JP2003295769A - Thin film self-adhesive sheet for producing marking sheet, thin film marking sheet, and marking sheet-stuck article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thin marking sheet which sheet which has physical properties durable to an applying condition of a resin protective layer provided after adhesion and which is excellent in flexibility, heat resistance and gas permeability, and to provide a thin film self-adhesive sheet for producing the same. <P>SOLUTION: The thin film self-adhesive sheet of this invention has constitution that an adhesive layer 2 of 5 to 25 μm film thickness is laminated on one surface of a base material 1 which has 5 to 30 μm film thickness and is made of nonstretched film of polyurethane resin of polyester series or polycarbonate series having 80 to 190°C softening point. Further, a decorative display layer is provided on another surface of the base material of the thin film self-adhesive sheet to produce the thin film marking sheet. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a marking sheet used for decoration, an adhesive sheet for producing the marking sheet, and an article to which the marking sheet is attached. In particular, markings for design (decoration) of articles requiring a top (over) coat (articles that form a transparent or translucent protective layer continuously from the marking sheet attached to the outer surface to the surface of the adhered article), The present invention relates to a thin film marking sheet useful for legal plates, caution labels, etc.

[0002]

2. Description of the Related Art There are various types of articles whose surface is protected by a transparent or translucent resin layer after the articles are colored, marked, or decorated with a label or the like. For example, automobiles, motorcycles, bicycles, There are various products such as fishing rods, golf clubs, tennis rackets, sports equipment such as surfboards, and other synthetic resin molded products. In these articles, in order to form the transparent or translucent resin layer that is the protective layer, acrylic-melamine-based, acrylic-epoxy-based, two-component urethane-based paints are generally used as the physical properties of the article and the environment in which it is used. Is appropriately selected and used by By the way, in these articles, the marking member used for decoration is required to have physical properties capable of withstanding the coating conditions of these protective layers.

In recent years, from the viewpoint of solvent regulation, there is a tendency to thin the protective layer in order to reduce the amount of solvent used. However, when the above-mentioned protective layer is provided on the marking material after the marking material is attached, if the marking material has a thickness, the thickness of the protective layer is sufficient to cover the step between the marking material and the article to be adhered due to the thickness. Will be needed. Therefore, in order to reduce the thickness of the protective layer, it is necessary to reduce the thickness of the marking material as well.

Further, in order to reduce the thickness of these protective layers, it is required that the surface strength of the protective layer does not decrease. Therefore, the resin constituting the protective layer should be one having a higher hardness than before by curing. As a result, the internal stress during curing increases. As a result, there is a problem that the marking member is affected and the marking material itself is cracked, or the protective layer at the edge portion of the marking material is cracked. Further, there is a problem that the marking material is required to have higher heat resistance so as to withstand heating during curing of the protective layer. Further, there is a problem that the marking material swells due to the outgas generated from the adhered article. Furthermore, the adhesive used for sticking the marking material may be discolored by the outgas generated from the adherend, but if the marking material has a transparent portion, the discoloration can be easily seen through the protective layer, This causes visual problems. In particular, in the case of white and light-colored adherends, discoloration of the pressure-sensitive adhesive is a serious problem.

