JPS5835145B2 - laminated film - Google Patents

Description

[Detailed description of the invention] The invention is scratch resistant, wear resistant and flexible.

The present invention provides a laminated film with improved chemical resistance, weather resistance, water resistance, and good flatness.

As has been well known, the surface of flexible organic polymer solids has a soft surface and is easily scratched, resulting in poor transparency and appearance, making it difficult to improve.

For this reason, the 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.

Previously, we discovered a surface-curing paint based on silicon compounds that is extremely hard and has excellent scratch resistance, but depending on the type of flexible polymer, it may not exhibit adhesive properties and peel off easily. many.

Methods of using epoxy resin, acrylic resin, aminosilane resin, etc. as the primer 2 for hard silicon compound coating have already been proposed, but hard silicon compounds have poor flexibility, flatness, pot life, and take a long time to cure. The drawbacks are that it takes time, and the adhesion and weather resistance and water resistance are insufficient, and there is a strong desire for improvement when using a base material made of a flexible polymer solid.

As a result of intensive research aimed at solving these drawbacks, the present inventors have arrived at the present invention, which is extremely effective.

The present invention improves adhesion when using a silicon compound with extremely excellent flexibility and flatness, and provides scratch-resistant buttons and abrasion resistance, as well as weather resistance, water resistance, chemical resistance,
The present invention provides a laminated film with excellent productivity and processability that satisfies stain resistance at the same time.

It is hard to scratch, does not curl or crack, and can be supplied continuously if necessary, making it extremely easy to work with.
Moreover, it is excellent thermally and optically, so it can be used effectively for various purposes.

By improving weather resistance and water resistance, it can be used for indoor and outdoor applications exposed to ultraviolet rays, such as when bonded to window glass to prevent glass from scattering and to control sunlight.

An example of its use is the following button.

Magnetic cards, magnetic tapes, magnetic disks, copy machine master belts or photosensitive drums, labels for construction materials and vehicles (
glass lamination, synthetic resin plate lamination, steel plate lamination, etc.)
For decoration, for miscellaneous goods (adhesive tape, etc.), for packaging, for printing/plate making, for protecting metals or metal compounds, etc.

In the present invention, on at least one surface of a base material made of a flexible organic polymer solid, (4) a monoethylenically unsaturated monomer containing a hydroxyl group (
(B) a monoethylenically unsaturated monomer containing a partial ester group of phosphoric acid (preferably 0.01 to 5 weight)
and (C) another ethylenically unsaturated monomer that can be copolymerized with these, and a primer layer of a composition consisting of a vinyl copolymer (I) consisting of and a polyisocyanate compound (2) is provided. It is a laminated film formed by laminating and integrating a layer made of a silicon compound thereon.

Preferred organic polymer films constituting the base material made of flexible organic polymer solids include, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene-2
, 6 naphthalene dicarboxylate, polyethylene-1
, 2-diphenoxyethane-P, polyester polymers such as P' dicarboxylate, polyolefins such as polypropylene and polyethylene, polyamides such as so-called nylon-6 and nylon-12, and five-membered ring imide bonds in the polymer main chain. Metals with polyimides, cellulose derivatives such as cellulose esters, polystyrene, polycarbonates, acrylic ester copolymers, methacrylic ester copolymers, polyvinyl chloride, polyethers, polyester ethers, copolymers with maleic acid or itaconic acid Organometallic polymers cross-linked by ions, etc.
It also includes copolymers or blends of these, but is not necessarily limited thereto.

Although these polymer films can be used in a single unstretched state, stretching, particularly biaxial stretching, improves mechanical properties, thermal properties, and dimensional stability, which is preferable.

Furthermore, these polymer films may be subjected to known surface treatments to improve adhesion, if necessary, such as corona discharge treatment, corona discharge treatment in an inert gas, flame treatment, reverse sputtering treatment, flame treatment loaded with an electrical charge, etc. It is possible to carry out a treatment such as by oxidation, or to provide a surface modification layer.

The thickness of the film layer is not particularly specified, but is, for example, 6μ to
A range of 500μ is desirable.

When it becomes thinner, workability becomes inferior.

Usually, 9μ to 200μ can be conveniently used.

The primer layer of the present invention is made of a vinyl polyol resin containing a partial ester group of phosphoric acid and a polyisocyanate compound.

