JPS63293099A - Transfer sheet - 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 [Industrial Field of Application] The present invention relates to a transfer sheet having a high quality burl feel and excellent abrasion resistance and chemical resistance.

[Conventional technology]

Conventionally, there are many transfer sheets that have a pearlescent feel. For example, one in which a releasable protective layer, a pearl layer, a colored layer, and an adhesive layer are laminated in this order on one side of a base sheet, or one in which a colored layer and an adhesive layer are laminated on one side of a base sheet. It is known that a metal vapor deposited layer is provided in between to impart a metallic feel and/or concealment properties.

Here, the release layer fill acts as a protective layer for the pattern 71 (pearl layer, colored layer, vapor deposited FJ) in the transfer layer formed after transfer.

[Problem that the invention seeks to solve]

Conventional transfer sheets have a releasable protective layer, pattern layer, and adhesive layer all made of dissolving paint or printing ink obtained by dissolving resin in a solvent. It is known that if the mold release protective layer lacks chemical and solvent resistance, it may cause significant changes (discoloration, disappearance), especially when it contains a Burr pigment or metal vapor deposited layer, which has poor scratch resistance and abrasion resistance. ing.

In recent years, there has been a demand for solvent resistance, scratch resistance, and abrasion resistance for the transferred surface, and methods such as applying a coating generally called a hard coat to the transfer surface after the transfer painting has been applied have been adopted. It is being

However, this method has the problem of increasing the number of steps and requiring painting and drying equipment, which has many disadvantages in terms of cost.

[Means for solving problems]

As a result of various studies aimed at solving the above problems, it was discovered that the above problems could be solved by imparting scratch resistance and abrasion resistance to the mold release layer, and the present invention was completed. .

That is, the present invention provides a transfer sheet in which a releasable layer, a pearl ink layer, a colored layer, and, if necessary, a metal deposited layer are sequentially provided on one side of a base sheet. However, (a) a curable compound having two or more acryloyl groups or methacryloyl groups in the molecule; and 0)) a transparent filler whose surface has been treated with an alkoxysilane having a radically polymerizable unsaturated bond in the molecule. , J is a transfer sheet comprising a cured layer of a composition containing a mixture of the following.

[Effect]

Since the transfer sheet of the present invention contains a filler in the releasable layer, the releasable layer can be dried to the touch without being crosslinked during formation, and adhesion with the next layer can be ensured. Moreover, as the compound constituting the mold release layer, a curable compound having two or more acryloyl groups or methacrylic groups in the molecule is used, and this is cured to form the mold release layer, so it is made of conventional thermoplastic resin. It can exhibit physical and chemical properties that are superior to those found in other materials.

〔Example〕

First, the releasable protective layer, which is a characteristic feature of the transfer sheet of the present invention, will be explained.

As component (a), which is one of the components constituting the #-type protective layer in the transfer sheet of the present invention, a compound having two or more acryloyl groups or methacryloyl groups in the molecule is used.

Specific examples of component (a) include ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and trimethylolpropane di(meth)acrylate. ) acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate
Acrylate, Polyethylene glycol diglycidyl ether di(meth)acrylate, Propylene glycol diglycidyl ether di(meth)acrylate, Polybrobylene glycol diglycidyl ether di(meth)acrylate, Sorbitol tetraglycidyl ether tetra(meth)acrylate, Polyurethane(meth)acrylate ) acrylate, melamine (meth)acrylate, and other polyfunctional (meth)acrylates, but other than these can also be used.

In order to obtain good scratch resistance, among the above-mentioned polyfunctional (meth)acrylates, (meth)acrylic equivalent is 90.
200 is preferable.

Examples of the alkoxysilane (also referred to as a silane coupling agent) having a radically polymerizable unsaturated bond in the r molecule for treating the transparent filler in the component (r) include γ-methacryloxypropyltrimethoxy. Silane, γ-methacryloxypropylmethyldimethoxysilane, T-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyldimethylethoxysilane, T-acryloxypropyltrimethoxysilane, γ −
Acryloxypropylmethyldimethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropyltriethoxysilane, T-acryloxybrobylmethyldiethoxysilane, γ-acryloxypropyldimethylethoxysilane, vinyltriethoxysilane, etc. can be mentioned.