Conventionally, in the marking materials used in the above-mentioned applications, various films such as a stretched polyester film, a hard, semi-hard or soft vinyl chloride resin film, a polyurethane resin film, etc. are used as the substrate on which the adhesive layer is provided. It is used. However, the marking materials using these films have not been able to sufficiently cope with the above problems. For example, stretched polyester and rigid vinyl chloride have poor gas permeability,
In particular, when the film is made thin, there is a problem in that the gas that is locally accumulated causes swelling, resulting in poor appearance and that the coating film has high hardness and cracks are likely to occur. Also,
When a vinyl chloride resin film as described in JP-A-62-240372 is used, it is excellent in curved surface followability and gas permeability, but it is brittle when the article is placed at a low temperature. There is a problem that it is easy to improve the quality and cracks occur. Further, when the protective layer is applied as an overcoat layer and cured (baked at high temperature), the pressure-sensitive adhesive layer provided on the base material is discolored by the generated outgas. Further, a marking material using a certain type of non-stretching, non-yellowing type polyurethane film is tough and hard to crack, has flexibility even at low temperature, is not easily embrittled, and has good gas permeability, but is particularly filled. In transparent applications where agents and anti-blocking agents are not used, surface tack remains and it is difficult to form a thin film. Further, it is softened by heat during baking of a coating and cannot be used for this application. Furthermore, since it has a very good gas permeability, it will penetrate the adhesive when it is attached to an adherend such as an acrylic-melamine resin paint used for body painting of automobiles that generates reactive gas during baking. There is a problem that the amount of the generated gas is large, and the pressure sensitive adhesive is discolored by the reactive gas in a shorter time.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems in the prior art, and an object of the present invention is to apply the resin protective layer under the following coating conditions. Another object of the present invention is to provide a thin marking sheet having physical properties capable of withstanding, and having excellent flexibility, heat resistance, and gas permeability. Another object of the present invention is to provide a thin film pressure sensitive adhesive sheet for producing the above thin film marking sheet. Still another object of the present invention is to provide an article having a protective layer formed by sticking the above-mentioned thin film marking sheet.

[0007]

The thin film pressure-sensitive adhesive sheet of the present invention is for producing a marking sheet and has a softening point of 8
A film thickness of an unstretched film of a polyester-based or polycarbonate-based polyurethane resin at 0 to 190 ° C. 5
It is characterized in that a pressure-sensitive adhesive layer having a film thickness of 5 to 25 μm is laminated on one surface of a base material having a thickness of ˜30 μm.

The first aspect of the thin film marking sheet of the present invention is produced by using the above-mentioned thin film pressure-sensitive adhesive sheet and comprises a polyester or polycarbonate polyurethane resin having a softening point of 80 to 190 ° C. A pressure-sensitive adhesive layer having a thickness of 5 to 25 μm is laminated on one surface of a base material made of an unstretched film having a thickness of 5 to 30 μm, and the other surface of the base material is
A decorative display layer is provided. In the second embodiment, a film having a softening point of 80 to 190 ° C., which is a non-stretched film of a polyester-based or polycarbonate-based polyurethane resin and having a thickness of 5 to 30 μm, is formed on one surface of a base material via a decorative display layer. The pressure-sensitive adhesive layer having a thickness of 5 to 25 μm is laminated.

In the marking sheet-adhered article of the present invention, the above-mentioned thin film marking sheet is adhered to the surface of an adherend article, and a transparent or semitransparent protective layer is formed over the surface of the adherend article including the thin film marking sheet. It is characterized by

In the present invention, the above thin film adhesive sheet,
The adhesive layer in the thin film marking sheet and the article to which the marking sheet is attached has an acrylic copolymer having a carboxyl group in the side chain and an average molecular weight of 100,000 to 1,000,000, two or more epoxy groups and a third. It is preferable that a resin composition having a gel fraction of 20 to 90%, which is crosslinked with a polyglycidylamine having one or more primary nitrogen atoms, is used as a main component.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described below with reference to the drawings. FIG. 1 is a schematic cross-sectional view of a thin film pressure-sensitive adhesive sheet for producing a marking sheet of the present invention. In FIG.
The pressure-sensitive adhesive layer 2 is provided on one surface of the base material 1, and the release paper 3 is temporarily attached to the surface thereof to form the thin film pressure-sensitive adhesive sheet for producing a marking sheet of the present invention.

2 to 4 are schematic cross-sectional views of the thin film marking sheet according to the first aspect of the present invention. In FIG. 2, the decorative display layer 4 is provided on the other surface of the base material 1 of the thin film pressure-sensitive adhesive sheet shown in FIG. 1 to form the thin film marking sheet of the first aspect of the present invention. In addition, in FIG.
A light-transmitting protective layer 5 is formed on the surface of the decorative display layer 4 of FIG. Further, FIG. 4 shows a case where two different decorative display layers, for example, the printing ink layer 4a and the foil pattern forming layer 4b are provided on the other surface of the base material 1.

