JPS62277440A - Polyester laminate - Google Patents

Abstract

PURPOSE:A laminate having improved wear resistance, adhesiveness, water resistance and weather resistance, obtained by forming a cured film containing a (meth)acrylic acid ester on the surface of a polyester transparent base material and making a cured film containing an organosilane compound of the cured film on the cured film. CONSTITUTION:A liquid material having a (meth)acrylic acid ester polymer containing an epoxy group in the molecule is applied to the surface of a transparent polyester base material having 10mum-500mum thickness and cured to form a first layer and further the outside of the first layer is coated with a liquid material containing an organosilane compound and the liquid material is cured to give a second layer. A mixture of inorganic particles having 1-200nm particle diameters and a partial hydrolyzate of a silicon compound shown by the formula (R<1> is 1-6C alkyl, etc.,; R<2> is 1-6C hydrocarbon; R<3> is epoxy group, etc.,; n is 2 or 3; m is 0 or 1) is used as the liquid material containing the organic silane compound.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention (Field of Industrial Application) The present invention is a method of coating the surface of a base material of a polyester film or sheet with a liquid substance that has good adhesion to the polyester film. A first layer is formed by curing, and a liquid material containing a silicon-based resin is coated and hardened on the first layer to form a second layer.
The present invention relates to a coated polyester resin film molded article having excellent abrasion resistance, adhesion, water resistance, and weather resistance.

<Prior art> In general, biaxially oriented polyester A-based resin films are widely used as transparent materials due to their excellent mechanical properties and transparency, but they lack abrasion resistance and are easily scratched on the surface. It has the following drawbacks. In order to improve these drawbacks, a method of coating with a thermosetting resin has been proposed.

For example, Tokko Showa 1.0-! ;3703 is a scratch-resistant laminate obtained by applying a polyester resin as an undercoat layer on a polyethylene terephthalate molded product, and coating and curing a topcoat containing a vinyl polymer mainly composed of melamine group-containing (meth)acrylate. is disclosed.

In addition, in Japanese Patent Publication No. 40-1T3J03, 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 then A wear-resistant laminate is disclosed, which is obtained by coating and curing a top coat containing a hydrolyzate of colloidal silica and an epoxy group-containing alkoxysilane as main components.

<Problems to be solved by the invention> However, the above-mentioned special public official Akiotsu 0-! ;3703 odor ℃
In addition, in Japanese Patent Publication No. 113303, there was a problem in that hardness decreased and adhesion was easily caused by immersion in boiling water.

Means for Solving the Problems> The present inventors have made extensive efforts to eliminate these drawbacks and provide a polyester resin molded article with improved abrasion resistance, adhesion, and water resistance. As a result of research, it has been found that the first layer is coated with a specific organic polymer to improve the adhesion of a composition mainly composed of silicon-based resin and inorganic particles to a polyester resin base material. It has been found that the abrasion resistance, water resistance, and weather resistance of polyester-based fat-saving laminates can be improved by coating and curing a composition containing inorganic particles as main components on a layer of olefin.

That is, the present invention provides an acrylic ester or methacrylic ester polymer containing an epoxy group in the molecule on the surface (at least one surface in the case of a sheet-like substrate) of a transparent polyester substrate having a thickness of 10 μm to 50 μm. A first layer formed by applying and curing a liquid material containing an organic silane compound, and a liquid material containing an organic silane compound, especially the following components a and b a; Particle particle /~1100n inorganic particle b General formula (
1) A polyester laminate having a layer of λ formed by applying and curing a liquid material containing a partial hydrolyzate of a silicon compound represented by the formula %.

Examples of the polyester transparent sheet having a thickness of 10 μmm to 50 It used in the present invention include saturated polyester sheets and films such as polyethylene terephthalate and polybutylene terephthalate.

The acrylic ester or methacrylic ester polymer containing an epoxy group in the molecule used in the present invention refers to a polymer of 1'acrylic ester or methacrylic ester containing an epoxy group in the molecule, or the ester as described below. It is a copolymer with an acrylic ester or a methacrylic ester represented by the general formula (2).

This copolymer preferably contains at least 1 mol %, more preferably at least 10 mol %, of a component derived from an acrylic ester and/or a methacrylic ester containing an epoxy group in its molecule.

