JPS6137499A - Ultraviolet barriering transfer material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to a UV-shielding transfer material.

Various transfer materials have been known for transferring metal vapor deposited layers and colored resin layers containing dyes and pigments, but all of them have poor weather resistance, and after being transferred to the desired transfer surface, the vapor deposited metal layer cannot be transferred. The disadvantage is that the gloss, the elegant luster of the colored resin layer, and the color are quickly lost.

The present invention has been made to solve the above-mentioned problems, and the transferred metal vapor deposited layer retains its metallic luster for a long period of time, or the colored resin layer has an elegant and clear appearance without fading. The purpose of the present invention is to provide an ultraviolet-shielding transfer material that can maintain beautiful color and gloss.

The first UV-shielding transfer material according to the present invention includes a base film, a transparent or semi-transparent mold release agent layer laminated on one side of the base film, and a UV-absorbing first resin layer coated with MIWI thereon. , a second resin layer laminated on this ultraviolet absorbing resin layer, and a heat-sensitive adhesive layer laminated on this second resin layer, and the ultraviolet absorbing resin layer The second transfer material is characterized by containing fine particulate iron oxide as an absorbent as a main component, and the second transfer material is
A metal vapor-deposited layer is vapor-deposited on the resin layer, and a heat-sensitive adhesive layer is laminated on this metal-deposited layer.

The ultraviolet-shielding transfer material according to the present invention will be explained below based on the drawings showing examples.

FIG. 1 is a sectional view of a main part of a first transfer material according to the present invention. The base film 1 to be used is not particularly limited, but usually
Flexible synthetic resin films such as polyester, polyamide, polyimide, polycarbonate, polyvinyl chloride, polypropylene, and polyethylene, and laminates thereof are preferably used. If necessary, cellophane or glassine paper may also be suitably used.

A transparent or translucent mold release agent rrJ2 is laminated on one side of such a base film (2). The mold release agent is not particularly limited, and various conventional mold release agents such as silicone 4M resin, fluorine resin, fatty acid ester, fatty acid amide, acrylic resin, waxes, cellulose resin, rosin and its derivatives, etc. One kind or a mixture of two or more kinds of styrenic resins and the like can be used as appropriate. The release agent layer is usually formed by applying a solution of these release agents to one side of a base film and drying it.

In the first transfer material according to the present invention, a substantially transparent or translucent ultraviolet absorbing resin layer 3 is laminated as a first resin layer on such a release agent layer. This first resin layer is made by uniformly dispersing an ultraviolet absorber mainly consisting of substantially transparent fine particulate iron oxide in 43J resin, and the iron oxide has good ultraviolet absorbability. It is preferable that the average particle diameter is 0.1 μm or less. In the present invention, the iron oxide mentioned above includes hydrated iron oxide.

In particular, according to the present invention, the ultraviolet absorber includes 60 to 95 parts by weight of finely divided iron oxide with an average particle size of 0.1 μm or less and 40 to 95 parts by weight of finely divided titanium oxide with an average particle size of 0.1 μm or less.
5 parts by weight, and by forming the ultraviolet absorber into a mixture of particulate 6 oxide and titanium oxide at a predetermined ratio, the ultraviolet absorbency of the ultraviolet absorbing resin layer is particularly improved. . In particular, the ultraviolet absorber preferably comprises 70 to 90 parts by weight of the above-mentioned iron oxide and 30 to 10 parts by weight of titanium oxide. In the present invention, titanium oxide includes hydrated titanium oxide.

The resin for forming such a UV-absorbing resin layer is not particularly limited, but cellulose derivative resins such as cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, and unsaturated polyester resins are usually preferred. used. UV absorption 1
The content of iron oxide and titanium oxide in the secondary fat layer is:
A range of 10 to 30% by weight based on the resin composition is suitable; when it is less than the above, UV absorption is poor, while when it is blended in a larger amount than the above, the transferred laminate may suffer from peeling between the eyebrows. This is not preferable because it may result in the formation of a ray of water, reduce the transparency of the ultraviolet absorbing resin layer, and make the color of the colored layer unclear. The thickness of such a UV absorbing resin layer is
Usually, a range of 0.5 to 1 μm is suitable.

In addition, in the present invention, in addition to iron oxide and titanium oxide as described above, conventionally known ultraviolet absorbers such as (2-hydroxy-5-methylphenyl) are added to the resin forming the ultraviolet absorbing resin layer. A benzotriazole-based ultraviolet absorber such as benzotriazole and other organic ultraviolet absorbers may be further included.

A second resin layer 4 is laminated on the ultraviolet absorbing resin layer as the first resin layer.