FIG. 5 is a schematic sectional view of the marking sheet according to the second embodiment of the present invention. In FIG. 5, the base material 1
The pressure-sensitive adhesive layer 2 is provided on one surface of the base material via the decorative display layer 4, and the light-transmitting protective layer 5 is provided on the other surface of the base material.

FIG. 6 is a schematic sectional view of the marking sheet-adhered article of the present invention, in which the thin film marking sheet 10 of the present invention is adhered to the article A to be adhered, and the transparent resin protective layer 6 is provided. Is provided on the surface of the article to be adhered so that the entire thin film marking sheet attached is covered.

Next, each layer constituting the thin film pressure-sensitive adhesive sheet and the thin film marking sheet of the present invention will be described. The base material 1 is made of an unstretched film of a polyester-based or polycarbonate-based polyurethane resin having a softening point of 80 to 190 ° C. Specific examples of the polyester-based or polycarbonate-based polyurethane resin include a bifunctional long-chain polyol composed of a polyester polyol or a polycarbonate polyol having a molecular weight of 400 to 8000 forming a soft segment, and a short-chain glycol forming a hard segment. Those having a linear structure composed of three components, i.e., diisocyanate, are preferably used. Due to the agglomeration of hard segments, this polyurethane exhibits tough physical properties like a crosslinked polymer even in a non-crosslinked linear urethane resin.

Examples of long-chain polyols of polyester urethane include condensed polyester polyols and lactone polyester polyols. Examples of condensed polyester polyols include ethylene glycol and
Propylene glycol, 1,4-butanediol, 1,
3-butanediol, 1,4-butenediol, 1,3
-Butenediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,5-pentanediol, and other polyhydric alcohols, and, for example, adipic acid, sebacic acid, azelaic acid,
Fatty acids such as terephthalic acid, isophthalic acid, maleic acid,
Alternatively, polyester diols obtained by condensation reaction with an aromatic carboxylic acid may be mentioned. Examples of the lactone polyester polyol include polycaprolactone glycol, polypropiolactone glycol,
Examples thereof include polyvalerolactone glycol. Examples of the long-chain polyol of polycarbonate urethane include ethylene glycol, propylene glycol, 1,
4-butanediol, 1,3-butanediol, 1,5
By a dealcoholization reaction or a dephenolation reaction of a polyhydric alcohol such as pentanediol, 3-methyl-1,5-pentanediol, methyloctanediol, or 1,9-nonanediol with, for example, diethyl carbonate or diphenyl carbonate. The polycarbonate diol obtained can be mentioned.

Examples of the short-chain glycol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol,
1,4-bis (β-hydroxyethoxy) benzene, neopentyl glycol, methyloctanediol, 1,
9-nonanediol, bisphenol, cyclohexanedimethanol, dimethylolpropane and the like can be mentioned.

As the diisocyanate component, for example,
Phenylene diisocyanate, tolylene diisocyanate (TDI), 1,3-xylylene diisocyanate,
1,4-xylylene diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenyl Propane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-
Aromatic diisocyanates such as 4,4'-diisocyanate and 4,4'-diphenylpropane diisocyanate, isophorone diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (MD
Aliphatic diisocyanates such as I), hydrogenated TDI,
Examples thereof include alicyclic diisocyanates such as hydrogenated MDI. These can be used alone or as a mixture of two or more kinds. In particular, when no yellowing or yellowing is required, an aliphatic diisocyanate or an alicyclic diisocyanate is preferably used.

Further, the polyurethane resin must be soluble in a solvent. For example, at a concentration of 10% or more, preferably a viscosity of 500 to 10,000 cps / 2
Those which form a coating solution at 5 ° C. are preferably used.
These polyurethane resins have various softening points on the market, depending on the types and ratios of the soft segment portion and the hard segment portion, the type of diisocyanate, and the like.