That is, (4) a monoethylenically unsaturated monomer containing a hydroxyl group (preferably 4 to 70% by weight), and (B) 'J
a monoethylenically unsaturated monomer (preferably 0.01 to 5 weight ratio) containing a partial ester group of phosphoric acid, and (C) another ethylenically unsaturated monomer that can be copolymerized with these. This is a composition consisting of a vinyl copolymer (I) consisting of a polyisocyanate compound (I) and a polyisocyanate compound (I).

To further explain the above composition, if the amount of (4) is less than 4 monomers, it becomes difficult to react with isocyanate groups, that is, to form urethane bonds.

Moreover, if (B) exceeds 5 monomers, the pot life will be shortened when mixed with polyisocyanate, and insoluble matter will be produced, which is not preferable.

0. If the amount is less than '01 monomer, the catalytic effect of the urethanization reaction will decrease, and the reaction will require a considerable amount of time, and furthermore, the weather resistant adhesiveness will decrease when combined with the silicon compound layer of the present invention. It is coming.

Among the monoethylenically unsaturated monomers that can be used in the present invention,
(4) Those containing hydroxyl groups include β-hydroxyethyl acrylate, β-hydroxypropyl acrylate, β-hydroxybutyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl methacrylate, β-hydroxybutyl methacrylate, glycerin and trimethylol. Monoesters of propane etc. and acrylic acid, similar esters of methacrylic acid, N-methylolacrylamide, N-methylolmethacrylamide, and monoethylenically unsaturated compounds containing such hydroxyl groups.

(B) Examples of compounds containing a partial ester group of IJ acid include the following compounds.

(However, in the formula, R1 represents hydrogen or a methyl group, R2 represents an alkylene group such as an ethylene group or a propylene group, or a halogenated alkyl group such as a chlorobrene group, and R3 represents a hydroxyl group or a rogen atom such as chlorine or bromine.

) Examples include mono(2-hydroxyethyl acrylate) acid phosphate, mono(2-hydroxyethyl methacrylate) acid phosphate, mono(3-
Examples include chloro-2-hydroxypropyl methacrylate) acid phosphate.

Among the monoethylenically unsaturated monomers, (0 (4) above,
Monomers that can be copolymerized with the monomer (B) include, for example, esters of acrylic acid or methacrylic acid having a side chain having 1 to 15 carbon atoms, or vinyl acetate, vinyl chloride, acrylonitrile, methacrylate, or styrene. , vinyltoluene, α-methylstyrene, etc.

The polyisocyanate compounds to be mixed with the vinyl copolymer include aliphatic polyisocyanates (eg, hexamethylene diisocyanate, lysine diisocyanate, 2,2,4-)limethylhexamethylene diisocyanate, and the like.

) and its reaction derivatives with water-containing polyalcohols (for example, adducts of 3 moles of hexamethylene diisocyanate and water, adducts of hexamethylene diisocyanate and trimethylolpropane, etc.).

), alicyclic polyisocyanates (e.g. isophorone diisocyanate, 3-isocyanatomethyl, 3.5
,5-)! J Methyl cyclohexyl isocyanate, 1
, 3-bis(incyanatemethyl)cyclohexane,
4,4-methylenebiscyclohexyl isocyanate,
Methyl cyclohexylene diisocyanate etc.) and its adduct with polyalcohol containing water, or xylylene diisocyanate and its adduct with polyalcohol containing water, etc. Also, aromatic polyisocyanate (
Examples include tolylene diisocyanate (tolylene diisocyanate) and its adducts with polyalcohols containing water.

Further, various derivatives containing an average of two or more incyanate groups in the molecule of the above compound can also be included.

In the present invention, doluol, quijirole,
Use butyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, etc. as a polymerization initiator, add benzoyl peroxide for a peroxide catalyst, or add azobisisobutyronitrile for an azo catalyst, and heat at an appropriate temperature. The mixture is heated under the conditions for 3 to 15 hours, and the reaction is carried out at a level that gives a high polymerization rate.

If necessary, dilute with a solvent to obtain an appropriate viscosity and non-volatile content.

A urethane resin paint can be produced by mixing the above-mentioned polyisocyanate compound or its derivative, or a cellulose derivative, epoxy resin, or polyester can be added to the above-produced material as a modifier. A resin coating for a primer can be produced by mixing resins, amine resins, etc., and the above-mentioned polyinsyanate or its derivatives.

