is desirable. A more preferable range is 3 near
The ratio is 2:1. Furthermore, the glass transition temperature of the mixture of acrylic resin and inorganic fine particles is -10°C or higher, and the glass transition temperature of the mixture coating film (after curing) of polyurethane resin, acrylic resin, and inorganic fine particles is 60°C or higher. ℃
The amount of the inorganic fine particles mixed is preferably 5 to 40 beads ff1% based on the total weight of the anionic group-containing polyurethane and the acrylic resin.

In addition, in order to improve the pot life of the liquid used to form the first layer or to obtain a desired thickness, the first layer may be coated with the above-mentioned solvent depending on the coating method and coating conditions. The solid content of the liquid used to form the layer is adjusted to tA, but it is approximately 1-40.
Preferably, it is %. , more preferably 5-3
It is 0% by weight.

The first layer is formed by applying a liquid material containing the above-mentioned components used to form the first layer to a polyester film and baking the resulting coating film at a temperature lower than the heat distortion temperature of the polyester film. can get. At that time, the film is subjected to alkali treatment, flame treatment, corona discharge treatment, plasma treatment, polishing, sandblasting, etc., as necessary.

The coating method may be the commonly used dipping method, spraying method, roller coating method, flow coating method, etc., and may be appropriately selected depending on the desired product for the polyester film.

The preferred thickness of the first layer obtained is 0.01-10 μm
, more preferably 0.05-5 μm.

If it is thinner than 0.05 μm, the adhesion will be reduced, and if it is thicker than 10 μm, there will be problems such as a decrease in the flexibility of the coating film or a cloudy coating.

Particle system 11-100n which is component a used in the present invention
The inorganic particles of m are S i 02, Al2O3, ZrO
2, T i 02, S b 205, S n 02, Y
b2O3, Yb2O3, Ta2O3, Y2O3, Ce2
It is a one-particle powder such as O3, or a colloidal solution in which these particles are dispersed in water or an organic solvent-based dispersion medium.

Examples of the silicon compound represented by the general formula (1) used in the present invention include the following.

Namely, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, vinyltriacetoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyljethoxysilane, γ-methacryloxypropyltrimethoxysilane , γ
-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane,
N-bis(β-hydroxyethyl)-γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ
-aminopropyl(methyl)dimethoxysilane, γ-
Mercabutobrovir trimethoxysilane, 3°3.3-
Examples include trifluoropropyltrimethoxysilane.

In the present invention, the partial hydrolyzate of one or more selected from the silicon compounds represented by the general formula (1) refers to the alkoxy group or alkoxyalkyl group in the silicon compound in which part or all of the alkoxy group or alkoxy alkyl group is substituted with a hydroxyl group. Contains some naturally condensed hydroxyl groups. These hydrolysates can be obtained by hydrolysis in a mixed solvent such as water and alcohol in the presence of an acid, as is known. When the silicon compound represented by the general formula (1) is used without being hydrolyzed, the cured coating film becomes white and the scratch resistance is also insufficient.

When using the silicon compound represented by the general formula (1) as a hydrolyzate, better results are often obtained by mixing and co-hydrolyzing the compounds simultaneously rather than by hydrolyzing them separately. Moreover, it is more preferable to hydrolyze in the coexistence of particles.

The liquid material used to form the second layer in the present invention contains a solid content of 1 to 70% by weight, and an a component of 1 to 80% by weight based on the total solid content; -9
It is preferable that 9% by weight of component b is contained, and in addition, it contains a solvent, a curing catalyst, and various additives if desired. More preferred ranges for component a and component b are 5-60% by weight and 40-95% by weight, respectively. Solvents that may be included in the composition for forming the second layer include monohydric or polyhydric alcohols, ketones, Nisdels, ethers, cellosolves, halides, carboxylic acids, and aromatic compounds. , ether alcohol, ketone alcohol, etc., and one or more of these can be used as a mixed solvent. In particular, lower alcohols such as methanol, ethanol, propatool, isopropanol, and butanol; cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and acetic acid cellosolve; lower alkyl carboxylic acids such as formic acid, acetic acid, and propionic acid; toluene, It is preferable to use aromatic compounds such as xylene; esters such as ethyl acetate and r/Fu butyl; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone alone or as a mixed solvent.