When the softening point of the polyurethane resin is lower than 80 ° C., surface tack remains and it is difficult to form a film into a thin film especially in transparent applications where no filler, antiblocking agent or the like is used. The paint is softened by the heat during baking, resulting in a problem that it cannot withstand the use of the application of the present invention. On the other hand, if the temperature is higher than 190 ° C., there is a problem that the solubility in an organic solvent is remarkably reduced and coating becomes difficult.

The unstretched film of the polyurethane resin can be manufactured, for example, by the casting method, and the film thickness thereof needs to be set in the range of 5 to 30 μm. When the film thickness is less than 5 μm, the strength is low and the handling becomes difficult. Further, when the top coat is applied, the solvent contained in the top coat paint permeates the film, corrodes the adhesive and deteriorates the appearance. Problems such as occur. On the other hand, if the thickness is more than 30 μm, it may not be possible to produce a thin film marking sheet having a desired thickness, and the economical efficiency is impaired.

As the pressure-sensitive adhesive layer provided on one surface of the substrate or on the decorative display layer, any known pressure-sensitive adhesive can be used, but the average molecular weight having a carboxyl group in the side chain is from 100,000 to 100,000. A resin composition having a gel fraction of 20 to 90%, which is obtained by crosslinking a 1,000,000 acrylic copolymer with a polyglycidylamine having two or more epoxy groups and one or more tertiary nitrogen atoms, as a main component. Those that do are preferred.

As the acrylic copolymer containing a carboxyl group in the side chain, for example, a (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms and a copolymerizable unsaturated monomer containing a carboxyl group are essential components. Molecular weight 10
It is a copolymer in the range of 10,000 to 1,000,000. Examples of the (meth) acrylic acid alkyl ester having 1 to 12 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth). Acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate,
Examples thereof include n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and isobornyl (meth) acrylate. These can be used alone or in combination. As the copolymerizable unsaturated monomer containing a carboxyl group, for example, acrylic acid, methacrylic acid and the like are preferably used.

Furthermore, the acrylic copolymer having a carboxyl group in its side chain may contain, in addition to the above-mentioned monomers, other copolymerizable unsaturated monomers copolymerizable therewith. Other copolymerizable unsaturated monomers include acrylamide, (meth) acrylonitrile, N-substituted acrylamide, N-methylol acrylamide, hydroxyethyl acrylate, hydroxymethyl methacrylate, hydroxypropyl methacrylate, vinyl acetate, styrene and the like.

In the acrylic copolymer containing a carboxyl group in the side chain, the proportion of the copolymerizable unsaturated monomer containing a carboxyl group is generally set in the range of 1 to 25% by weight.

In producing this copolymer, the number of carbon atoms is 1
To 12 (meth) acrylic acid alkyl ester and a carboxyl group-containing copolymerizable unsaturated monomer, and optionally other copolymerizable unsaturated monomer are appropriately selected, and a polymerization initiator is added to a required amount. , A solvent and the like, and the copolymerization reaction is continued to obtain a desired molecular weight by a conventional method, and the reaction may be terminated when the desired molecular weight is reached, whereby a molecular weight range of 100,000 to
A desired copolymer containing a carboxyl group in the side chain of 1,000,000 can be obtained.

As the solvent used in the above copolymerization reaction, water, benzene, toluene, xylene, ethyl acetate,
Examples thereof include methyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, n-propanol, isopropanol, sec-butanol, t-butanol, n-hexane, cyclohexane and n-heptane. Examples of the above-mentioned polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, methyl ethyl ketone peroxide, cyclohexane peroxide, cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, lauroyl peroxide and acetyl peroxide. Examples thereof include peroxides such as oxides, azo initiators such as α, α′-azobisisobutyronitrile, and 4,4′-azobis-4-cyanovaleric acid. If necessary, n-butyl mercaptan, lauryl mercaptan, thioglycolic acid, mercaptans such as 2-mercaptoethanol, carbon tetrachloride and the like can be added as a molecular weight modifier. When water is used as the solvent, various known surfactants can be used.