Compositions of a plastic base material and a hard silicone resin compound using acrylic resin as a primer have also been proposed;
The base material is limited to materials with low crystallinity, such as polymethyl methacrylate, which have a crystallinity of less than 20 at the stage of practical use, and highly crystalline materials such as polyethylene terephthalate, which have a crystallinity of 20 or more. When combined with flexible substrates, they exhibit significantly inferior properties compared to the compositions of the present invention.

The structure according to the invention includes polyester, polyolefin,
It exhibits excellent adhesive properties and weather resistance that have not been achieved with known techniques on flexible substrates such as polyamide.

It is particularly useful for structures containing flexible substrates made of polymeric materials, such as polyesters, polyolefins, etc., which are known to be ineffective for adhesion by so-called solvent bonding methods.

The above-mentioned primer layer is diluted with a solvent together with other organic polymer resins and additives as necessary, and applied using a conventional coating method such as a gravure method, an air knife method, a metering bar method, etc.
It is applied by reverse roll method, dipping method, spray method, etc. and then dried.

The coating thickness is not particularly specified, but it is 0.01μ to 5μ, preferably 1
The preferred range is 0.05μ to 2μ.

If the film thickness is increased, the adhesion with the silicon compound layer will decrease and cracks will be more likely to occur, which is not preferable.

The silicon compound used in the present invention has the general formula % An organic group in which carbon is directly bonded to silicon, including thyl, alkyl halide, vinyl, phenyl, methacryloxy, glycidoxy, mercapto, amino, etc., where X is a halogen group, alkoxy group (methoxy, ethoxy, propoxy, butoxy, methoxy-ethoxy, etc. with 6 or less carbon atoms) or acyloxy group, n and m are each integers,
The main component is a prepolymer obtained by hydrolyzing one or more residues of a compound represented by m = 3 or (a value that satisfies m - and) m - 4, n + m = 4). , curing agents, curing catalysts, additives (e.g. adhesion promoters, antistatic agents, pH adjusters, wetting improvers, plasticizers, stabilizers, antioxidants, ultraviolet absorbers, lubricants, antifoaming agents) as necessary. , thickeners, colorants, etc.), or dissolved in a solvent to adjust the concentration and viscosity, and then cured by heating or radiation such as ultraviolet rays, β rays, and γ rays. It is.

In the case of two or more types, they may be hydrolyzed individually and then mixed, or two or more types may be mixed and then hydrolyzed.

Of course, it also includes those that have been precondensed in the form of a solution.

Among these, m=3, m-3$-, and m=4 are preferably selected and used.

Other silicon compounds (for example, γ-glycidoxypropylalkyldialkoxysilane, dialkyldialkoxysilane,
It is also permissible to blend hydrolyzable bifunctional compounds such as diaryldialkoxysilane and alkylaryldialkoxysilane or their hydrolysates) or organic polymer resins.

Here, from the viewpoint of wear resistance and durability, the blending amount is desirably less than 500 parts by weight.

The flexibility and curl resistance (flatness) of the silicon compound layer can be further improved by using the following composition as a main component:
It is particularly preferable as a material constituting the layer.

(2) A composition comprising a compound containing an epoxy group, a silanol group, and/or a siloxane group in the molecule, and an aluminum specific compound curing agent.

(2) A composition comprising a mixture of two or more selected from the compound (2) above, a compound containing a silanol group and/or a siloxane group, a button, and an epoxy compound, and an aluminum specific compound curing agent.

The above aluminum specific compound curing agent has the general formula kl-YI.
ZC3-1) (Y is -OR'(R' is lower alkyl) or halogen, and -OR' is particularly preferred.

Z is a β-diketone compound, a β-ketoester compound, or a residue of a β-ketoester compound.

l is 0.1 or 2.

), for example, acetylacetone aluminum salt, aluminum dialkoxide monoalkyl acetoacetate, etc. are preferably used.

It is also possible to use a mixture of two or more of these.

The amount of the aluminum specific compound curing agent added is 0.0001 to 1 part by weight of the compound in (1) or the mixture in (2) above.
0.5 parts by weight, particularly preferably 0.005 to 0.1 parts by weight, is suitable; less than this will result in insufficient curing, while more than this will reduce the transparency of the coating film or resin. This results in defects such as deterioration.

