JPS61143199A - Sheet for transfer china-painting - 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 Application Field] The present invention relates to a transfer painting sheet used when forming a transfer layer on a transfer target, and is characterized by stain resistance, scratch resistance, and resistance. The object of the present invention is to provide a sheet for transfer painting, which allows obtaining a transfer layer having excellent physical properties such as chemical resistance and solvent resistance.

[Conventional technology]

BACKGROUND ART Traditionally, transfer painting methods are often used to paint objects that are difficult to print directly. For example, there are many transfer sheets called hot stamps, which are used as a method for simple marking on paper, synthetic leather, plastic molded products, etc., and are effectively used in a wide variety of applications. Most of them have a base sheet such as polyester film, acrylic resin,
It has a multilayer structure in which a pattern layer, a metal vapor deposition layer, an adhesive layer, etc. are formed through a release layer made of rubber resin, vinyl resin, etc., and the transfer layer is formed after the transfer process. In this case, the releasable layer acts as a so-called protective layer that covers and protects the pattern layer.

By the way, in the transfer painting sheet used in the conventional transfer painting method, the above-mentioned releasable layer, pattern layer, and adhesive layer of the sheet are made of paint or printing obtained by dissolving a resin in a solvent. In particular, in order to provide scratch resistance to the releasable layer serving as a protective layer, this layer is made of a composition containing silicone oil. things are being used.

[Problem that the invention seeks to solve]

However, in the conventional transfer painting sheet, the above-mentioned pass-through layer, release layer, etc. are formed from a paint or printing ink in which a resin is dissolved in a solvent, so it is difficult to use the paint or printing ink. It is not resistant to solvents such as ester solvents, ketone solvents, aromatic solvents, etc., and its use is restricted in areas where solvent resistance is required. , marks, etc. are often screen printed, and there are drawbacks such as the inability to correct defective products using screen printing. However, in order to form a releasable layer having solvent resistance, it is sufficient that the releasable layer is formed of a polymer having a crosslinked structure, but conventional methods such as thermosetting, e.g. A method using a crosslinking agent such as incyanate or epoxy has the disadvantage that the releasable layer is difficult to peel off from the base sheet during transfer, and the releasable layer cannot perform its original function.

In addition, although the abrasion resistance of the releasable layer obtained from a composition containing silicone oil is improved by the addition of silicone oil, migration of the silicone oil (f) and damage to the releasable layer during transfer may occur. Re-transfer to the transfer layer surface is usually carried out to correct the problem of unstable peeling force or defective transfer layer.

It has drawbacks such as being unable to be painted.

[Means for solving problems]

The transfer painting sheet of the present invention is provided with a pattern layer, an adhesive layer, etc. via a release layer formed on one side of a base sheet, and the release layer includes an organopolysiloxane unit. A vinyl polymer [A] bonded in a block or graft form, a modified derivative of the polymer [A] [B], or both of these polymers [A], (B
).

The transfer painting sheet of the present invention having the above-mentioned structure is characterized by its releasable layer, so the releasable layer will be explained below.

The releasable layer in the transfer painting sheet of the present invention is a vinyl polymer [A] in which organopolysiloxane units are bonded in a block or graft form, or the polymer (:A). 'fr:.

Modified derivative [B] or both polymers of these [
A), CB), etc., and coated on at least one side of the base sheet with a coating agent containing the above-mentioned vinyl polymer [A], etc., and dried, etc. to improve mold releasability. Method of forming a layer and the vinyl polymer [A
] etc. by coating at least one side of the base sheet with a coating agent containing a composition produced by heating or the like, and then performing a post-treatment such as heating to form the above-mentioned vinyl polymer [A] on the base sheet. ] etc. to form a releasable layer.

One of the methods for obtaining a vinyl polymer [A] in which organopolysiloxane units are bonded in a block or graft form is to obtain an organopolymer having at least one siloxane unit represented by the general formula or in the molecule. This is a method of polymerizing siloxane and a radically polymerizable monomer.