Specific examples of polyglycidyl amine include N, N-glycidyl aniline, N, N-diglycidyl toluidine, mN, N-diglycidyl aminophenyl glycidyl ether, triglycidyl isocyanurate, N, N. , N ', N'-tetraglycidylaminodiphenylmethane, N, N, N', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane and the like. be able to.

The adhesive layer is formed by adding the above copolymer in a solvent to
It can be formed by adding the above polyglycidyl amine in the range of 0.005 to 2.0% by weight, preferably 0.01 to 1.0%, and applying this on a predetermined substrate. . In that case, the carboxyl group of the copolymer reacts with the epoxy group of polyglycidyl amine to form a pressure-sensitive adhesive layer made of a resin composition having a gel fraction of 20 to 90%. The thickness of the pressure-sensitive adhesive layer is preferably set in the range of 5 to 25 μm. In addition, it is preferable to temporarily attach release paper, for example, a paper surface-treated with a silicone release agent or the like, to the surface of the pressure-sensitive adhesive layer.

The decorative display layer provided on the thin film marking sheet of the present invention is not particularly limited, and decorative effect,
Any material may be used as long as it produces a display effect.
Further, the method for forming the same is not particularly limited. The decoration display layer may be composed of a plurality of layers.

The decorative display layer is, for example, metal vapor deposition, printing,
Alternatively, it can be formed by pasting (foil stamping) a thin film of a decorative material. The decorative display layers of various aspects can be formed by these methods, and examples of the method for forming the glittering decorative pattern include those formed by the following method. (1) A glittering decorative pattern in which a metallic glittering foil pressing material such as a gold foil, a silver foil, a hologram film, and a light interference film is attached. (2) A metallic pattern printed using an ink containing metal powder such as aluminum powder.
(3) A glittering decorative pattern formed by vacuum-depositing a metal such as aluminum or tin on a substrate. The hologram film is formed by recording an interference fringe formed by causing a signal wave diffracted by an object and a reference wave to interfere with each other on a photosensitive resin film such as a thermoplastic resin recording material.

In the case of forming a decorative pattern such as a character or a pattern using the colored printing ink, for example, screen printing, offset printing, gravure printing, flexo printing, etc.
A known printing method can be used. The printing ink layer may have only one layer, or may have a plurality of layers. Also,
A transparent or translucent clear ink layer may be provided.

A light-transmitting protective layer may be provided on the surface of the decorative display layer of the thin film marking sheet of the first aspect of the present invention and on the other surface of the base material of the thin film marking sheet of the second aspect. For the light-transmitting protective layer, general synthetic resin for printing ink can be used. Specifically, phenol resin, melamine resin, ketone resin, vinyl chloride-vinyl acetate resin, butyral resin, acrylic resin, polyester resin, alkyd resin, polyamide resin, epoxy resin,
Examples thereof include polyurethane resin, nitrocellulose resin, ethyl cellulose and chlorinated rubber resin. Particularly preferably, a good transparency, a solvent or a polyacrylic polyol or polyester polyol having excellent solvent resistance alone, or a mixed resin, a polyisocyanate prepolymer is mixed and reacted, a polyurethane-based two-part curing resin, an acrylate monomer, A UV curable acrylic resin containing an oligomer as a main component can be used.

The above-mentioned light-transmitting protective layer may contain various additive components, if desired, within a range not impairing the object of the present invention.
For example, an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a flame retardant, a coloring agent such as a dye or a pigment, and the like can be appropriately added.

In the thin film marking sheet of the first aspect of the present invention, the total thickness of the decorative display layer and the light transmissive protective layer is preferably in the range of 2 to 30 μm. Further, the thin film marking sheets of the first and second aspects of the present invention preferably have an overall thickness of 12 to 60 μm.