Examples of transparent fillers include Sing (silica) and A
The powder particle size of ltos (alumina) is lomμ~1
A material having a particle diameter of 0 μm is suitable, and examples of commercially available products include “Aerosil” and “Aluminum Oxide-C” manufactured by Nippon Aerosil ■, and “Syloid” manufactured by Fuji Davison ■. SiO□ (silica) powder, A1.0. (
Alumina powder is particularly preferred since it can maintain the transparency of the releasable protective layer, but any other transparent filler may be used.

The method of treating the transparent filler with the above-mentioned silane camping agent is not particularly limited and any known method may be used. For example, as a dry method, a predetermined amount of the silane camping agent is added to the transparent filler while vigorously stirring it. There are spraying methods, and wet methods where a transparent filler is dispersed in a solvent such as toluene, and then a predetermined amount of silane coupling agent is added and reacted, but the latter method is recommended for uniform treatment. Wet methods are preferred.

The amount of silane coupling agent to be treated (required amount) for the transparent filler is such that the minimum coverage area of the silane coupling agent is 10 to 100 per specific surface area of the transparent filler of 100.
It is preferable to have a processing amount such that the minimum coverage area is less than 10, and there is no effect, and when it exceeds 100, no improvement in performance is observed.

The mixing ratio of the above-mentioned polyfunctional (meth)acrylate and the treated transparent filler should be such that the transparent filler is added to the extent that the polyfunctional (meth)acrylate does not become sticky. It is preferable to use 10 to 200 parts by weight of the transparent filler per 100 parts by weight of the (meth)acrylate.In order to use the polyfunctional (meth)acrylate and the treated transparent filler as a coating agent, a predetermined amount of the polyfunctional (meth)acrylate and the treated transparent filler can be used. A transparent filler treated with functional (meth)acrylate,
If necessary, a solvent may be added and kneaded using a dispersing machine such as a sand mill or a roll.

Further, it is preferable to add a polymerization inhibitor such as handquinone or hydroquinone monomethyl ether to this coating agent in order to improve the storage stability.

Furthermore, in order to improve coating suitability, the coating agent may contain cellulose resins such as ethyl cellulose and nitrocellulose, rubber resins such as polyester resin, polyurethane resin, rosin ester resin, cyclized rubber, and chlorinated polyolefin. Polymers such as resins and acrylic resins may be used, and colorants such as pigments and dyes may also be added as appropriate.

The method of forming a releasable layer on the upper surface of the base sheet using the coating agent is the same as the conventional method of applying a coating agent, such as a halo coating method, a gravure coating method, a screen coating method, There are coating methods such as fountain coating method.
Base sheet, such as polyester film, polyamide film, cellophane film, acetate film,
A solid content of 1 to 6 g/n is applied to the surface of a base sheet such as a polypropylene film, a metal foil, etc. alone or a laminated sheet of two or more of them as necessary. Just apply it to a certain extent and let it dry.

After forming the releasable protective layer on the base sheet by the method described above, at least one layer such as a pattern layer or an adhesive layer is preferably provided on the releasable layer, and then the moldable protective layer is cured. - Methods of curing include irradiation with ionizing radiation and methods using radical polymerization initiators, but a method using ionizing radiation is preferred from the viewpoint of completing curing in a short time. As ionizing radiation, electron beams, Ultraviolet rays, T-rays, etc. can be used, and in the case of electron beams and T-rays, the irradiation dose is preferably about 1 to 20 Mrad.

In addition, the degree of ultraviolet irradiation is such that as aggravating agents, benzoin ethers such as benzoquinone, benzoin, and benzoin methyl ether, halogenated acetophenones, and diacetyl compounds that generate radicals when irradiated with ultraviolet rays are used at 1 to 20% of the coating agent. It is preferable to use it by adding it in weight%.