By this method, the vinyl polymer [A]? The organopolysiloxane used in obtaining the organopolysiloxane may be one having at least one siloxane unit represented by the general formula (1) or general formula (2) as a siloxane unit bonded to a silicon atom. There are no particular restrictions on the molecular structure or the bonding positions of the siloxane units represented by the general formula (11 or general formula (2)), and the molecular structure may be either a linear structure or an 8-molecular chain structure. In addition, this organopolysiloxane has a molecular chain terminal such as a triorganosilyl group such as a trimethylsilyl group, a hydroxydiorganosilyl group such as a hydroxydimethylsilyl group, or a mercazotozorobyl dimethyl group. As the organic group bonded to the silicon atom other than the siloxane unit represented by the silicon formula (2), for example, organopolysiloxane having a methyl group, ethyl group, propyl group, phenyl group, trifluorozolobyl group, etc. is preferable. Furthermore, it goes without saying that this organopolysiloxane has no restrictions on the arrangement order of the siloxane units represented by the general formula (11) or general formula (2) and other organosiloxane units. All the units of the organopolysiloxane may be represented by the general formula (1) or general formula (2).

The other component, the radically polymerizable monomer, used to obtain the above-mentioned vinyl polymer [A]'a in the above method is a monomer represented by the general formula, for example, methyl methacrylate. , methyl acrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate,
Butyl methacrylate, isobutyl acrylate, inbutyl methacrylate, t-butyl acrylate, t-
Butyl methacrylate, isoamyl acrylate, inamyl methacrylate, cyclohexyl acrylate,
Cyclohexyl methacrylate, 2-ethylhexyl acrylate, 'l-ethylhexyl methacrylate, N-methylolacrylamide, 2-hydroxyethyl acrylate, 2-hydroquinethyl methacrylate,
2-Hydroxyzorobyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxy-3-phenoxyzorobyl methacrylate, 2
-Hydroxy-3-phenoxyzolopyl acrylate, acrylic acid, methacrylic acid, acryloyloxyethyl monosuccinate, glycidyl methacrylate, 2-aziridinylethyl methacrylate, allyl 2-aziridinylzolopionate, acrylamide, methacrylamide, Dia7 Containing active hydrogen and diisocyanates such as tonacrylamide, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-acrylamido-2-methylpropanesulfonic acid, and equimolar adducts of 2.4-)luene diisocyanate and 2-hydroxyethyl acrylate. Adducts with radically polymerizable monomers, vinyl esters of fatty acids such as vinyl acetate and vinyl zolopionate, styrene, and α-methylstyrene.

Monomers such as vinyltoluene, maleic anhydride, itaconic acid, and mixtures of these monomers can be used.

Another method for obtaining a vinyl polymer (A:l) in which organopolysiloxane units are bonded in a block or graft form is to add the above-mentioned radically polymerizable monomer to a mercazo polymer, which is added as necessary. Polymerization is performed in the presence of a polymerization degree regulator such as ethanol, mercaptozolopionic acid, and dodecyl mercaptan to form hydroxyl and carboxyl groups.

After obtaining a vinyl polymer having a functional group such as an epoxy group, an incyanate group, or an amino group, the vinyl polymer having this functional group is combined with a methyloxy group, a hydroxyl group, a carboxyl group, an amino group, or an epoxy group. This is a method in which a bonding reaction with a reactive organopolysiloxane having a mercapto group or the like is carried out, if necessary, in the presence of a polyvalent incyanate compound, a polyvalent engineered boxy compound, or the like.

In addition, the vinyl polymer [which is the reaction product of the vinyl polymer having the functional group obtained by polymerizing the radically polymerizable monomer described above and the reactive organopolysiloxane]
In the case of a releasable layer consisting essentially of A],
In the case where the bonding reaction between the two is performed by post-treatment such as heating, a coating agent containing a vinyl polymer having a functional group and a reactive organopolysiloxane is applied to at least one side of the base sheet. By coating and then applying post-treatment steps such as heating,
A releasable layer in the transfer painting sheet of the present invention can be formed.

There are no particular restrictions on the ratio of the organopolysiloxane and the radically polymerizable monomer in the vinyl polymer [A] that substantially constitutes the releasable layer of the transfer painting sheet of the present invention. No, but 10,000 parts of radically polymerizable monomer per 10xx parts of organopolysiloxane
It has been confirmed that a layer having sufficient mold release performance to achieve the object of the present invention can be formed in a wide range of ratios from 0.00 to 1 part by weight.