Curing catalysts include ammonium perchlorate, ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium thiocyanate, perchloric acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, sulfonic acid, paratoluenesulfonic acid, boron trifluoride, and its electron carrier. Complex with body; 5nC14, Zn
C11, FeCl3, AlCl3.5bC1s, T I
Lewis acids such as Cl a and their complexes; Organic acid metal salts such as sodium acetate, zinc naphthenate, cobalt naphthenate, zinc octylate, and tin octylate; Metal borofluoride salts such as zinc borofluoride and tin borofluoride; Boric acid organic esters such as ethyl borate, methyl borate, etc.;
Alkali such as sodium hydroxide and potassium hydroxide; titanate esters such as tetrabutoxytitanium and tetraisopropoxytitanium; chromium acetylacetonate, titanyl acetylacetonate, aluminum acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate Metal acetylacetonates such as n-butylamine, di-n-butylamine, tri-n-butylamine, guanidine, biguanide, imidazole, and other amines; ammonium trifluoromethylsulfonate, potassium trifluoromethylsulfonate, trifluoromethyl Highly fluorinated aliphatic sulfonates such as sodium sulfonate: NHa(CF3SO2)2c
Br, K(CF3SO2)CH,Ba[(CF3SO2
) Highly fluorinated aliphatic sulfonyl compounds such as 2CHco2,
Examples include ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and benzyltrimethylammonium hydroxide.

Among these curing catalysts, ammonium perchlorate, ammonium chloride, and Fa't are curing catalysts that have good coating film hardness and transparency, and have a good liquid pot life.
Perchlorates, hydrochlorides, sulfates, carboxylates, highly fluorinated fats represented by ammonium, ammonium nitrate, sodium acetate, ammonium trifluoromethylsulfonate and bis(trifluoromethylsulfonyl)bromomethylammonium Group sulfonates, ammonium hydroxides, and highly fluorinated aliphatic sulfonyl compounds are suitable.

As the curing catalyst used to form the second layer, one or more of the above-mentioned various curing catalysts may be used in combination, and the amounts of these curing catalysts added are as follows:
0.05-20% by weight, more preferably 0.1% by weight based on the solid content of the liquid used to form the second layer
-10% by weight.

Typical additives mixed into the liquid used to form the second layer are flow control agents, such as fluorine surfactants, alkylene oxides and dimethylsiloxane. Block copolymers and the like can be mentioned. A small amount of these flow control agents is sufficient, and 0.01% of the total liquid used to form the second layer is sufficient.
-5wt J1%, more preferably 0.03-3wt%. Further, small amounts of antioxidants, ultraviolet absorbers, etc. can also be added.

Coating methods for forming the second layer include the commonly used dipping method, flow coating method, barcoder method, doctor blade method, spraying method, reverse roll coater method, gravure roll coater method, etc. After coating the first layer on the polyester film, which has been coated and baked in advance, the first layer is cured by baking for 1 minute to 1 hour at 70°C or higher and below the deformation temperature of the base material to improve weather resistance, adhesion, and A coating film with excellent heat resistance and scratch resistance can be obtained.

The preferred thickness of the second layer is 1-30μ, more preferably 2-10μ. If it is less than 1μ, the scratch resistance will not be sufficient, and if it is more than 30μ, cracks will easily occur.

In addition to the above materials, materials having photochromic, electrochromic, or thermochromic properties may be mixed into the first and/or second layer.

According to the present invention, the anionic group-containing polyurethane resin, acrylic resin, and inorganic Since the first IZ containing the system fine particles has good adhesion to both the polyester film and the second layer, the first layer is an adhesion improving layer between the polyester film and the second layer. Furthermore, by coating and curing the first layer with a pre-formed product containing a specific silicone resin and inorganic particles as main components, it also acts as a layer for improving the scratch resistance of the polyester film.