The above-mentioned thin film marking sheet of the present invention may be attached to the surface of a desired adherend, but after attachment, the entire surface of the adhered thin film marking sheet is covered on the surface of the adherend. It is preferable to form a transparent or translucent resin protective layer (top coat clear layer). Thereby, an article having a beautiful appearance can be obtained. Examples of the resin composition used for the top coat clear layer include alkyd resins, phenol resins, urea resins, melamine-alkyd resins, acrylic-melamine resins, unsaturated polyester resins, epoxy resins, polyurethane resins, acrylic resins, and the like. Examples include synthetic resins for paints.

[0037]

Example 1 (1) Preparation of non-stretched urethane film Polycarbonate-based polyurethane resin (Nipporan 5196 manufactured by Nippon Polyurethane Co., Ltd.) having a softening point of 90 ° C. was placed on a support film made of a biaxially stretched polyester film having a thickness of 100 μm. And was dried at 80 ° C. for 10 minutes to prepare a laminated film in which an unstretched urethane film having a thickness of 10 μm was formed on the support film.

(2) Preparation of thin film pressure-sensitive adhesive sheet A pressure-sensitive adhesive layer-forming coating solution having the following composition was coated on a release paper surface-treated with a silicone resin and dried at 80 ° C. for 10 minutes to give a pressure-sensitive adhesive having a film thickness of 10 μm. Layers were formed. Then, the unstretched urethane film surface of the laminated film obtained in (1) above and the pressure-sensitive adhesive layer surface are bonded together, the support film is peeled off, and the pressure-sensitive adhesive is aged and cured by standing at 30 ° C. for 7 days. A thin film pressure-sensitive adhesive sheet having the layer structure shown in FIG. 1 was produced.

<Coating liquid for forming adhesive layer> 95 parts by weight of n
2 parts butyl acrylate and 5 parts by weight acrylic acid
It was dissolved in 100 parts by weight of ethyl acetate, the dissolved oxygen was replaced with nitrogen, and the mixture was reacted at 70 ° C. for 8 hours in the presence of 0.3 parts by weight of benzoyl peroxide to give a solid content of 33.3.
%, A resin liquid of a copolymer having a weight average molecular weight of 400,000 was obtained. With respect to 100 parts by weight of the solid content of this resin liquid,
0.07 parts by weight of N, N, N ', N'-tetraglycidyl-m-xylylenediamine was added to prepare a coating liquid for forming a pressure-sensitive adhesive layer.

The gel fraction was measured as follows. That is, the above-mentioned pressure-sensitive adhesive layer-forming coating liquid was applied onto a support film made of biaxially stretched polyester having a thickness of 25 μm,
It was dried at 0 ° C. for 10 minutes to form a pressure-sensitive adhesive layer having a film thickness of 10 μm. After a release paper surface-treated with a silicone resin was stuck thereon, the adhesive was left to stand at room temperature for 7 days to age and cure the adhesive. After cutting this laminated sheet into a size of 100 × 100 mm, the release paper was peeled off and the weight (A: weight of the support film and the pressure-sensitive adhesive) was measured. Then 200
The adhesive was completely peeled off from the support film by immersing in ml of toluene at 23 ° C. for 24 hours. By filtering the obtained liquid material, a pressure-sensitive adhesive component insoluble in toluene (gel component) and a pressure-sensitive adhesive component dissolved in toluene were separated. The toluene-insoluble adhesive component was dried at 80 ° C. for 24 hours to completely remove the toluene. Then, the weight (B) of the support film and the weight (C) of the adhesive component (gel component) insoluble in toluene were weighed, and the gel fraction was determined by the following formula. Gel Fraction = C / (A−B) The gel fraction of the resin composition forming the pressure-sensitive adhesive layer was 63 to 76% (sample number = 10).

Example 2 The following metallic transfer foil was transferred to the non-stretched urethane film surface (front side) of the thin film pressure-sensitive adhesive sheet obtained in Example 1 by pressurizing and heating, and the thickness having the layer constitution shown in FIG. 2 was obtained. 25
A thin film marking sheet having a foil pattern forming layer (decoration display layer) of μm was produced.