The thickness of the silicon compound layer is not particularly specified, but may be, for example, 0.
．． The range of 5μ to 30μ is 9 cases.

If it is too thin, the abrasion resistance will not be sufficient, and if it exceeds 30 μm, the curing time will be longer, the flatness will be lowered, and cracks will occur, which is not desirable.

As a means for coating such a layer, a commonly used coating method can be easily used as in the case of the primer layer.

When these compositions are laminated directly onto a base film, the adhesion to the base film is poor and peeling occurs, as well as differences in properties from the base film, such as creep property, elongation, elastic recovery, and elastic stress. Large cracks may occur,
Curling occurs and it becomes difficult to maintain flatness, which is of no use.

By providing a primer layer made of a vinyl polyol resin containing a partial ester group of phosphoric acid and a polyisocyanate compound, the present invention can improve the drawbacks caused by using the flexible base material and has scratch resistance. sex,
No reduction in wear resistance, no cracking, flexibility, flatness, chemical resistance, stain resistance, water resistance (
It is possible to provide a laminated film that simultaneously provides properties such as heat resistance (including hot water resistance and moisture resistance), weather resistance, and transparency.

As a variant of the composition of the present invention, a polymeric 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.

One of the features of the composition of the present invention explained above is that the hard silicon compound coating layer is highly flexible, does not generate cracks due to bending action, and does not generate cracks even when exposed to hot water or light. Don't do it.

Cracks caused by bending are affected not only by the properties of the hard coating layer itself but also by its adhesion to the base material and the mechanical properties of the primer layer.

In the composition of the present invention, although the silicon compound coating layer has abrasion resistance that can withstand steel wool abrasion, no cracks occur even when it is wound around a cylinder with a diameter of 10 mm.

It also does not crack when immersed in boiling water, accelerated weathering 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 base material, 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 decline in
It has become possible to manufacture a laminated film with satisfactory performance using the configuration specified in the present invention.

For example, when the monoethylenically unsaturated monomer containing a partial ester group of phosphoric acid is removed from the primer composition of the present invention, the primer composition of the present invention can be used for an accelerated weathering test with water spray in a few minutes or several minutes. It does not lose its adhesive strength in a tenth of a minute and can be peeled off without resistance in a cellophane adhesive tape peel test.

Another feature of the present invention is that dyeability can be imparted by selecting a silicon compound.

Furthermore, the composition of the present invention provides superior performance through short drying and curing processes compared to known silicon compound coatings, and is useful as a manufacturing technology.

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

The numbers of copies and buns in the examples are by weight unless otherwise specified.

Example 1 The paint used for the primer layer was prepared as follows.

The above composition was reacted at 85°C for 5 hours.

The viscosity of the resulting reaction product was 20-50 poise.

100 parts of the above reaction product was added with ``dismodule N-7''.
5" (manufactured by Bayer, 75 multi-solution of hexamethylene diisocyanate trimer) was added, mixed well, and diluted with toluene/butyl acetate - 1/1 to prepare a 10φ nonvolatile content primer paint. .

Example 2 Example 1 (1
) with a solid content coating amount of 0.3 g/m'
It was coated so as to have the following properties, dried and cured at 1400C for 3 minutes, and then rolled up.

On top of this, methyltrimethoxysilane and butylsilicate (molar ratio 5:1) were respectively hydrolyzed with an aqueous hydrochloric acid solution, sodium acetate was added as a hardening agent, acetic acid was added as a cheap agent, and epoxy was added as an adhesion promoter. A liquid containing a resin, a thickener, and a wetting improver was applied using a roll coater so that the solid content was 3 g/m.
It was dried and cured at 140° C. for 3 minutes to obtain a laminated film with good flatness.

The obtained performance was as shown in Table-1.

The button test method is as follows.

(The following examples and comparative examples are the same.

) (1) Visually inspect the appearance for optical non-uniformity, cracks and other defects.

(2) Rub with abrasion-resistant steel wool #0000 to check for scratch resistance.

The judgment was made as follows.

A...It won't get scratched even if it is rubbed strongly.

B... If you rub it quite strongly, it will get a little scratched.

C: Even weak friction causes damage.

(3) Adhesive strength Strongly attach cellophane adhesive tape to the coating surface and
Peel off sharply in the direction.

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

Δ: Peeling area of paint film is less than 50%.

×: Peeling area of paint film is 50 or more.