Furthermore, the adhesion and scratch resistance are good even after a durability wipe test.

Furthermore, the first layer has excellent coefficient of friction, anti-blocking properties, etc., and has excellent winding properties of the film after coating.

<Examples> The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. In addition, parts and % in Examples indicate parts by weight and % by weight, respectively.

(1) Preparation of the liquid used to form the first layer; a) HYDRAN AP-20, an anionic group-containing polyester polyurethane resin (manufactured by Dainippon Ink and Chemicals Co., Ltd.: solid content: 30%) 33g and colloidal silica/acrylic composite particle emulsion 1? A certain VO
NCOAT DV-804 (Dainippon Ink Chemical Co., Ltd.'a
Co., Ltd.: solid content 31.3%, acrylic resin: 39 g of silica = 1:1), 100 g of distilled water, 20 g of isopropyl alcohol, and a small amount of anionic fluorosurfactant were mixed to prepare it.

b) 45 g of HYDRAN AP-40 (manufactured by Dainippon Ink & Chemicals Co., Ltd.: 22% solids), which is an anionic group-containing polyester polyurethane resin, and VONCO, which is a colloidal silica/acrylic composite particle emulsion.
AT DV-804 (manufactured by Dainippon Ink & Chemicals Co., Ltd.: solid content 31.3%, acrylic resin: silica = 1:
1) 20g, 130g of distilled water, and a small amount of anionic fluorine-based surfactant were mixed to prepare.

C) 30 g of anionic group-containing polyester polyurethane HYDRAN AP-20 (manufactured by Dainippon Ink & Chemicals Co., Ltd.: 30% solids) and colloidal silica/acrylic composite particle emulsion VO
NCOAT DV-759 (Dainippon Ink and Chemicals)
Co., Ltd.: solid content 40.8%, acrylic resin: silica = 1: ]) 30 g, m distilled water 150 g, and a small amount of anionic fluorine-based surfactant were mixed.

d) 60 g of HYDRAN AP-20 (Dainippon Ink & Chemicals Co., Ltd.!!: 30% solids) which is an anionic group-containing polyester polyurethane resin, 10 g of distilled water
0 g of isopropyl alcohol and 20 g of isopropyl alcohol and an anionic fluorine-based surfactant.

e) 100 g of HYDRAN AP-40, which is an anionic group-containing polyester polyurethane resin (manufactured by Dainippon Ink & Chemicals Co., Ltd.: 22% solids), 10 g of distilled water
0 g and a small amount of anionic fluorine-based surfactant were mixed.

f) 50 g of colloidal silica/acrylic composite particle emulsion VONCOAT DV-759 (manufactured by Dainippon Ink and Chemicals Co., Ltd.: solid content 40.8%, acrylic resin: silica = 1: 1), 150 g of distilled water and a small It was prepared by mixing a certain amount of anionic fluorosurfactant.

g) VONCOAT DV-804, a colloidal silica/acrylic composite particle emulsion (manufactured by Dainippon Ink & Chemicals Co., Ltd.: solid content 31.3%, acrylic resin: silica" 1:1) 40 g, distilled water 130 g and a small It was prepared by mixing a certain amount of anionic fluorosurfactant.

(2) W8 preparation of the liquid used to form the second layer; a) 1152 parts of colloidal silica (manufactured by Yasan Kagaku Kogyo Co., Ltd.; Snowtex C9 solid content 20%) and m3 of ice vinegar
4.6 parts of γ-glycidoxyprobyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.; KBM403)
A mixture of 813.3 parts and 701.5 parts of methyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. fi!; KBMI 3) was added dropwise, and after hydrolytic condensation, ethyl cellosolve 96
8.8 parts and a small amount of a flow control agent were added to prepare a stock solution. The solids content of this stock solution was 35%.