<Metallic Transfer Foil> The structure of the metallic transfer foil is shown in FIG. In the figure, 7a is a support film, 7b is a release layer, 4b-1 is a protective layer, 4b-2 is a metal vapor deposition layer, 4b.
b-3 is an adhesive layer. A polyester film (12 to 25 μm) that is suitable for vacuum deposition as a supporting film and is excellent in heat resistance, transparency, flexibility, mechanical strength, and dimensional stability.
m thickness) is commonly used. A release layer is provided on the support film to facilitate transfer when heated and pressed, and a protective layer or a protective colored layer is provided to protect the metal vapor deposition layer provided thereon and to impart a color effect. . After transfer by heating and pressing, the release layer 7b and the supporting film 7
A is peeled off to form a foil pattern of 4b-1 to 3 on the adherend.

Example 3 On the surface of the foil pattern forming layer of the marking sheet having the foil pattern forming layer obtained in Example 2, a polyurethane two-component curing resin was applied by silk screen printing, and the temperature was raised to 80 ° C. And drying for 30 minutes to form a light-transmitting protective layer having a film thickness of 5 μm, and having a layer structure shown in FIG.
A king sheet was produced.

Example 4 On a non-stretched urethane film of the thin film pressure-sensitive adhesive sheet obtained in Example 1, a silk screen ink prepared by dispersing a pigment in a polyurethane two-component type curable resin was applied by a silk screen printing method. It was applied and dried at 80 ° C. for 30 minutes to form a printing ink layer having a film thickness of 5 μm. Then, a foil pattern forming layer was formed thereon in the same manner as in Example 2, and a light-transmitting protective layer was further formed in the same manner as in Example 3 to have a layer structure shown in FIG. A thin film marking sheet was prepared.

Example 5 On the unstretched urethane film of the laminated film obtained in Example 1 (1), acrylic UV was applied by offset printing.
An offset ink formed by dispersing a pigment in a curable resin was printed at a film thickness of 1 μm or less and UV-cured with a predetermined light amount to form a decorative display layer. Then, the pressure-sensitive adhesive layer formed in the same manner as in Example 1 (2)
It is attached to the decorative display layer, the support film is peeled off, and
The pressure-sensitive adhesive was aged and cured by leaving it at 7 ° C. for 7 days. afterwards,
On the exposed unstretched urethane film, a polyurethane two-component type curing resin was applied by a silk screen printing method in the same manner as in Example 3 and dried at 80 ° C. for 30 minutes to obtain a light transmittance of 5 μm. A protective layer was formed to prepare a thin film marking sheet having a layer structure shown in FIG. 5 and having a thickness of 25 μm.

Example 6 After the release paper of the marking sheet obtained in Example 2 was peeled off, it was pasted on an acrylic-melamine resin paint-coated iron plate, which is the adherend, and the acrylic resin of the same composition as the paint was placed on it. After applying the transparent composition of the melamine resin, it was baked and cured at 140 ° C. for 20 minutes to obtain the marking sheet-adhered article of FIG. 6 having the acrylic-melamine resin cured product as the transparent resin protective layer.

[0047]

Since the thin film marking sheet of the present invention has the above-mentioned constitution and is produced by using the thin film pressure sensitive adhesive sheet, the protective layer provided after sticking has high solidification, thinning, and high hardness, It can be used for high temperature baking.
Therefore, the thin film marking sheet of the present invention is useful for sticking to an article requiring a top (over) coat for use, for example, automobiles, motorcycles, bicycles, fishing rods, golf clubs, tennis rackets, surfboards. It is used as a design marking, legal plate, caution label, etc. in sports goods such as and other synthetic resin molded products.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of a thin film pressure-sensitive adhesive sheet for producing a marking sheet of the present invention.

FIG. 2 is a schematic cross-sectional view of an example of the thin film marking sheet of the present invention.

FIG. 3 is a schematic cross-sectional view of an example of the thin film marking sheet of the present invention.

FIG. 4 is a schematic cross-sectional view of an example of the thin film marking sheet of the present invention.

FIG. 5 is a schematic cross-sectional view of an example of the thin film marking sheet of the present invention.