(4) Hot water resistance Shown as adhesive strength after being immersed in boiling water (95°C or higher) for 1 hour.

Judgment is based on adhesive strength. (5) Immerse the sample in a chemical-resistant chemical and measure the time at 1 when an abnormality occurs.

(Room temperature: 20 to 25°C) (6) Evaluate performance after 200 hours of irradiation using a weather resistant sunshine carbon weatherometer.

Judgment is based on adhesive strength.

When the laminated film of the present invention was wound around a cylinder with the coated surface facing outward, the outside diameter of the cylinder at which cracks occurred was 6 mm, and it had excellent flexibility.

Furthermore, no cracks were observed after 200 hours of weather-off exposure.

The stain resistance against marker ink and lipstick was also good.

Example 3 In Example 2, a laminated film was produced according to Example 2 using the primer prepared in Example] (2).

The obtained performance was as shown in Table 1, and the same results as in Example 2 were obtained.

Comparative Example 1 Example 1 (3
) with a solid content coating amount of 0.3 g/m2
The film was coated so as to have the following properties, dried and cured at 140°C for 3 minutes, and then rolled up.

A silicon compound layer was provided thereon in accordance with Example 2 to obtain a laminated film.

The performance was as shown in Table-1. Comparative Example 2 A laminated film was obtained in the same manner as in Comparative Example 1, except that the primer prepared in Example 1 (4) was used instead.

The performance was as shown in Table-1.

Comparative Example] Although the initial performance of both No. 2 and No. 2 reached a certain level, the adhesive strength significantly decreased in oral and weather resistance accelerated tests, making them unusable.

Example 4 A primer layer was provided on one side of a 25μ thick biaxially oriented polyethylene terephthalate film (Toshiba Co., Ltd.) in accordance with Example 2, and then γ-glycidoxypropylene was added on top of the primer layer. To 100 parts of the hydrolyzate obtained by hydrolyzing biltrimethoxylan with an aqueous O,O]N hydrochloric acid solution, 20 parts of ``Dinacol EX-314'' (an epoxy compound manufactured by Nagashio Sangyo ■) and 5 parts of acetylacetone aluminum salt were added. Then, a paint containing a methacrylic acid ester copolymer as an adhesion promoter, a solvent, and a 2 part 1 mixture of isopropyl alcohol/n-butyl alcohol was added and mixed with a roll so that the solid content coating amount was 3 g/m. It was coated using a coater, dried and cured at 140'C for 2 minutes, and then continuously wound up.

The workability was excellent, and the flatness and flexibility were extremely good.

When it was wrapped around a cylinder with the coated side facing outward, no cracks were observed even though the cylinder had an outer diameter of 3m7n.

There were no practical problems with abrasion resistance, adhesion, and chemical resistance.

Example 5 A laminated film was obtained according to Example 4 using a silicon compound obtained by adding 20 parts of a hydrolyzate of γ-glycidoxypropylmethyljethoxysilane in an aqueous solution of hydrochloric acid to the silicon compound of Example 4. .

The silicon compound layer of the laminated film is coated with disperse dye sapphire.
When immersed in a dye bath consisting of a 3% aqueous solution of Flu 4G (manufactured by Ciba Geigi) for 10 minutes under SO'C, a laminated film having a good uniform dyed layer was obtained.

No decrease in wear resistance was observed.

Example 6 Biaxially oriented polypropylene film with a thickness of 40μ
Wet tension (JIS K-67
68) After corona discharge treatment to give 48 dyne/CmK, one side of the film was coated in accordance with Example 3 to obtain a laminated film.

The drying conditions were as follows: the primer layer was heated at 1300° C. for 5 minutes, and the silicon compound layer was heated at 135° C. for 10 minutes.

This laminated film has no cracks and has strong adhesive strength.
Hot water resistance and steel wool abrasion tests were good.

Claims (1)

[Scope of Claims] 1. On at least one surface of a flexible organic polymer solid substrate, (4) a monoethylenically unsaturated monomer containing a hydroxyl group; and (1) a partial ester group of phosphoric acid. A vinyl copolymer (I) consisting of a monoethylenically unsaturated monomer contained therein, and another ethylenically unsaturated monomer that can be copolymerized with these, and a polyisocyanate compound (2). A laminated film formed by providing a layer of a composition consisting of the above, and then laminating and integrating a layer consisting of a silicon compound thereon.