In addition, in the method using a radical polymerization inhibitor, 0.1 to 1% by weight of a polymerization inhibitor such as various peroxides such as benzoyl peroxide or α,α1-azobisisobutylnitrile is added to the coating agent. It is sufficient to add a certain amount and heat above the decomposition temperature, but as a whole, the releasable layer composed of a polymer crosslinked by thermosetting has a large peeling force from the base sheet after the transfer is completed. , it is preferable to have a crosslinked structure introduced by irradiation with ionizing radiation.

In addition, after providing a release layer on the base sheet, a transparent thermoplastic resin layer (ink adhesive layer) is provided on the release layer, and after curing the release layer using the method described above, the image is printed. It is also possible to adopt a method of providing a layer or an adhesive layer, and this method is particularly preferred when the curing means is ultraviolet irradiation.

To form the burl layer and the colored layer, printing and drying are performed using printing ink containing a burl pigment and a coloring agent. Metal powders, such as aluminum powder, bronze powder, can also be used instead of Burl pigments.

Further, when providing a vapor deposition layer, a single layer of vapor deposition anchor may be provided so that metal atoms are attached smoothly.

This vapor deposition anchor layer is also formed by printing and coating.

Next, a coating agent containing a thermoplastic resin as a main component is applied to the surface of the releasable protective layer including the obtained pattern layer so as to cover the surface of the pattern layer and the surface of the releasable protective layer and dried. Then, an adhesive layer is formed to form a transfer sheet.

〔Effect of the invention〕

According to the above-mentioned present invention, a transfer sheet can be provided that has excellent scratch resistance, abrasion resistance, and solvent resistance on the surface after transfer, and has a high-quality pearlescent feel.

[Specific examples]

The mixture [A] above and below was heated under reflux for 10 hours to surface-treat the silica powder to obtain a reaction mixture of treated silica [X], which was used to prepare a coating agent [C].

Itsutsu IL Yu/”- Silica powder・・・・・・・・・・・・−・−・・−・
・−・−・−・−・・−・−・・・500 parts by weight (manufactured by Nippon Aerosil ■, Aerosil #200) T-methacryloxypropyltrimethoxysilane・−・・
・・・・・・・・・−・・・−・・・・・−・−・−・
−・・−・−・−・−312 parts by weight (Shin-Etsu Chemical ■
(manufactured by KBM503) Dilute hydrochloric acid water (adjusted to pH = 3)
・70 parts by weight toluene--
・・・・・−・・−・−・−・−・・−・5000 weight 1 part Next, a coating agent [c] having the following composition was produced.

Coating Ha-treated silica [mouth] −・−・・−・・−・−・・−・・
・−・・−・・・・−・・45 parts by weight dipentaerythritol hexaacrylate・−・−・・・・・・−・・
・・−・−・−・・−・−・−・・−45tlc1
Part polymethyl methacrylate・・・・・・・・・・・・・・・・
−・・・10 parts by weight toluene・・・−・−・・−・・−
・・−・−・・−１−−−−・・・・−−−−
---...250ffi 1 part methyl ethyl ketone...
250 parts by weight A 25 μm thick polyester film (manufactured by Toshi ■, Lumirror) was used as the base sheet, and one side of the film was coated with the above film. The obtained coating agent [C] was applied uniformly over the entire surface using a gravure diagonal plate with a plate depth of 140 μm, the solvent was evaporated by passing it through a drying hood at 80°C, and the applied coating agent layer was dried to the touch. , a releasable protective layer was obtained.

On the surface of the obtained releasable protective layer, a coating agent having the following composition [2] was applied uniformly over the entire surface using a diagonal gravure plate with a plate size of 140 μm, and the solvent was evaporated by passing it through a drying hood at 140 ° C. Dry the applied coating agent,
An ink adhesive layer was formed.

