JPS5925673Y2 - Laminated film for transfer - Google Patents

Description

[Detailed Description of the Invention] The present invention provides a transfer laminated film with good flatness and a protective film with improved scratch resistance and abrasion resistance.

In order to improve the abrasion resistance of substrates or products that have traditionally been prone to scratches, glass, metal, or resin with high surface hardness is deposited or coated on the surface to improve the mechanical and chemical properties of the surface. is being done.

However, in the case of rigid base materials, productivity and workability may decrease, and when applied to products, the range of use may vary depending on processability or processing conditions, such as the effects of heat and radiation during drying and curing. However, there was a strong desire for improvement.

This invention solves these problems and improves productivity and
It is possible to provide a new transfer laminated film that has excellent processability and has a protective layer that satisfies scratch resistance, abrasion resistance, weather resistance, water resistance, chemical resistance, and stain resistance at the same time.

It has good flatness and can be continuously fed, so it has extremely good workability, and it is also excellent in thermal and optical properties, so it can be effectively used as a protective film for various purposes.

An example of the application is as follows.

Magnetic cards, magnetic tapes, magnetic disks, various silver salts and diazonium, pre-imaged films such as electrophotography, microfilm jackets, optical masks, copying machine master belts or photosensitive drums, labels, synthetic resin substrates (
Polymethyl methacrylate-1~, polycarbonate), A
BS resin, etc.), building materials, vehicles, decorations (displays, stamping foils, etc.), miscellaneous goods, packaging, printing,
For use in plate making, protection of gold layers or metal compounds, etc.

Examples of the cross-sectional configuration of the present invention are shown in Figures 1 and 2.
As shown in Fig. 3, the base film layer A is basically made of a flexible organic polymer solid, the silicon compound layer B,
This is a transfer laminated film in which the heat-sensitive or pressure-sensitive adhesive layers C are laminated in the order of ABC.

In Figure 1, C is a heat-sensitive adhesive layer, C in Figure 2 is a pressure-sensitive adhesive layer, D is a release material such as release paper, C is a pressure-sensitive adhesive layer in Figure 3, and D is a release agent. It is a layer.

Preferred organic polymer films constituting the base film layer A made of a flexible organic polymer solid include, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6 naphthanone dicarboxylate, and polyethylene-1,2 enoxyethane. Polyester polymers such as p and p' dicarboxylate, polyolefins such as polypropylene and polyethylene, polyamides such as so-called nylon 6 and nylon 12, polyimides having a five-membered ring imide bond in the polymer main chain, and cellulose derivatives such as cellulose esters. , polystyrene, polycarbonate, acrylic ester copolymer, methacrylic ester copolymer, polyvinyl chloride, polyether, polyester ether, etc., and also includes copolymers or blends of these, but is not necessarily limited to these. .

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

The thickness of the film layer A is not particularly specified, but is, for example, 6 μm.
A range of ~200μ is desirable.

The thinner the material, the lower the workability, and the thicker the material, the higher the cost.

Generally, 12μ to 100μ can be particularly preferably used.

A major object of the present invention is to provide a layer B made of a silicon compound and expose the layer B to the surface after transfer to form a protective film, improve wear resistance, and provide substantial durability.

The silicon compound layer B used in the present invention has the general formula % an organic group in which carbon is directly bonded to silicon, including alkyl halides, vinyl, phenyl, methacryloxy, glycidoxy, mercapto, etc., X is a halogen group, an alkoxy group ( methoxy, ethoxy, propoquine, butoxy, methoxy-ethoxy, etc.) or acyloxy group, n and m are each integers, m = 3 or m = 3 and m = 4, n + m =
The main component is a prepolymer obtained by hydrolyzing one or more of the compounds shown in Table 4), and if necessary, a curing agent, a curing catalyst, and an additive (
For example, it is mixed with adhesion promoters, antistatic agents, PH adjusters, wetting improvers, plasticizers, stabilizers, antioxidants, ultraviolet absorbers, lubricants, antifoaming agents, thickeners, colorants, etc. Alternatively, dissolve it in a solvent and heat it, or use ultraviolet rays, beta rays,
It is a composition obtained by curing with radiation such as gamma rays.

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, those precondensed in a solution state are also included.

When m=4 alone, the flatness is impaired and cracks are likely to occur, which is not preferable.

In addition, other silicon compounds such as γ-glycidoxypropylmethyldiakoxysilane, dialkyldialkoxysilane, diaryldialkoxysilane,
It is also permissible to use a hydrolyzable bifunctional compound represented by alkylaryldialkoxysilane or a hydrolyzate thereof) or an organic polymer resin.

The flexibility, dyeability, and curl resistance of the eight layers can be further improved by using the following composition, which is particularly preferred as a constituent of the eight layers.