Examples of acrylic esters or methacrylic esters containing an epoxy group in the molecule include glycidyl acrylate and glycidyl methacrylate. In addition, examples of acrylic esters or methacrylic esters represented by general formula (2) include (meth)
Acrylic acid, (meth)methyl acrylate, (meth)
Ethyl acrylate, propyl (meth)acrylate, (
Butyl meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, dicyclopentenyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate
Acrylate, butylene glyfur mono (meth)acrylate, glycerol mono (meth)acrylate,
polyethylene glycol mono(meth)acrylate,
Polypropylene glycol mono (meth)acrylate, r-(meth)acryloxypropyltrimethoxysilane, r-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, r-(meth)acrylic Roxypropylmethyljetoxysilane, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dibutylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminopropyl (meth)acrylate, dibutylaminopropyl (meth)acrylate ) acrylate, methacrylamide, methylol(meth)acrylamide, butoxymethyl(meth)acrylamide, and the like.

In the present invention, the liquid material used to form the above-mentioned olefin layer contains one or more kinds of acrylic ester or methacrylic ester polymers containing the above-mentioned epoxy group in the molecule, Furthermore, if desired, it contains one or more monopolymers or copolymers of acrylic esters or methacrylic esters represented by the general formula (2). This liquid contains at least 7% by weight of solids, and contains at least 0.01% by mole of a component derived from (meth)acrylic acid ester containing an epoxy group in the molecule, based on one unit of total Preferably, at least O0j mol% is contained. In addition to the above-mentioned components, a solvent and various additives are added as desired to form a liquid product.

Examples of solvents include altools such as methanol, ethanol, isofuropal, butanol, and diacetone alcohol-A; seven-cellosolves such as methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, and butyl cellosolve; ethyl acetate, butyl acetate, and ethylene glycol diacetate. , acetic acid esters such as ethyl cellosolve acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisopropyl ketone; and toluene, dichloromethane, etc., and these may be used as a mixture.

Examples of additives include flow control agents, ultraviolet absorbers, antioxidants, curing agents, and crosslinking agents. Examples of the flow agent include commercially available heptadonated surfactants, block copolymers of alkylene oxide and dimethyl siloxane, and the like. 1L, preferably 0~
It is 3% by weight.

As a UV absorber, 2-hydroxy-Hiro-methoxybenzophenone! -Hydroxy-g-octoxybenzophenone, 2. ≠-dihydroxybenzophenone, +
Benzo7enes such as 2,2/-dihydroxy-1l-methoxybenzophenone; 2-(2'-hydroxy-51-methylphenyl)benzotriazole, λ-(
21-hydroxy-51 phenyl)benzotriazole, 2-(2'-human a+cc t-butylphenyl)
Examples include benzotriazoles such as -5-chlorobenzotriazole; cyanoacrylates such as ethyl-2-cyano-3+37-diphenylacrylate.

These may be used alone or in combination of two or more,
O ~, based on 100 parts by weight of the total polymer in the liquid material used to form the first layer! 171) parts by weight are used.

As antioxidants, 2. O-G-tert-butyl-P-cresol, 2 or J-tert-butyl-Hiro-methoxyphenol, stearyl-β-<3. S-di-tert-butyl-ψ-hydroxyphenyl)propionate, j, 2/-methylenebis-(dermethyl-tert-butylphenol), u,ul-thiobis-(3-methyl-tert-butyl 7ethyl) ), ≠+ll-butylidene-bis(3-methyl-ot-
tert-butylphenol), ha/,! -Tris-
(+2-methyl-Hiro-hydroxy=!; -tert-
butylphenyl)butane, /, 3. j-) dimethyl-2
, ψ, tris(3,j-di-tert-butyl-hydroxybenzyl)benzene, tetrakis-[methylenej (3/, s/-di-tert-butyl-4/-human) roxyphenyl)propionate, methane, Dilauryl thiodipropionate, simyristylthio dipropionate, triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite,! , 4”-butylidene-bis-(3-methyl-ot-t
Examples include ert-butylphenyl-di-tridecyl) phosphite, tris (nonylphenyl) phosphite, etc., which may be used alone or in combination of two or more. 0 based on 100 parts by weight of the total polymer contained in the liquid material used
~Otsuo parts by weight Preferably 0 to 30 parts by weight are used.