Coating Nipolymethyl methacrylate・・・・・・・・・・・・・・・・・・
・-30 parts by weight methyl ethyl ketone ・・・・・・・・・～・
・・−−1−−−・・・・・・・・・・−・・85 parts by weight toluene・・・・・・・−・・・−・・・・・・・・・・・・
・−・・−・−・−・−・−・・・・−・・−・・
-85 heavy a part Then, an electron beam accelerated to 175 KV in a nitrogen gas atmosphere was applied from the coated surface side to the
The releasable protective layer was crosslinked and cured by Mrad irradiation.

Next, on the ink adhesive layer, a gravure ink with the following compositions [E] and [F] was printed on the entire surface using a halftone gravure plate, and passed through a drying hood at 80°C to form a burl layer and a colored layer.

lArashitachiyu Dogami polymethyl methacrylate-・・・・・・・・・・・・・・・
・・・・10 parts by weight Pearl material・・・・・・・・・−・
−・−・・−・・−・・−・・−・−・−・・
−・20 parts by weight methyl ethyl ketone・−・−・−・
・−・・・・−・−・〜・−35 parts by weight toluene−
・・−・−・−・−・−・−・−・・・・−・・
−−１−−−−−−・・・・−・−・−・−・・−・・
・35 parts by weight l Arashi l Eyu L Polymethyl methacrylate - - - - - - - - - - - -
−・・10 parts by weight of titanium oxide −・・・・−・・・・・−
・・−・−・−・・−・・・・−・・−・・・−・・
・・・,・−・−・30 parts by weight methyl ethyl ketone・−
・・・−・−・−・・・−・・・・・−・−・30 parts by weight toluene−・・・・・・・−・・・・・・・・・・・・・
・・・−・・・−・−・−・−・・・−・・・・−・・
-30 parts of the following composition [g] was further coated to form a single layer of a vapor deposition anchor.

- Polymethyl methacrylate polyol - - - - - - - - - - - - - -
−・・−・・−・−25 parts by weight of nitrified cotton・・・・−・
・・・－・・−・・−・・・・・・−・・−・−・・−
・・・・・・・・・−・・−・−・−−11−−−−
−-・5 parts by weight hexamethylene diisocyanate −・・−・−・−・−・−・−・・・・・・・・−・−
13 parts by weight Ethyl acetate
・・・－・・・・・・・・・・・・・・・・・・－・・−・
- 80 parts by weight of vapor deposition anchor layer formed on top of a layer with a thickness of 50 parts by weight;
The aluminum layer was deposited to form an aluminum laminate layer.

The following compositions [1] and 2) were applied in order on the aluminum binding layer to form an adhesive layer to obtain a transfer sheet.

m2m Vinyl chloride/vinyl acetate copolymer resin-・-・・・−・−・・〜・・・−・・−−−1−−
---20 parts by weight of ethyl acetate--
・−・−−１−−−−・−・−・・−・・・・−−−−
−−−・・−・−・−40 parts by weight toluene−・−・
・−・−・・−・−・・−・・−・−・−・・・・−・
・−・−・−・−・−40 parts by weight l hill l engineering uniacrylic resin−・・・・−−1−−−−・・・・・・−
−−−１−−・・−・−・・・・−・・・−=・・20
Part by weight Toluene...
−−１−−−・−・−・・−・−−−１−−−−−−・
...--40 parts by weight methyl ethyl ketone--
・・−・・−・−・−・・・・・・−・・−・・4
0 parts by weight The obtained transfer sheet was placed on a separate As resin plate with the adhesive layer side of the transfer sheet in close contact with the As resin plate, and the pressure was 6.5 g/g using a silicone rubber roller with a surface temperature of 2000°C. c■, traveling speed 15 tatm/sec
After that, the polyester film of the transfer sheet was peeled off and the adhesive layer, pattern layer (pearl layer/colored IW) and releasable protective layer were transferred to the surface of the As resin plate. Peeling between the sheet and the releasable protective layer could be performed smoothly and reliably.

Comparison i± A transfer pattern was applied to an As resin plate in the same manner as in Example 1, except that a transfer sheet obtained by forming a releasable layer with a polymethyl methacrylate resin was used.

The As resin plates with transfer decoration obtained in Example 1 and Comparative Example 1 are shown below. ~5. It was tested using the method.