This stock solution contains CH2-CHCH20-C3H8-3i-0+, s\
17.5% of γ-glycidoxypropyltrimethoxysilane hydrolyzate, calculated as CHsSiO75, 10% of methyltrimethoxysilane hydrolyzate, calculated as CHsSiO75
．． 5% and 7% colloidal silica calculated as 5102.

The thus obtained ternary cohydrolyzate stock solution 714.
3 parts of ethyl cellosolve, 288.2 parts of ethyl cellosolve, and 2.5 parts of ammonium perchlorate were mixed to adjust the solid content to 25% to prepare a liquid material used to form the second layer.

b) 400 parts of colloidal silica (manufactured by Yasan Kagaku Kogyo Co., Ltd.; Snowtex C2 solid content 20%) and 24 parts of glacial acetic acid
γ-Glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.; KBM403) 664.8%
After hydrolytic condensation, 649.6 parts of methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.; KBMI3) was added dropwise and 687.8 parts of ethyl cellosolve and a small amount of a flow control agent were added to prepare a stock solution. . The solid content of this stock solution was 34.7%.

This stock solution contains CH2-CH-CH2-0-CzHs-3i -0+,
γ-glycidoxypropyltrimethoxysilane hydrolyzate 17.35% calculated as s\ 1 , CH35io+, s
It is believed to contain 13.88% methyltrimethoxysilane hydrolyzate calculated as SiO2 and 3.5% colloidal silica calculated as SiO2.

The ternary cohydrolyzate stock solution obtained in this manner 720.
5 parts, 1277 g B of ethyl semivine and 2.5 parts of ammonium perchlorate were mixed to adjust the solid content to 25%,
A liquid material used to form the second layer was prepared.

C) 320 parts of colloidal silica (8san Kagaku Kogyo Co., Ltd. i!; Snowtex C1 solid content 20%) and 2 parts of glacial acetic acid
3.4 parts of γ-glycidoxib a pyrutrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.; KBM403) 33
8.9 parts, methyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.)
A mixture of 974.3 parts of KBMI3) and 55.5 parts of tetraethoxysilane was added dropwise, and after hydrolytic condensation, 481 parts of ethyl cellosolve, 481 parts of isobutanol and a small amount of a flow control agent were added to adjust the stock solution to V4.

The solids content of this stock solution was 28.6%.

This stock solution contains CH2-CHCH2-0-C3H6-5i -0+, s
γ-Glycidoxypropyltrimethoxysilane hydrolyzate calculated as \ 1 8.58%, CH35iO+, methyltrimethoxysilane hydrolyzate calculated as s 1
7.16%, 2.288% colloidal silica calculated as 5IO2 and 0.572% tetraethoxysilane calculated as SiO2.

The thus obtained ternary cohydrolyzate stock solution 874.
1 part, 27.6 parts of ethyl cellosolve, 2 parts of isobutanol
7.6 parts of methanol, 13.8 parts of methanol, 55.2 parts of distilled water, and 1.75 parts of CHsCOON & 3 H2O are mixed to adjust the solids content to 25% and used to form the second layer. A liquid product was prepared.

(3) Preparation of evaluation sample; Pre-cleaned biaxially stretched polyester film (manufactured by Kaneni Co., Ltd.; Tetron, 0 type, film thickness 10)
The liquid material used to form the first layer adjusted above was applied to one side and dried in a hot air drying oven for 150 µm.
It was baked for 10 minutes at a temperature of 0.degree. C. to cure and form a first layer having a thickness of about 0.1 .mu.m.

Next, the liquid material used to form the second layer prepared above is applied onto the first layer, and dried in a hot air drying oven for 15 minutes.
Bake at 0°C for 10 minutes to harden to a thickness of approximately 2.5μm.
A second layer was formed to produce a polyester laminate.

Additionally, a first layer of polyester laminate and a second; Δ
A polyvinyl butyral film having a thickness of 0.761 nm In was sandwiched with the laminated surface facing outward to produce a laminated glass, which was used as an evaluation sample.

