JPS5913341B2 - laminated film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a laminated film with improved scratch resistance, abrasion resistance, flatness, weather resistance, and water resistance.

As is well known, the surface of the base material made of flexible organic polymers or organometallic polymers is soft.
It has the disadvantage that it is easily scratched, and its transparency and appearance deteriorate, so improvements are desired.

For this reason, properties such as mechanical and chemical properties of the surface have been improved by depositing, coating, or laminating glass, metal, or resin with high surface hardness on the surface of the base material. 10 Previously, we discovered a surface-curing paint with excellent scratch resistance that has an extremely hard layer mainly composed of silicon compounds laminated on the surface, but some types of flexible polymers do not exhibit adhesion and can be easily scratched. It often peels off.

15 The present inventors have conducted extensive research to solve these drawbacks.
As a result, we have arrived at the present invention, which is free from the above-mentioned drawbacks and is highly effective.

The present inventors have already proposed a treatment method in which a silicon-based compound is applied after applying a layer mainly composed of an epoxy resin and at least one of polyalkylene imine, polyalkylene amine, and polyamide resin. However, the present invention makes it possible to further improve quality, that is, weather resistance and water resistance, by using a specific epoxy resin.

25 The present invention improves the adhesion of a layer made of a silicon-based compound to a flexible organic polymer or organometallic polymer substrate, and improves scratch resistance, abrasion resistance, flatness, weather resistance, and water resistance. The purpose of the present invention is to provide a laminated film that satisfies the following requirements at the same time.

It is scratch resistant, does not curl or crack, and has excellent chemical, thermal, and optical properties, so it can be used as a base material for magnetic tapes, building materials, decorations, miscellaneous goods, and even plate-making. It can be used effectively for various purposes. By improving the special VC weather resistance and water resistance, it can be used indoors and outdoors where ultraviolet rays are exposed, such as when laminated with window glass, to exhibit remarkable effects in preventing glass from scattering and controlling sunlight. In the present invention, on at least one surface of a base material made of a flexible organic polymer or organometallic polymer solid, one part of dimer acid diglycidyl ester, a polyalkylene imine, a polyamide resin, and a compound having the general formula R'Si(0R)3 (R is an alkyl group having 1 to 6 carbon atoms, k is an organic group containing -NH2 or (} and) -NH-), at least one of aliphatic diamines, alicyclic diamines, and heterocyclic diamines A layer having 0.05 to 3 parts of
1 of the compound, where N and m are each an integer from O to 4, satisfying Cn+m=4.
It is a laminated film formed by laminating and combining composition layers containing a species or two or more kinds of hydrolysates as main components.

Preferred organic polymers or organometallic polymers constituting the base material include, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6 naphthalene dicarboxylate, polyethylene-1,2 diphenoxyethane-P,P' dicarboxylate. Polyester polymers such as esters, polyolefins such as polypropylene and polyethylene, polyamides such as so-called nylon-6 and nylon 12, polyimides having five-membered ring imide bonds in the polymer main chain, cellulose derivatives such as cellulose esters, polystyrene, polycarbonates, These include acrylic ester copolymers, methacrylic ester copolymers, polyvinyl chloride, polyether, polyester ether, copolymers with maleic acid or itaconic acid, and organometallic polymers crosslinked with metal ions. It also includes, but is not necessarily limited to, copolymers or blends.

Although these polymers can be used in an unstretched state, it is preferable to subject them to stretching force, particularly biaxial stretching, since this improves mechanical properties, thermal properties, optical properties, and dimensional stability.

Furthermore, these polymer films may be subjected to known surface treatments to improve adhesion as necessary, such as corona discharge treatment, corona large discharge treatment in an inert gas, flame treatment, reverse squirting treatment, electric charge treatment, etc. It is possible to perform a treatment using a flame loaded with , or to provide a surface modification layer. The epoxy resin used in the primer of the present invention has dimer acid diglycidyl ester as a main component.