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

The aluminum specific compound curing agent has the general formula Al-Yl.
Z3-1 [Y is 1OR'(R' is lower alkyl) or halogen, and -0R' is particularly preferred.

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

■ is 0. 1 or 2], and 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 thickness of the eight layers is not particularly specified, but is, for example, 0.5μ to 3μ.
A range of 0μ is desirable.

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 preferable.

The heat-sensitive or pressure-sensitive adhesive layer C and the release layer of the present invention are not particularly limited, and may be appropriately selected from those commonly used.

The C or D layer may be provided by any method such as thermal melting, application of an organic solvent solution, aqueous solution, or water dispersion, or lamination of a film-like coating.

When a heat-sensitive adhesive layer is provided even in the zero layer, a release layer D may be provided, but it is usually not necessary.

(Figure 1) However, when providing a pressure-sensitive adhesive layer, a release layer is required (Figures 2 and 3), and the transfer laminated film with this structure can be manufactured continuously, and Since it can be used by continuously transferring and pasting onto other base materials or products, significant labor savings and cost reductions are possible.

Examples of the adhesive layer C include saturated polyester resin, unsaturated polyester resin, alkyd resin, phenol resin, urea resin, melamine resin, epoxy resin, urethane resin, vinyl resin, acrylic resin, polyolefin (polyethylene, polypropylene, etc.). ), natural resins (e.g. pine resin, dammar, terpene resin, coumaron indene resin, natural rubber), water-soluble resins (e.g. polyvinyl alcohol, methylcellulose polyethyleneimine), synthetic rubbers, etc., and copolymers or blends of these resins. It may be a thing.

Whether these adhesives are heat-sensitive or pressure-sensitive depends on the degree of polymerization, copolymerization requirements, blending requirements, additive requirements, etc., and the key is whether they have fluidity under normal usage conditions. Those shown are pressure-sensitive adhesives, and those that are non-flowing under the conditions of use but become fluid when thermal energy is applied are generally used as heat-sensitive adhesives.

For example, adhesives with a high degree of aggregation are in a solidified state under normal use conditions, but become fluid when heated, and are therefore commonly referred to as heat-sensitive adhesives.

On the other hand, those with a low degree of polymerization are used as pressure-sensitive adhesives.

Additives (for example, antistatic agents, antioxidants, ultraviolet absorbers, adhesion promoters, wetting improvers, plasticizers, lubricants, thickeners, colorants, etc.) can be added to such adhesives as appropriate.

The thickness of the adhesive layer C is preferably 100 μm or less, preferably 50 μm or less, so that the effect of the structure of the present invention can be fully exhibited.

When it gets thicker, it takes more time to apply and dry it, which causes problems in workability.

Another reason why it is desirable to have a thin adhesive layer is that the wear-resistant coating is more effective when there are fewer intervening soft layers.

Examples of the release layer include silicone resin (trifunctional silicone release agent mainly composed of polymethylsiloxane, nitrocellulose, water-soluble cellulose ether, metal soap, fatty acid amide, petroleum resin, etc.).

A release agent may be directly attached as a release layer, or a release material attached to a paper or plastic substrate may be used.

In the layered film for transfer of the present invention, a release layer can be provided between the base film layer A and the silicon compound layer B, if necessary.

Furthermore, surface treatments (e.g., corona discharge treatment, corona discharge treatment in an inert gas, flame treatment, reverse sputtering treatment, treatment with charged flame, etc.) are applied between each layer to improve adhesion. A surface modification layer may be provided, and a colored layer, vapor deposited layer, printed layer, etc. may be provided if necessary.

By applying the surface treatment to the silicon compound layer B in particular,
The adhesion between silicon compound layer B and adhesive layer C is further strengthened,
Improves the durability of the laminate after transfer.

Coloring is possible by adding a coloring agent to the coating material or installing a new colored layer as shown above, but another feature of the present invention is that dyeability can be imparted by selecting a silicon compound. .

Staining may be performed before or after transfer.

The method of using the present invention will be explained with reference to FIG.

After the transfer laminated film (2) produced by continuous winding is bonded under pressure to a substrate E requiring a protective layer, the base film layer A is peeled off to obtain a film (2) having a protective layer B.

The substrate E may be a flexible sheet or a hard plate.

Appropriate modifications and variations are within the scope of the present invention.

For example, it also includes a composition in which a colored layer and a metal vapor deposition layer are provided between the silicon compound layer B and the adhesive layer C to create a stamping foil, and a pattern is transferred using a mold.

In this way, productivity, workability, abrasion resistance, durability, weather resistance,
A laminated film for transfer is obtained which has a new structure that has excellent stain resistance and allows dyeability to be imparted to the silicon compound layer if necessary.