1. Scratch resistance test The transferred painted surface was tested using a friction tester [manufactured by Suga Test Instruments,
FR-2 type] steel wool 00 under overcurrent of 500g
A reciprocating test was conducted 100 times using No. 00 (manufactured by Sankyo Sangyo ■).

2. Solvent resistance test: Apply ethyl alcohol (E L
OH), methyl ethyl ketone (MEK), and toluene were added dropwise and the mixture was heated for 20 minutes while covering with a watch glass to prevent evaporation.
Changes in appearance after being left for a period of time were investigated.

3. Moisture and heat resistance test After the As resin plate with the transferred painting was left in an atmosphere of 60° C. and 90% humidity for 24 hours, changes in appearance were examined.

4. 8 liquids of 10% hydrochloric acid solution and 10% aqueous sodium hydroxide solution were each dropped into the chemical-resistant test transfer section, covered with a watch glass and allowed to stand for 20 hours, then washed with water and dried to examine changes in appearance.

5. Abrasion resistance test Using an RCA abrasion tester, abrasion test with a load of 275g (computer tape, puff color, oil-free crystal 11/1
Abrasion tests were conducted using a 6-inch width) to determine the number of times the paint film peeled off.

Test results (test items) (Example 1) (Comparative example 1)
Scratch resistance test No scratches Significantly scratched solvent resistance test tOH No change No change MEK No change Crank-generated toluene No change No change Test items) (Example 1) (Comparative Example 1) Added thermal resistance test No change Crack generation chemical resistance test 10xllCl aqueous solution No change No change I
OχN a O11 aqueous solution Slightly cloudy Whitening abrasion resistance test 400 times 30 times based on
The thickness is 38μ using the coating agent [Nu] with the composition below.
Coat the entire surface uniformly with a gravure diagonal plate with a plate depth of 100 μm on one side of the polyester film [made by Diafoil ■].
It was dried to obtain a releasable protective layer.

Coating Nu-treated silica [mouth]・・・−−−−−−−−−−−−・−・
-------1 ・40 parts by weight (same as that used in Example 1) Pentaerythritol tetraacrylate------
1-----・---------40 parts by weight Polymethyl methacrylate--10 parts by weight Benzoquinone------- 1-・-・----
1--------------・-----5 parts by weight Ultraviolet sensitizer-----1--
−−−−・−−−−−−−−・−−1−−−−・・5
ffi quantity part [Ciba Geigy 1L Irugaki Air 184] Toluene --- 1-1 --- --- --- --- ---
-250 parts by weight of methyl ethyl ketone -250 parts by weight of the obtained releasable protective layer, apply a coating agent with the following composition,
At the same time as drying, the thin protective layer was cross-linked and cured by passing it 10 cm below an ultraviolet lamp with an output of 160 Kw/c at a running speed of 10 m/11 nm.

Uni Uni! ! "1 [ru] Polymethyl methacrylate...--2
0 parts by weight Methyl ethyl ketone tentene - 40 parts by weight Toluene - - - - - - - -
・−・−・・−−−−−・−−−−m=−・−40ff
i part or less, a pearl layer, a colored layer,
A transfer sheet was prepared by providing a vapor deposition anchor layer, an aluminum vapor deposition layer, and an adhesive layer, and transfer painting was applied to an AS resin plate in the same manner as in Example 1.

The surface properties of the transfer layer subjected to iTJ were similar to those of Example 1.

Claims (2)

[Claims] (1) In a transfer sheet which has a releasable layer, a pearl ink layer, a colored layer, and, if necessary, a metal vapor deposited layer in this order on one side of a base sheet, the releasable layer is (a) in the molecule. (b) a transparent filler whose surface is treated with an alkoxysilane having a radically polymerizable unsaturated bond in the molecule; A transfer sheet comprising a hardened layer of a material. (2) The transfer sheet according to claim (1), wherein the release layer is constituted by a cured layer in which a curable compound is crosslinked and cured by irradiation with ionizing radiation.