FIG. 6 is a schematic cross-sectional view of a marking sheet-adhered article of the present invention.

FIG. 7 is a schematic cross-sectional view of the metallic transfer foil used in Example 2.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Substrate, 2 ... Adhesive layer, 3 ... Release paper, 4 ... Decorative display layer, 4a ... Printing ink layer, 4b ... Foil pattern forming layer, 5 ... Light-transmitting protective layer, 6 ... Transparent resin protective layer, 10 ... Marking sheet, A ... Adhered article.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09J 133/02 C09J 133/02 163/00 163/00 201/00 201/00 G09F 3/02 G09F 3 / 02 B G F terms (reference) 4F100 AB01D AK41A AK45A AK51A AL06A AT00A BA02 BA03 BA04 BA10A BA10D CB05B EH66D GB90 HB00C HB31D JA04A JD02 JJ03 JDF08 FA06 FA06 FADF01 DF01 FA06J0108J0108J0108J0108J0108J010813A01A4A02 HC01 JA09 JB09 KA16 NA21 PA23

Claims (12)

[Claims] 1. A pressure-sensitive adhesive layer having a film thickness of 5 to 25 μm is laminated on one surface of a substrate having a film thickness of 5 to 30 μm, which is made of an unstretched film of a polyester or polycarbonate polyurethane resin having a softening point of 80 to 190 ° C. A thin film pressure-sensitive adhesive sheet for producing a marking sheet, comprising: 2. The pressure-sensitive adhesive layer comprises an acrylic copolymer having a carboxyl group in a side chain and having an average molecular weight of 100,000 to 1,000,000, two or more epoxy groups and a third copolymer.
The thin film pressure-sensitive adhesive sheet for producing a marking sheet according to claim 1, which is formed mainly of a resin composition having a gel fraction of 20 to 90%, which is crosslinked with a polyglycidylamine having one or more primary nitrogen atoms. . 3. A pressure-sensitive adhesive layer having a film thickness of 5 to 25 μm is laminated on one surface of a substrate having a film thickness of 5 to 30 μm, which is made of an unstretched film of a polyester-based or polycarbonate-based polyurethane resin having a softening point of 80 to 190 ° C. A thin film marking sheet comprising a decorative display layer provided on the other surface of the base material. 4. The thin film marking sheet according to claim 3, wherein a light transmissive resin layer is provided on the surface of the decorative display layer. 5. A substrate having a thickness of 5 to 30 μm, which is made of a non-stretched polyester or polycarbonate polyurethane resin having a softening point of 80 to 190 ° C., and has a thickness of 5 to 25 μm on one surface thereof through a decorative display layer. A thin film marking sheet having a pressure-sensitive adhesive layer laminated. 6. The thin film marking sheet according to claim 5, wherein a light transmissive resin layer is provided on the other surface of the base material. 7. The pressure-sensitive adhesive layer comprises an acrylic copolymer having a carboxyl group in a side chain and having an average molecular weight of 100,000 to 1,000,000, two or more epoxy groups and a third copolymer.
The thin film marking sheet according to claim 3 or 5, which is formed by mainly using a resin composition having a gel fraction of 20 to 90%, which is crosslinked with a polyglycidylamine having one or more primary nitrogen atoms. 8. The thin film marking sheet according to claim 3, wherein the decorative display layer is formed by at least one of metal vapor deposition, printing, and sticking of a glittering material thin film. 9. The thin film marking sheet according to claim 4, wherein the light transmissive resin layer is an acrylic resin or a polyester resin crosslinked by a urethane bond. 10. The thin film marking sheet according to claim 3, wherein the entire thickness is 12 to 60 μm. 11. The thin film marking sheet according to claim 4, wherein the total thickness of the decorative display layer and the transparent resin layer is 2 to 30 μm. 12. The thin film marking sheet according to claim 3 is attached to the surface of an adherend, and a transparent or semitransparent protective layer is formed over the surface of the adherend including the thin film marking sheet. An article to which a marking sheet is attached.