This second resin layer usually contains a dye and/or a pigment and is colored depending on the purpose of transfer. The dyes or pigments used for this coloring are commonly used organic solvent-soluble dyes or organic/inorganic pigments, and the pigments include:
For example, extender pigments, fluorescent pigments, phosphorescent pigments, metal powders, metal vapor deposited layers, etc. are used. This second resin layer is made of a heat-resistant resin made of one or a mixture of two or more of acrylic resin, vinyl chloride-vinyl acetate copolymer resin, polyurethane resin, urea resin, melamine resin, polyester resin, epoxy resin, etc. Plastic or thermosetting resins are used. Also,
A solvent-free ultraviolet curable resin coating may be applied and cured by ultraviolet irradiation, and this may be used as the second resin layer. At this time, as the ultraviolet curable monomer, acrylic ester type, epoxy type, urethane type, polyester type, etc. are used as appropriate. If necessary, a sensitizer, prepolymer, polymerization initiator, stabilizer, etc. are used in combination.

A heat-sensitive adhesive rN6 is laminated on the second resin layer. As the heat-sensitive adhesive, those conventionally used in the production of transfer materials can be used as appropriate. For example, thermoplastic resins or thermal It is an adhesive made of curable resin. The adhesive may contain pigments such as titanium oxide, calcium carbonate, barium sulfate, magnesium carbonate, lithopone, Kurji, clay, white carbon, extender pigments, and the like as fillers.

Next, FIG. 2 shows a second ultraviolet-shielding transfer material according to the present invention.

That is, the second ultraviolet-shielding transfer material according to the present invention comprises a base film 1, a transparent or translucent release agent layer 2 laminated on one side of the base film 1, and a 1M ultraviolet-absorbing layer layered thereon. A first resin layer 3, a second 114 fat eyebrow 4 and 1 laminated on this ultraviolet absorbing resin layer, a metal vapor deposition layer 5 deposited on this second resin layer, and this metal It consists of a heat-sensitive adhesive layer 6 laminated on a vapor deposited layer, and is characterized in that the ultraviolet absorbing resin layer contains fine particulate iron oxide as a main component as an ultraviolet absorber.

Here, the metal vapor deposition layer includes not only a metal but also a metal oxide vapor deposition layer, and the method of forming this metal vapor deposition layer is not limited at all, and a conventionally known method is used to form the second metal vapor deposition layer. is formed on the resin layer. Therefore, for example, any method such as a vacuum deposition method, a high-frequency induction heating method, an electric resistance heating method, a sputtering method, an ion blating method, an electron beam heating method, etc. can be adopted, and the metal to be vapor-deposited is also aluminum. , silver, gold, copper, zinc, nickel, chromium, etc., as well as alloys of these and various compounds are used as appropriate.

As described above, since the first ultraviolet-shielding transfer material according to the present invention has a substantially transparent or semi-transparent ultraviolet-absorbing resin layer between the second resin layer and the release agent layer, When this transfer material is thermophilically adhered to the desired surface to be transferred and the base film is removed, that is, when the transfer is performed, the second resin layer is covered with the transparent or translucent ultraviolet absorbing resin layer. As a result, ultraviolet rays are blocked. Therefore, it is possible to impart weather resistance to the second resin layer and the adhesive layer, maintain clear color and gloss over a long period of time without fading, and maintain good adhesion. Further, in the second ultraviolet-shielding transfer material according to the present invention, the second resin layer and the metal vapor deposited layer are protected by the ultraviolet-absorbing resin layer, as in the first ultraviolet-shielding transfer material, and the metallic luster is maintained for a long period of time. And the color and gloss caused by the second resin layer can be maintained.

As described above, the UV-shielding transfer material according to the present invention has an excellent ability to shield UV rays, so it can be used as a packaging sheet for pharmaceuticals, cosmetics, food products, etc. that are susceptible to deterioration due to UV rays, or as packaging for clothing that is prone to discoloration due to UV rays. It can be widely applied as a transfer material to plastic products such as toys, fishing equipment, and lighting equipment.

The ultraviolet-shielding transfer material according to the present invention will be described below with reference to Examples. Note that in the following, parts indicate parts by weight.

Example 1 As a resin composition for forming an ultraviolet absorbing resin layer, 9 parts of iron oxide with an average particle size of 0.02 μm and an average particle size of 0
．． 1 part by weight of titanium oxide having a diameter of 0.05 μm was added to 50 parts of methyl ethyl ketone containing 10 parts of an unsaturated polyester resin to prepare a resin liquid in which the pigment was uniformly dispersed.