4) Performance evaluation of coating film; Scratch resistance: Scratch resistance was examined by rubbing with #0000 steel wool and judged as follows.

A: Even if it is strongly rubbed, it will not become biased.

B: Slight scratches occur when rubbed strongly.

C: Even weak friction creates bias.

Adhesion: In the so-called cross-cut tape test, 11 parallel lines were drawn vertically and horizontally at 1 mm intervals on the surface of the paint film, and 100 squares were cross-cut, and then cellophane adhesive tape was attached on top of the cross-cuts. The number of squares that did not peel off among 100 squares after peeling the tape was expressed.

Hot water resistance: The abrasion resistance and adhesion of the coating film after immersion in boiling water for 2 hours were examined. The sides of the laminated glass for evaluation were covered with aluminum tape to prevent water from entering the polyvinyl butyral film.

Weather resistance: In the so-called sunshine weather-o-meter test, the glass surface was irradiated with water at 63±3°C and water was showered for 12 minutes out of every hour.
The adhesion of the coating film after 1000 hours and the appearance of the coating film after 3000 hours, that is, cracks in the coating film, were evaluated.

(5) Evaluation Results Table 1-4 shows the combinations of the first layer and the second layer and the results.

Table 1 Table, 2 Initial performance Table, 3 Hot water resistance Table 4. Weatherability

Claims (1)

[Claims] 1. Formed by applying a liquid material containing an anionic group-containing polyurethane resin, an acrylic resin, and inorganic fine particles to the surface of a polyester film base material having a thickness of 10 μm to 500 μm, and curing it. A polyester laminate comprising a first layer and a second layer formed by coating and curing a liquid material containing an organic silane compound on the outside of the first layer in contact with the first layer. 2. The liquid material containing the organic silane compound has the following components a and b a; inorganic particles with a particle size of 1-100 nm b; general formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R^1 in the formula is an alkyl group, alkoxyalkyl group, or acetyl group having 1-6 carbon atoms, and R^2 is an alkyl group having 1-6 carbon atoms.
R^3 is a hydrocarbon group, or an organic group containing an epoxy group, (meth)acryloyl group, vinyl group, allyl group, mercapto group, halogen atom, amino group, ureido group, or amide group, n 2, 3 or 4, m is 0 or 1) The polyester laminate according to claim 1, which is a liquid material containing a mixture of partial hydrolysates of silicon compounds. 3. The liquid material containing the organic silane compound contains 1-70% by weight of solid components, and the component a is 1-80% by weight of the total solid content.
, the polyester laminate 4 according to claim 2, which contains 20 to 99% by weight of the component b; claim 1, wherein the polyester film base material is a biaxially oriented polyethylene terephthalate film.
Polyester laminate described in Section 1. 5. The silicon compound represented by the general formula (1) is tetraalkoxysilane, methyltrialkoxysilane or γ
-Glycidoxypropyltrialkoxysilane.The polyester laminate according to claim 2, which is glycidoxypropyltrialkoxysilane. 6. The polyester laminate according to claim 2, wherein the inorganic particles are colloidal silica. 7. The polyester laminate according to claim 1, wherein the liquid containing the organic silane compound used to form the second layer further contains perchlorate or sodium acetate. 8. The first layer has a thickness of 0.01-10 μm,
A polyester laminate according to claim 1, wherein said second layer has a thickness of 1-30 .mu.m. 9. The liquid material for forming the first layer contains anionic group-containing polyurethane and acrylic resin in a weight ratio of 1:9 to 3:1, and contains inorganic fine particles. The polyester laminate according to claim 1, which contains 5 to 40% by weight of the anionic group-containing polyurethane and the water-based acrylic resin. 10. The polyester laminate according to claim 8, wherein the inorganic fine particles are silica fine particles. 11. The polyester laminate according to claim 1, wherein the anionic group-containing polyurethane is an anionic group-containing polyester polyurethane.