Dimer acid has the general formula HOOC-R1COOH (Tatashi R
" is a dimer of unsaturated fatty acids represented by a hydrocarbon having 24 to 40 carbon atoms. Most preferably, linoleic acid dimer or linolenic acid dimer is used. The dimer content is at least 50%, preferably 6001) The above also includes those containing a small amount of trimer or monomer, or modified products. Dimer acid diglycidyl ester can be mixed with dimer acid in the presence of an amine catalyst such as a tertiary amine. After reacting with epichlorohydrin, this reaction product can be produced by dechlorination and dehydrogenation with caustic alkali.

It can also be produced by reacting an alkali salt of dimer acid with epichlorohydrin in the presence of a rogen catalyst. The modified dimer acid diglycidyl ester can be produced by mixing dimer acid diglycidyl ester and bisphenol A diglycidyl ether or by reacting it with bisphenol A glycidyl ether.

In the present invention, the main component is dimer acid diglycidyl ester, but other epoxy resins may be mixed and used within a range that does not impair the effects of the present invention.

Other components of the primer include polyalkyleneimine, polyamide resin, and the general formula R'Si(0R)3 (R is an alkyl group having 1 to 6 carbon atoms, and R' is -NH2 or (
Compounds represented by (organic group containing -NH-),
It is selected from at least one of polymeric aliphatic diamines, alicyclic diamines, and heterocyclic diamines.

Low-molecular amines, which are normally used as curing agents for epoxy resins, not only have a short lifespan and poor workability, but also have poor flexibility, adhesion, film strength, water resistance, and chemical resistance. This is undesirable because it has the fatal disadvantage of decreasing the scratch resistance and also causes the loss of the properties of the silicon compound, which has excellent scratch resistance. Examples of the present invention include polyamide resins obtained by reacting polyethylene imine, polypropylene imine, dimer acid or trimer acid with alkylene polyamines,
N-β(aminoethyl)γ-aminopropyltrimethoxysilane, r-aminopropyltriethoxysilane, and the like are preferably used. Also aliphatic or (mortal)
The alicyclic diamine can be selected from substances that cure epoxy resins by curing at room temperature, and those with a relatively large molecular weight, such as those with a carbon number of 5 or more, are preferable, and hexamethylene diamine, trimethylhexamethylene diamine, etc. are suitable. be. Furthermore, as a heterocyclic diamine or its modified product, 3,9bis(3aminopropyl)2,4,8,10
Tetraoxaspiro[5,5]undecane is one example, and modified products thereof can be obtained by reaction with monoepoxy compounds such as butyl glycidyl ether and other alkyl glycidyl ethers. The ratio of dimer acid diglycidyl ester and the composition is 1 to 0.05 for the former.
~3 parts are required.

If the amount of the former is increased more than this, not only will the adhesion between the substrate and the silicon compound decrease, but the adhesiveness will become too strong, which may lead to a significant decrease in workability. On the other hand, if the latter amount is increased more than this, weather resistance, water resistance, and chemical resistance may deteriorate, which may cause problems in use. The above primer layer is
If necessary, it is dissolved in a solvent together with other additives, applied by a conventional coating method such as a gravure method, an air knife method, a metal ring method, a reverse roll method, or a dipping method, and then dried.

Coating film thickness is 0.01μ to 5μ, preferably 0.05μ
A range of ~2μ is preferable. If the film thickness exceeds 5 μm, cracks are likely to occur in the silicon compound layer, which is undesirable. The general formula R/Si (
A compound containing -NH2 or NH- represented by 0R)3 is known as a primer for hard silicon compound coating, but when this substance alone is combined with a flexible base material, there is a strong tendency for cracks to occur; Water resistance is also insufficient, making it impractical.

Compositions of plastic base materials and hard silicone resin compounds that use acrylic resin as a primer are also known, but the base materials are limited to materials with low crystallinity such as polymethyl methacrylate and polycarbonate at the stage of practical use. However, when it contains a highly crystalline flexible substrate such as polyethylene terephthalate, it exhibits significantly inferior properties compared to the composition of the present invention. The construction according to the invention exhibits excellent adhesion and weather resistance on flexible substrates such as polyester, polyolefin, polyamide, etc., not achieved with the prior art.