Curing catalysts and crosslinking agents are not necessarily required. However, the organic solvent in the liquid used to form the second layer erodes the layer, resulting in a loss of adhesion between the second layer and the first layer, or between the transparent polyester sheet and the second layer. Adhesion with the first layer may be reduced. In order to prevent corrosion of the first layer and improve water resistance, it is preferable to include a curing catalyst and a crosslinking agent in the liquid material used to form the first layer. Further, by forming a crosslinked structure in the first layer, the water resistance of the laminate can be improved. Examples of the curing catalyst include hydrochloric acid, ammonium chloride, ammonium nitrate, ammonium thiocyanate, ammonium chlorate, dimethylaminopropylamine, etc., and the amount used is generally 0.03 to 10% by weight based on the resin solid content. It is appropriate to use it in proportion.

Examples of the crosslinking agent include various epoxy resins derived from bisphenols such as triglycidyl tris (2-hydroxyethyl) in cyanurate, resorcin diglycidyl ether, bisphenol A diglycidyl ether, and bisphenol S diglycidyl ether. The amount used is generally based on the solid content of the resin. ;
Oj! ! Suitably, it is used in a proportion of ffi%.

A liquid substance containing the above-mentioned components used to form the first layer is applied to a polyester transparent sheet, and the resulting coating film is baked at a temperature lower than the heat deformation temperature of the polyester transparent sheet. A layer of / is obtained. At that time, the film may be treated with alkali or
Electric discharge or plasma treatment, flame treatment, polishing or sandblasting treatment, etc. are performed.

Application methods include the commonly used dipping method, spraying method, roller coating method, and flow coating method.
It may be selected as appropriate depending on the desired product for the polyester transparent sheet.

The preferred thickness of the first layer obtained is 0.05 to 70 μm
, more preferably (7,j~j;ltm.0.0
If it is smaller than 5 μm, the adhesion will decrease, and if it is larger than 70 μm, the coating film may become cloudy or cracks may occur. Depending on the coating method and conditions, the solid content of the liquid used to form the tusk layer is adjusted using the above-mentioned solvent to obtain the desired thickness, but in order to form the first layer, The solid content of the liquid used for this is approximately 1~. 20
Weight%.

Particle size of component a used in the present invention/~11007
The inorganic particles at t are Sin. , AA? 203. Z
rO2°TiO2,5b2051Sn02. yb2o
3. yb2o5. Ta2O3゜Y2O3, Ce2O3
These include ultrafine particle powders such as, and colloidal solutions prepared by dispersing them 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. S7: Trimethylmethoxysilane, dimethyltrimethoxysilane, methyltrimethoxysilane, tetraethoxysilane,
Phenyltrimethoxysilane, phenylmethyldimethoxysilane, vinyltriethoxysilane, vinyltris(
β-methoxyethoxy)silane, vinyltriacetoxysilane, r-methacryloxypropyltrimethoxysilane, γ-amino/propyltriethoxysilane, N-(β
-aminoethyl)-r-aminopropyltrimethoxysilane, N-bis(β-hydroxyethyl)-γ-ami/
Propyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyl(methyl)dimethoxysilane,
r-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, 3,3. Examples include J-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 a partial hydrolyzate in which a part or all of the alkoxy group or alkyl group in the silicon compound is a hydroxyl group. It includes substituted hydroxyl groups and substituted hydroxyl groups that are partially naturally condensed. 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 in the art. If the silicon compound represented by the general formula (1) is used without being hydrolyzed, the cured coating will whiten and the abrasion resistance will be insufficient.
When using the silicon compound represented by the formula as a hydrolyzate, better results are often obtained by mixing and co-hydrolyzing the compounds at the same time than by hydrolyzing them separately. Moreover, it is more preferable to hydrolyze in the coexistence of particles.

In the present invention, the liquid material that is used to form the second layer contains a solid content of /~70% by weight, and 1~0% by weight of component a based on the total solid content. ．． ! (1
) -99mffi% of the oxidation component is preferably contained, and in addition, an organic solvent, a curing catalyst, and various additives are also contained if desired.