A transparent wax-based mold release agent was coated on one side of a polyester film with a thickness of 12 μm and dried, and then the resin liquid was coated and dried so that the thickness of the dried coating was 0.5 μm to form an ultraviolet absorbing resin layer. After that, a colored resin layer was formed on this resin layer.The colored resin layer was made of 10 parts of acrylic resin, 10 parts of polyurethane resin, 1 part of dye Neozapon Yellow (manufactured by BASF), and pigment Hoster Print Yellow HR ( A UV-absorbing resin layer is prepared by dissolving 2 parts of aluminum gold M powder (manufactured by Hoechst), 2 parts of aluminum gold M powder, and 3 parts of a metal vapor deposited layer in a mixed solvent consisting of 40 parts of methyl ethyl ketone, 10 parts of ethyl acetate, and 10 parts of methyl isobutyl ketone. It was formed by coating and drying.

Next, aluminum was deposited on the colored resin layer to a thickness of 400 mm using a conventional vacuum deposition method.

Further, a heat-sensitive adhesive consisting of a methyl acrylate copolymer, a vinyl acetate resin, and calcium carbonate as a filler was applied thereon and dried to obtain an ultraviolet-shielding transfer material according to the present invention.

The laminate transferred to the object to be transferred using this transfer material is subjected to JI test using a sunshine type weather meter (manufactured by Suga Test Instruments 011).
A weather resistance test was conducted according to SK51 inch. As a result of visual observation of the colored resin layer and the vapor deposited aluminum layer every 50 hours, no change was observed in the colored resin layer and the vapor deposited aluminum layer of the transfer material according to the present invention even after 400 hours.

Example 2 As a resin composition for forming an ultraviolet absorbing resin layer, 7 parts of iron oxide with an average particle iM of 0.02 μm and 9 parts of titanium oxide with an average particle size of 0.05 μm were mixed with 20 parts of cellulose acetate butyrate. In addition to 50 parts of a mixed solution of toluene and methyl ethyl ketone containing the above pigment, a resin liquid in which the above pigment was uniformly dispersed was prepared.

After coating a fatty acid amide mold release agent on one side of a 25 μm thick polyester film and drying it, the above resin liquid was applied and dried so that the thickness of the dried coating film was 1 μm to form an ultraviolet absorbing resin layer, and then, A colored resin layer was formed on this. This colored resin layer contains 10 parts of epoxy resin, 15 parts of melamine resin, and a luminescent pigment (LC-YIA manufactured by Shinroihi Co., Ltd.).
10 parts and fluorescent pigment (FM-100 manufactured by Shinroihi) 5
A resin composition was prepared by dissolving 10 parts of toluene, 30 parts of methyl ethyl ketone, 20 parts of ethyl acetate, and 10 parts of ethyl glycol, and this was applied to a thickness of 1 μm on the ultraviolet absorbing resin layer. and dried to form.

After the colored resin layer is formed, a heat-sensitive adhesive consisting of methyl acrylate copolymer, vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer, and thermoplastic polyurethane resin is further applied thereon. After drying, an ultraviolet-shielding transfer material according to the present invention was obtained.

This transfer material was subjected to a weather resistance test in the same manner as in Example 1. As a result, even in the transfer material according to the present invention, no change occurred in the colored layer even after 400 hours had elapsed.

Example 3 As a resin composition for forming an ultraviolet absorbing resin layer, 8 parts of iron oxide with an average particle diameter of 0.02 μm and an average particle f+
o, 2 mHk parts of 5 μm titanium oxide and 50 parts of methyl isobutyl ketone and methyl ethyl ketone resin solution containing 20 parts of cellulose acetate butyrate,
A resin liquid in which the above-mentioned intermediate material was uniformly dispersed was prepared.

A mixed mold release agent of silicone resin and acrylic resin was dried on one side of a polyester film with a thickness of 19 μm, and then the above resin liquid was applied so that the thickness of the dried film was 0.8 μm, and after drying. A second resin layer was formed on this coating film. The second Glue I fat layer was formed by dissolving 5 parts of urea resin and 15 parts of acrylic resin in a mixed solvent consisting of 30 parts of methyl ethyl ketone, 10 parts of butyl acetate, and 10 parts of ethylene glycol, and applying and drying the solution. .

Next, on this second resin layer, aluminum is deposited to a thickness of 350 mm using a normal vacuum deposition method, and on top of this, methyl methacrylate resin, ethylene ethyl acrylate copolymer resin, petroleum resin and filling Apply a heat-sensitive adhesive made of white carbon as an agent, dry it, and apply ultraviolet rays according to the present invention! ! A masking transfer material was obtained.

This transfer material was subjected to a weather resistance test in the same manner as in Example 1. As a result, in the transfer material according to the present invention, no change occurred in the second resin layer and the vapor-deposited aluminum layer even after 400 hours had passed. .