It is also particularly useful in configurations that include flexible substrates made of polymeric substances that are known to be ineffective for bonding by so-called solvent bonding methods. The silicon compound layer used in the present invention has the general formula RnSiXm (R is an organic group in which carbon is directly bonded to silicon, including methyl, ethyl, propyl, butyl, vinyl, phenyl, methacryloxy, glycidoxy, merkabuto, amino, etc.); X is a halogen group,
One or two compounds represented by an alkoxy group (methoxy, ethoxy, propoxy, butoxy, etc. having 6 or less carbon atoms), N and m each being an integer from O to 4, and a value satisfying n+m-4) A curing catalyst, additives (e.g., adhesion promoter, antistatic agent, PH adjuster, wetting improver, plasticizer, stabilizer, antioxidant, ultraviolet absorber, etc. agent, lubricant,
Examples include compositions obtained by dissolving it in a solvent together with antifoaming agents, thickeners, coloring agents, etc., and curing it by heating or by radiation such as ultraviolet rays, β rays, and γ rays.

Of course, those precondensed in a solution state are also included. Among the silicon compounds represented by the general formula RnSiXml, particularly preferred are m=3 or (} and) m-
The compound is selected from one or more of the compounds consisting of 4.

When these compositions are laminated directly onto a base film, the adhesion to the base film is poor and the composition peels off, and there are also differences in properties from the K1 base film, such as creep properties, elongation, elastic recovery properties, and elastic stress. When people listen to music, a crack occurs,
It is useless because it curls and cannot maintain flatness.

By providing a primer layer containing dimer acid diglycidyl ester, the present invention can improve the above-mentioned disadvantages caused by using a flexible base material, without reducing the scratch resistance and abrasion resistance at all. It is possible to provide a laminated film that does not generate cracks and has flatness, chemical resistance, water resistance (including hot water resistance and moisture resistance), weather resistance, transparency, etc. at the same time. Also, as a modification of the composition of the present invention, a polymer layer can be provided between the primer layer and the silicon compound layer.

The polymer layer is preferably a material that has excellent weather resistance and does not exhibit stickiness at room temperature, such as a polymer or copolymer of methacrylic acid ester. Various additives such as known ultraviolet absorbers and colorants can be mixed into this polymer layer.
To summarize the features of the composition of the present invention explained above, the hard silicon compound coating layer is highly flexible and does not generate cracks due to bending action, and does not generate cracks even when exposed to hot water or light. That's true.

Cracks due to bending are affected not only by the performance of the hard coating layer itself but also by the adhesion to the substrate and the mechanical properties of the primer layer. In the composition of the present invention, the silicon compound coating layer has scratch resistance that can withstand steel wool abrasion, but does not cause cracks even when wound around a core having a diameter of 10 mm. Furthermore, cracks do not occur even when immersed in boiling water, accelerated weather resistance tests, or exposed outdoors. Another feature of the composition of the present invention is that it has excellent adhesive strength and weather resistance.

Regarding weather resistance, it is assumed that the resin itself has good weather resistance, but when using a flexible substrate, it is necessary to have good initial adhesion and to improve adhesion by UV irradiation and a wet-dry cycle with water. The most important thing is that there is no deterioration, and it has become possible to manufacture a laminated film with satisfactory performance only with the configuration specified in the present invention. For example, a composition in which an epoxy compound prepared from bisphenol A and epichlorohydrin is used in place of the dimer acid diglycidyl ester specified in the present invention exhibits a fraction or number of failures in accelerated weathering tests with water spraying. Zero adhesive tape, which does not lose its adhesive strength in a tenth of a short time, peels off without resistance in the peel test. Further, the composition of the present invention exhibits superior adhesion and weather resistance after a short drying time compared to known silicon compound coatings, and is useful as a manufacturing technique.

The thickness composition ratio of each layer of the base material, primer layer, and silicon compound layer is not particularly limited, but the ratio is, for example, 1:(1 to
1"6): Can be freely changed from (1 to 10-4).

Examples will be described below, but the invention should not be limited thereto.

Example 1 One side of a biaxially oriented polyethylene terephthalate film (for example, Toray Industries Ltd., manufactured by Kiki Co., Ltd., Lumira 1γ) with a thickness of 50 μm was
11 IC shows black 1 to 6 compositions of brimer (xylene/butanol = Z weight ratio.

5% solution) was applied so that the solid content coating amount was 0.2 g/7rI, and dried at 140° C. for 3 minutes.