Solvents that may be included in the composition for forming the second layer include heptahydric or polyhydric alcohols, ketones,
Esters, ethers, cellosolves, halides, carboxylic acids, aromatic compounds, ether alcohols,
Examples include ketone alcohol, and one or more of these can be used as a mixed solvent. In particular, lower alcohols such as methanol, ethanol, propatool, impropatool, and butyl; cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; 1 lower alkyl carbons 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 butyl acetate; and ketones such as a7tone, 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, achlorine m, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, sulfonic acid, p-toluenesulfonic acid, boron trifluoride and its electron donor. Complex with; 5nc14.
'1n013. FeCl3, AIJO113+5
bc15. Lewis acids and their complexes such as 'ricl, organic acid metal salts such as sodium acetate, zinc naphthenate, cobalt naphthenate, zinc octylate, tin octylate; Gold heptadide m salts Boric acid organic esters such as ethyl diborate and methyl borate; Alkali such as sodium hydroxide and potassium hydroxide; Titanate esters such as tetrabutoxytitanium and tetraisopropoxytitanium; chromium acetylacetate Metal acetylacetonates such as nate, titanyl acetylacetonate, aluminum acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate: n-butylamine, di-n-butylamine, tri-n-butylamine, guanidine, biguanide, imidazole Highly fluorinated aliphatic sulfonates such as ammonium trifluoromethylsulfonate, potassium trifluoromethylsulfonate, sodium trifluoromethylsulfonate, NH, (CF
35o)O,Br,K(OFSo)O
Examples include highly fluorinated aliphatic sulfonyl compounds such as H, Ba (OF3So2)2Cl(]2.

Among these curing catalysts, ammonium perchlorate, ammonium chloride, ammonium sulfate, f[ammonium, sodium acetate, trifluoro Perchlorates, hydrochlorides, sulfates, carboxylates, highly fluorinated aliphatic sulfonates, and highly fluorinated aliphatic sulfonyls represented by ammonium methylsulfonate and bis(trifluoromethylsulfonyl)bromomethylammonium Compounds are suitable.

As the curing catalyst used to form the second layer, one or more of the various curing catalysts described above may be used in combination. The addition of these curing catalysts is
0.05 to 10 parts by weight, more preferably 0.05 to 10 parts by weight based on the solid content in the liquid material used to form the fang λ layer.
01 to 5% by weight.

Typical additives mixed into the liquid used to form the second layer are flow control agents, such as fluorosurfactants, alkylene oxides, and dimethylsiloxane. Examples include block copolymers. It is sufficient to add a small amount of these flow control agents, and the amount of the flow control agent to be added is 0.000% relative to the entire liquid material used to form the second layer.
0/~j% by weight, more preferably 0.03~3% by weight. Further, small amounts of antioxidants, ultraviolet absorbers, etc. can also be added.

Footing methods for forming the tooth layer include the commonly used dipping method, 70-coat method, barcoder method, doctor blade method, spraying method, etc.
70” after coating on the first layer of polyester transparent sheet substrate, which has been precoated and baked with a layer of
A coating film with excellent wear resistance, adhesion, heat resistance, and weather resistance can be obtained by curing the coating at temperatures above C and below the deformation temperature of the base material for j minutes to S hours.

The preferred thickness of the Oko layer is between 1 and 30 microns, more preferably between 3 and 75 microns. If it is less than 7 microns, the wear resistance will not be sufficient, and if it is more than 30 microns, cracks will easily occur.

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

Function> According to the present invention, the fang containing the acrylic ester or methacrylic ester polymer containing an epoxy group in the molecule between the transparent base material made of polyester and the second layer made of an organosilicon compound is provided. Since the layer has good adhesion to both the polyester transparent substrate and the second layer, the second layer has good adhesion between the polyester transparent sheet and the second layer. It acts as.

Furthermore, since the third layer contains an epoxy group, a crosslinked structure can be formed in the third layer when a curing catalyst is contained in the liquid material for forming the oxide layer. ,
In that case, the first layer also acts as a water-resistant and hot water-resistant layer of the laminate.

<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 the examples, part 1% means part by weight and 2% by weight, respectively.