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

Example 1 A release agent layer made of a silicone resin was applied to both sides of a biaxially stretched polyethylene terephthalate film ("Lumirror" manufactured by Toshiku Co., Ltd.) having a thickness of 38 μm, with a solid distribution amount of 0.
3 g/m2, then 0.01 N of γ-glycidoxypropyltrimethoxysilane was placed on one side.
To 100 parts by weight of the hydrolyzate obtained by hydrolysis with an aqueous hydrochloric acid solution, 20 parts by weight of Venacol EX-314 (an epoxy compound manufactured by Nagashio Sangyo), 4 parts by weight of acetylacetone aluminum salt, and isopropyl alcohol/as a solvent. A paint containing 120 parts by weight of n-butyl alcohol-2/1 (weight ratio) mixture was applied at a solid content of 3 g/m2, and dried and cured at 140°C for 3 minutes. .

After providing an adhesion promoting layer made of N-β (aminochel) r-aminopropyltrimethoxysilane on the layer,
A pressure-sensitive adhesive layer having a thickness of 5 μm made of an acrylic ester copolymer was provided, and a laminated film for transfer with good flatness was obtained by winding.

After applying pressure to the laminated film to the surface of an imaged silver salt optical mask and a magnetic card having a polyester film as a base, the polyethylene terephthalate film is peeled off and the silicon compound layer is applied onto the silver salt and magnetic coating film. It was established in

It had good abrasion resistance, no scratches occurred even when rubbed with steel wool #0000, and no deterioration in appearance was observed at all.

There were no practical problems with respect to transparency, optical uniformity, and durability.

Comparative Example 1 The complex salt optical mask and magnetic card in which no silicon compound layer was provided in Example 1 had poor abrasion resistance and were scratched even when lightly rubbed with #0000 steel wool.

After repeated use, the appearance deteriorated significantly and it became unusable.

When a printed circuit pattern was printed on a silver salt optical mask in close contact with a copper-clad printed circuit board, the number of uncorrected uses was 10 times or less, whereas the optical mask with the protective layer of Example 1 of the present invention has been used uncensored over 100 times.

Example 2 In Example 1, the silicon compound layer was obtained by hydrolyzing methyltrimethoxysilane and butyl silicate (molar ratio 5:1), respectively, with a hydrochloric acid solution, sodium acetate was added as a hardening agent, and sodium acetate was added as a stabilizer. A liquid containing acetic acid, an epoxy resin as an adhesion promoter, and a thickener was applied to a solid content of 4 g/m.
It was dried and cured at 0°C for 15 minutes to obtain a transfer laminated film.

Similar results as in Example 1 were obtained.

Example 3 The silicon compound layer of Example 1 was immersed in a dye bath consisting of a 5% by weight aqueous solution of disperse dye Sapphire Blue 4G (manufactured by Ciba-Geigi Co., Ltd.) at 80°C for 110 minutes.
A transfer laminated film having a uniform dyed layer was obtained.

Example 4 A biaxially stretched polypropylene film (“Trefazo BO” manufactured by Toshiku Co., Ltd.) with a thickness of 40μ was wetted with tension (JISK-6
768) After corona discharge treatment to 40 dyne/cm, a silicon compound layer was provided according to Example 1, and then a layer of saturated polyester resin was applied via an adhesion promoting layer mainly composed of epoxy resin. A heat-sensitive adhesive layer was provided and the film was wound up.

The obtained transfer laminated film was bonded to a polymethyl methacrylate casting plate having a thickness of 2 mm by heat-pressure bonding, and then the polypropylene film was peeled off.

The polymethyl methacrylate I plate having the protective layer had excellent abrasion resistance, no scratches, and no deterioration in aesthetic appearance was observed.

Adhesion and water resistance also showed satisfactory results.

The wear resistance of polymethyl methacrylate plates without a protective layer was significantly poor.

Example 5 A mymine compound layer obtained by adding 20 parts by weight of a hydrolyzate of γ-glycidoxypropylmethyljethoxysilane in an aqueous solution of hydrochloric acid to the silicon compound of Example 1 was dyed according to Example 3. As a result, a laminated transfer film having a thick and uniform dyed layer was obtained.

[Brief explanation of the drawing]

FIG. 1, FIG. 2, and FIG. 3 schematically show the cross-sectional structure of the laminated film for transfer according to the present invention. FIG. 4 shows a typical example of how to use the transfer laminated film. A... Flexible organic polymer film layer, B... Silicon compound layer, C... Heat-sensitive or pressure-sensitive adhesive layer, D...
・Release layer, E...Substrate for protective layer installation.

Claims (1)

[Scope of utility model registration request] Each layer of the base film layer A made of a flexible organic polymer solid, the silicon compound layer B, and the heat-sensitive or pressure-sensitive adhesive layer C,
A laminated film for transfer that is laminated in the order of A-B-C.