Here, the epoxy resin is dimer acid diglycidyl ester obtained from linoleic acid dimer with an average molecular weight of 8501 and an epoxy equivalent of about 435, and the polyamide resin is a reaction product of dimer acid and polyamine, and the amine value is about 35.
0 (e.g. Fuji Kasei Kogyo (Kikusei Tomide 235)
It is. On top of this, methyltrimethoxysilane and butyl silicate (molar ratio 5:1) were respectively hydrolyzed with a hydrochloric acid solution, sodium acetate was added as a hardening agent, acetic acid was used as a stabilizer, and epoxy resin was added as an adhesion promoter. ,
Furthermore, the solid content coating amount of the liquid with added thickener is 39/
It was applied to a coating thickness of 7r1 and dried and cured at 140°C for 10 minutes.

The obtained performance was as shown in Table 1. The test method is as follows (the same applies to the following examples).

(1) Cracks: Check with naked eye.

(2) Adhesive strength: Apply zero adhesive tape firmly to the paint surface and peel it off in the direction of 18.

Judgment ○: The coating film does not peel off at all.

Δ... Separation area of the coating film is less than 50 (fl).

×: Peeling area of the coating film is 50% or more. (3) Hot water resistance: Shown as adhesive strength after immersion in boiling water (95°C or higher) for 1 hour. Judgment is based on adhesive strength.

(4) Steel wool abrasion test: Rub with #0000 steel wool to check for scratch resistance.

(5) Weather resistance: Evaluate performance after 200 hours of irradiation using a Sunshine Carbon Weatherometer. When the laminated film of Flat 3 was wound around a cylinder with the coated side facing outward, the outer diameter of the cylinder where cracks occurred was 6 m1, and no cracks were observed at all after 200 hours of irradiation using a weatherometer. Comparative Example 1 A primer consisting of the epoxy resin shown in Table 2 and the polyamide resin shown in Example 1 was coated on one side of an axially stretched polyethylene terephthalate film (for example, Lumira 1 manufactured by Toray Industries, Inc.) with a thickness of 50 μm. It was coated at a ratio of 0.39/I and dried at 140°C for 5 minutes.

A layer made of a silicon compound was provided on this soil in the same manner as in Example 1 to obtain a laminated film. The results obtained were as shown in Table 3. Example 2 One part (solid content) of an epoxy resin consisting of the dimer acid diglycidyl ester shown in Example 1 was added to one side of a biaxially stretched polyethylene terephthalate film (for example, Lumira 1 manufactured by Toray Mai) with a thickness of 75 μm. , a primer (putanol solution) consisting of 0.25 part (solid content) of polyethyleneimine with a molecular weight of approximately 70,000 was applied at a solid content coating amount of 0.19/Trl.
It was applied and dried at 1400C for 3 minutes.

A silicon compound layer was provided thereon in accordance with Example 1 to obtain a laminated film. There were no cracks, and the adhesive strength, hot water resistance, and steel wool abrasion test were good. Even after 200 hours of irradiation using a weatherometer, no deterioration in the performance was observed at all. Comparative Example 2 In Example 2, diethylenetriamine (0.05 part per 1 part of epoxy resin) was added in place of polyethyleneimine.
When using the primer, cracks were observed due to bending, and the pot life of the primer paint was short, making continuous coating extremely difficult, making it unusable.

Example 3 A biaxially stretched polyethylene terephthalate film (for example, Lumira 1 manufactured by Toray Industries, Inc.) with a thickness of 25 μm was wetted with tension (
After corona discharge treatment to make it 72dynσi or more (according to JISK-6768), Example 1 was applied to one side of the corona discharge treatment.
1 part (solid content) of an epoxy resin consisting of dimer acid diglycidyl ester shown in 3,9-bis(3-aminopropyl)2,4,8,10-tetraoxaspiro
5] Heterocyclic polyamine consisting of a butyl glycidyl ether modified product of undecane (e.g. Epomade BOOl manufactured by MAINOMOTO Co., Ltd.) 0.28 part (solid content) Fu-Yobi N-
A primer (xylene/butanol solution) consisting of 0.03 parts (solid content) of a hydrolyzate of β(aminoethyl)γ-aminopropyltrimethoxysilane was applied with a solid content coating amount of 0.
．． 2f! /m'' and dried at 140°C for 5 minutes.