In addition, the performance evaluation of the coating film was performed using the following method. That is, wear resistance. ooo The scratch resistance was examined by rubbing with steel wool and judged as follows.

A: When there is no damage even if there is strong friction. B: Slight scratches occur when rubbed strongly.

C: Even weak II rubbing causes scratches.

Adhesion: In the so-called cross-cut tape test, 100 squares were cross-cut by making 71 parallel lines vertically and horizontally at l-distances with a knife on the surface of the paint film, and cellophane adhesive tape was attached on top of the cross-cuts. After that, peel off the tape 'T: 1
The number of squares that did not peel off among 00 squares was indicated.

Hot water resistance: Abrasion resistance of the coating film after 7 hours of immersion in boiling water,
Adhesion was investigated.

The liquid materials used to form the first layer and the second layer were prepared as follows.

(1) Preparation of liquid material used to form the first layer.

a) 70 parts of glycidyl methacrylate! -30 parts of hydroxyethyl methacrylate, 2 parts of ethyl cellosolve
A mixture of 30 parts of azobisisobutyronitrile and 1 part of azobisisobutyronitrile was stirred at 90'C for a period of time to copolymerize under a nitrogen atmosphere. Thereafter, 7 parts of 10 parts of ethyl cellosolve solution with a small amount of dimethylaminopropylamine and a small amount of a flow control agent were added to form the liquid used to form the first layer.

b) 5o parts of glycidyl methacrylate, jO parts of -monohydroxyethyl methacrylate, ethyl cellosolve, 23
0 parts, azobisisobutyronitrile 0. The ≠ part of the mixture was stirred at 90° C. for t hours under a nitrogen atmosphere to copolymerize. Thereafter, 70,911.7 parts of an ethyl cellosolve solution containing a small amount of dimethylaminopropylamine and a small amount of a flow control agent were added to obtain a liquid material used to form the first layer.

C) A copolymer of glycidyl methacrylate and 2-hydroxyethyl methacrylate was synthesized in the same manner as in a).

Also, dimethylaminoethyl methacrylate! A mixture of 9j parts of -1-hydroxyethyl methacrylate, 230 parts of ethyl cellosolve, and 0ψ parts of azobisisobutyronitrile was stirred at 90 DEG C. for an hour under a nitrogen atmosphere to copolymerize.

Then, the glycidyl methacrylate synthesized above and 2
70 parts of an ethyl cellosolve solution containing a copolymer of - and dodooxyethyl methacrylate, an ethyl heptarosol solution containing a copolymer of dimethylaminoethyl methacrylate and 2-hydroxyethyl methacrylate synthesized above tIs
1 part, tlt part of ethyl heptarosolve solution to which a small amount of flow control agent was added were mixed to form a liquid material used to form the first 1.

d) 70 parts of methyl methacrylate, 30 parts of non-hydroxyethyl methacrylate, ethyl cellosolve qOO
A mixture of 1 part and 3 parts of azobisisobutyronitrile O was stirred at 90'C for 1 hour under a nitrogen atmosphere to copolymerize. Thereafter, gtq parts of ethyl heptarosolve solution to which a small amount of flow control agent was added were mixed to form a liquid material used to form the first layer.

e) A copolymer of dimethylamine ethyl methacrylate and 2-hydroxyethyl methacrylate was synthesized in the same manner as in C). Thereafter, 3 parts of ethyl cellosolve solution tag to which a small amount of a flow control agent was added was mixed to form a liquid material used to form a layer of olefin.

(2) Preparation of the liquid used to form the second layer; a) γ-glycidoxypropyltrimethoxysilane 51<4.17 parts, colloidal silica (Nippon Kagaku Kogyo Co., Ltd.)
Made by Snowtex C1 (solid content 20%) to 3! ;, 2f
jM, and/, -N-hydrochloric acid! − Mix 〇 parts, ! ℃
After refluxing for 5 hours at
Wet out at °C. The resulting solution contained .psi.% r-glycidoxypropyltrimethoxysilane hydrolyzate, calculated as 8102, and IO% colloidal silica, calculated as 8102.