Comparative Example For comparison, transfer materials were obtained in the same manner as in Examples 1 to 3, except that no ultraviolet absorbing resin layer was provided, and weather resistance tests were conducted on these in the same manner as above. As a result, in all of the transfer laminates, the second resin layer and the decorative metal layer were discolored and deteriorated after 10 hours.

Reference Example 1 A printing ink containing 10% iron oxide with an average particle size of 0.05 μm was prepared and used in normal gravure printing so that the dry coating film was 3 μm on one side of a 0.03-thick polyethylene film. The film was printed and dried by heating at 120° C. for 1 minute to obtain an ultraviolet shielding film. The light transmittance of the ultraviolet shielding film thus obtained was measured using a spectrophotometer, and the results are shown in FIG.

FIG. 3 shows that the ultraviolet absorbing resin layer containing iron oxide effectively absorbs ultraviolet rays.

Reference example 2 Iron oxide with an average particle size of 0.05 μm and an average particle size of 0
．． 10% and 0.5% of titanium oxide with a diameter of 0.05 μm, respectively.
The printing ink contained was adjusted and printed on one side of a polyethylene film with a thickness of 0.03 mm using normal gravure printing so that the dried coating film was 5 μm, dried by heating at 140'C for 2 minutes, and exposed to ultraviolet rays. A shielding film was obtained. The light transmittance of the UV-shielding film was measured using a spectrophotometer, and the results are shown in FIG.

As is clear from FIG. 4, the ultraviolet absorbing resin layer containing the above components absorbed ultraviolet light over a wide range of ultraviolet regions.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view of a main part showing a transfer material according to the present invention, FIG. 2 is a cross-sectional view of a main part showing another embodiment of a transfer material according to the present invention, and FIGS. It is a graph showing the light transmittance of the ultraviolet ray blocking film containing the used ultraviolet absorber. l... Base film, 2... Mold release agent layer, 3... Ultraviolet absorbing resin layer, 4... Second resin layer, 5... Metal vapor deposited layer, 6... Heat sensitive adhesive layer. Patent applicant Nippon Kagaku Foil Kogyo Co., Ltd. Nakayama Kagaku Shikosho Co., Ltd. Figure 3 A (nrn)

Claims (10)

[Claims] (1) A base film, a transparent or translucent mold release agent layer laminated on one side of the base film, a first ultraviolet-absorbing resin layer laminated thereon, and a top layer of the ultraviolet-absorbing resin layer. and a heat-sensitive adhesive layer laminated on the second resin layer, and the ultraviolet absorbing resin layer mainly contains fine particulate iron oxide as an ultraviolet absorber. An ultraviolet-shielding transfer material characterized by containing: (2) The ultraviolet-shielding transfer material according to claim 1, wherein the ultraviolet absorber is made of fine particulate iron oxide. (3) The ultraviolet-shielding transfer material according to claim 1, wherein the ultraviolet absorber comprises 60 to 95 parts by weight of particulate iron oxide and 40 to 5 parts by weight of particulate titanium oxide. (4) The ultraviolet-shielding transfer material according to claim 2 or 3, wherein both the particulate iron oxide and the particulate titanium oxide have an average particle diameter of 0.1 μm or less. (5) The ultraviolet-shielding transfer material according to claim 1, wherein the second resin layer is made of a cured coating film of an ultraviolet-curable resin paint. (6) A base film, a transparent or translucent mold release agent layer laminated on one side of the base film, a first ultraviolet absorbing resin layer laminated thereon, and a top layer of the ultraviolet absorbing resin layer. It consists of a second resin layer laminated on the second resin layer, a metal vapor deposition layer deposited on the second resin layer, and a heat-sensitive adhesive layer laminated on the metal vapor deposition layer. 1. An ultraviolet-shielding transfer material characterized in that the resin layer contains finely particulate iron oxide as a main component as an ultraviolet absorber. (7) The ultraviolet-shielding transfer material according to claim 6, wherein the ultraviolet absorber is made of fine particulate iron oxide. (8) The ultraviolet-shielding transfer material according to claim 6, wherein the ultraviolet absorber comprises 60 to 95 parts by weight of particulate iron oxide and 40 to 5 parts by weight of particulate titanium oxide. (9) The ultraviolet-shielding transfer material according to claim 7 or 8, wherein both the particulate iron oxide and the particulate titanium oxide have an average particle diameter of 0.1 μm or less. (10) The ultraviolet-shielding transfer material according to claim 6, wherein the second resin layer is made of a cured coating film of an ultraviolet-curable resin coating.