A silicon compound layer was provided thereon in accordance with Example 1 to obtain a laminated film. No cracks were observed at the initial stage, after 6 months at room temperature, and after 200 hours of irradiation with a weatherometer, and the adhesive strength, hot water resistance, and steel wool abrasion test were all good.

Example 4 A methacrylic acid ester copolymer (methyl methacrylate/methyl acrylate = 90/10 weight ratio) was added between the primer layer and the silicon compound layer of the laminated film of Example 1 and 3 in a toluene/butyl acetate solution. As solid content coating amount 19/
m'' and dried at 140° C. for 1 minute.

The three-layer laminated film thus obtained was free from curls and cracks, had improved abrasion resistance, and had good weather resistance. The above methacrylic acid ester copolymer is applied directly to the base material without providing an epoxy resin-based brimer layer. In this case, the adhesion to the base material was poor and it could not be put to practical use. Example 5 Biaxially oriented polyethylene terephthalate J with a thickness of 38μ
Example 1 on one side of C Lum (Lumira 1 manufactured by Toray Industries, Inc.)
1 part (solid content) of an epoxy resin consisting of dimer acid diglycidyl ester shown in , and Nβ (aminoethyl)γ-
A primer (xylene/butanol solution) consisting of 0.14 parts (solid content) of aminopropyltrimethoxysilane was applied so that the solid content coating amount was 0.39/M2, and 1
It was dried at 40°C for 5 minutes.

On top of this, methyltrimethoxysilane and vinyltriethoxysilane (molar ratio 2:1) were hydrolyzed with a hydrochloric acid solution, and a curing agent, stabilizer, thickener, and adhesion promoter were added and blended. The solid content of the liquid applied was 2,59/T.
It was coated so that it was 140° C. and dried for 10 minutes at 140° C. to harden it. The obtained performance is shown in Table 4 together with comparative examples. The brimer compositions of Comparative Examples 3 and 4 are as follows.

Comparative Example 3: A methanol solution of N-β(aminoethino(c)γ-aminopropyltrimethoxysilane) was applied so that the solid content coating amount was 0.39/m″, and dried at 140 coating C for 5 minutes. .

Comparative Example 4: 1 part (solid content) of bisphenol A diglycidyl ether (epoxy equivalent weight 190) and 0.0 parts of N-β(aminoethyl)γ-aminopropyltrimethoxysilane.
A primer (xylene/butanol solution) consisting of 5 parts (solid content) was applied so that the solid content coating amount was 0.39/TIVζ, and dried at 14°C for 5 minutes.

In Comparative Examples 3 and 4, the initial performance reached a certain level, but cracks occurred and the adhesive strength significantly decreased over time and after the accelerated weather resistance test.

Example 6 A biaxially stretched polypropylene film with a thickness of 40 μm (for example, Torayuan BO manufactured by Toray Industries, Inc.) was wetted and subjected to tension (JIS).
K-6768) After corona discharge treatment to give 48 dyne/CTrL, one side of the film was coated according to Example 5 to obtain a laminated film.

The drying conditions were as follows: the primer layer was heated to 130° C. for 5 minutes, and the silicon compound layer was heated to 135° C. for 10 minutes. This laminated film had no cracks and had good adhesive strength, hot water resistance, and steel wool abrasion test.

Claims (1)

[Claims] 1. On at least one side of a base material made of a flexible organic polymer or organometallic polymer solid, 1 part of dimer acid diglycidyl ester, polyalkylene imine, polyamide resin, general formula R'Si(OR)_3 (however, R is an alkyl group having 1 to 6 carbon atoms, R' is -NH_2 or (and) an organic group containing -NH-), at least one kind of aliphatic diamine, alicyclic diamine, or heterocyclic diamine. A layer with the general formula R_nS_iX_m (wherein R is an organic group in which carbon is directly bonded to silicon, and X is a halogen group or an alkoxy group (having 6 or less carbon atoms ), n and m are integers from 0 to 4, respectively, and values that satisfy n+m=4)
A laminated film formed by laminating and combining composition layers whose main component is one or more hydrolysates of the compounds represented by the formula.