To a hydrolyzed M solution of r-glycidoxypropyltrimethoxysilane containing colloidal silica thus obtained/≠0 parts, ethyl cellosolve/≠9 parts, ammonium perchlorate 0. 7 parts, a small amount of a flow control agent was added to form a liquid material for forming a second layer.

b) γ-Glycidoxyprobyltrimethoxysilane iai part, methyltrimethoxysilane/73 parts, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtex C1 solid content 20%) -0 parts and O0/normal salt ugliness Aqueous solution/9
Mix 0 parts and 1. Hydrolysis was carried out by refluxing at ro-♂j°C for 2 hours.

The resulting solution was r-glycidoxypropyltrimethoxysilane hydrolyzate calculated as 15.3%, methyltrimethoxysilane calculated as CH3S101.5, 2%, and colloidal silica calculated as 5102 Otsu, /
It contained %.

f9 Add 0.37 parts of ammonium perchlorate, a small amount of 7-fu control agent, and ψ part of ethyl cellosolve to the thus obtained ternary co-hydrolysis solution to form a second layer. It was made into a liquid product.

C) 60 parts of γ-glycidoxypropyltrimethoxysilane, 73 parts of methyltrimethoxysilane, colloidal silica (manufactured by Nichikagaku Kogyo ■, Snowtex C1 solid content - 20%) 7! 1 part and 0 parts of normal acetic acid aqueous solution/0 parts were mixed and refluxed at ♂0 to t5°C for a period of time to perform hydrolysis.

The resulting solution was r-glycidoxypropyltrimethoxysilane hydrolyzate r,%%, 0H3SiO, calculated as methyltrimethoxysilane hydrolyzate, calculated as 77
．． Colloidal silica calculated as 3% and 51022. It included %.

In the thus obtained ternary cohydrolyzate solution, 41 parts of ethyl cellosolve and ammonium perchlorate O0 were added.
! parts, ammonium chloride 095 parts, sodium acetate 83 parts
A small amount of a flow control agent was added to obtain a liquid material for forming a second layer.

In advance, the liquid material used to form the first layer prepared above was coated on one side of a washed polyester transparent sheet (Toshishikikiki Lumirror film thickness/25 μrrL), and then dried at 730°C in a hot air drying oven. It was baked for 1j minutes to harden it to form a layer of about 0.7 μm thick.

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.
A polyethylene terephthalate laminate was prepared by baking and curing at 0° C.

Table 1 shows the combinations of the first layer and the O layer and the results.

table/ Table 1 Pecking

Claims (1)

[Claims] 1. By applying a liquid material containing a (meth)acrylic acid ester polymer containing an epoxy group in the molecule to the surface of a transparent polyester base material having a thickness of 10 μm to 500 μm, and curing it. A second layer formed by applying a liquid material containing an organic silane compound to the formed first layer and the outside of the first layer in contact with the first layer and curing the liquid material.
A polyester laminate comprising each layer of . 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 to 200 nm b; general formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [R^1 in the formula is an alkyl group or alkoxyalkyl group having 1 to 6 carbon atoms, R^2 is a hydrocarbon group having 1 to 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 is 2 or 3, m The polyester laminate according to claim 1, which is a mixture of partial hydrolysates of silicon compounds represented by 0 or 1. 3. The liquid material containing the organosilane compound contains 1 to 70% by weight of solid components, and 1 to 8% of the component a is expressed as a solid component based on the total solid content.
2. The polyester laminate according to claim 1, wherein the polyester laminate contains 20 to 99% by weight of component b. 4. The polyester laminate according to claim 1, wherein the polyester transparent substrate is made of polyethylene terephthalate. 5. Claim 2, wherein the silicon compound represented by the general formula (1) is methyltrialkoxysilane and/or γ-glycidoxypropyltrialkoxysilane.
Polyester laminate described in Section 1. 6. The polyester laminate according to claim 2, wherein the inorganic fine particles are colloidal silica. 7. The polyester laminate according to claim 1, wherein the liquid material applied to form the second layer contains perchlorate or sodium acetate. 8. The first layer has a thickness of 0.05 to 10 μm,
The polyester laminate according to claim 1, wherein the second layer has a thickness of 1 to 30 μm. 9. The polyester laminate according to claim 1, wherein the liquid material containing the (meth)acrylic acid ester polymer containing an epoxy group in the molecule further contains a curing catalyst and a crosslinking agent.