Incidentally, each polymerization to obtain the vinyl polymer [A] is performed by a conventionally known polymerization method, for example, benzoyl peroxide or t-butyl hydroperoxide.

Solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization, etc. using a polymerization initiator such as cumene hydroperoxide, α, α'-azodiine butyronitrile, etc. can be used.

Furthermore, as a component of the radically polymerizable monomer when forming the vinyl polymer [A]', one having a functional group such as a hydroxyl group, a carboxyl group, an epoxy group, an aziridinyl group, or an incyanate group is used. In this case, it is possible to thermally cure the mold release layer by utilizing the functional groups in the vinyl polymer [A] that substantially constitutes the mold release layer, and the heat resistance, It can be made into a releasable layer having excellent properties such as solvent resistance and plasticizer resistance. Incidentally, the formation of the heat-cured releasable layer involves (1) applying a coating agent containing a heat-curable vinyl polymer [A]e having the functional group to a base sheet, and then heating the base sheet (2) ) A coating agent containing two or more types of thermosetting polymers is applied to the base sheet and then heated. (3) A thermosetting crosslinking agent, such as a polyisocyanate group compound, a polyepoxy compound, or a polyaziridinyl compound, is added to the coating agent. Add a base compound, polyamino compound, etc., apply to the base sheet, and cure. (4) Apply a coating agent to which various catalysts such as dibutyltin laurylate, pyridine, etc. are added as necessary to the base sheet. , curing, and other methods can be used.

Further, the derivative CB) obtained by modifying the vinyl polymer [A] contains, for example, a hydroxyl group, a carboxyl group, an epoxy A vinyl polymer [A] obtained using a monomer having a functional group selected from A, aziridinyl, incyanate, etc., and modified by introducing a third component into the functional group. In Although,
As a typical example of this derivative CB), a radically polymerizable unsaturated group is introduced into the carboxyl group of the vinyl polymer [A] by, for example, addition reaction with glycidyl methacrylate. A releasable layer substantially composed of a polymer having a crosslinked structure introduced by irradiation with ionizing radiation is obtained, and the layer has not only scratch resistance and stain resistance but also chemical resistance and solvent resistance. It can be made to exhibit excellent properties against etc.

In addition, the method for introducing a radically polymerizable unsaturated group into the vinyl polymer [A] is as follows: (2) When the functional group is a carboxyl group or a sulfone group, a monomer having a hydroxyl group is subjected to a condensation reaction. (3) When the functional group is an epoxy group or an incyanate group.

Alternatively, in the case of an aziridinyl group, a monomer having a hydroxyl group or a monomer having a carboxyl group is subjected to an addition reaction. (4) If the functional group is a hydroxyl group or a carboxyl group, a monomer having an epoxy group or a monomer having an aziridinyl group is added. In addition, methods such as addition reaction of an equimolar adduct of a diincyanate compound and an acrylic acid ester monomer having a hydroxyl group are used. It is preferable to carry out the process in the presence of dry air while blowing dry air.

In addition, derivatives into which the radically polymerizable unsaturated group is introduced (
, B), in order to improve the crosslinking density of the derivative CB) by irradiation with ionizing radiation, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene Glycol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate,
Dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene glycol diglycidyl ether diacrylate, ethylene glycol diglycidyl ether dimethacrylate, polyethylene glycol diglycidyl ether diacrylate, polyethylene glycol diglycidyl ether dimethacrylate, propylene glycol diglycidyl ether diacrylate, propylene glycol diglycidyl ether dimethacrylate, polypropylene glycol diglydyl ether diacrylate, polypropylene glycol diglydyl ether dimethacrylate, flupitol tetraglycidyl ether tetraacrylate,
flupitol tetraglycidyl ether tetramethacrylate, etc., in an amount of 0.1 to 'io
.

It is preferable to mix about % by weight.

Methods for introducing a crosslinked structure into the derivative (B) include a method of irradiating with ionizing radiation and a method of using a radical polymerization initiator, but from the viewpoint of completing curing in a short time, a method using ionizing radiation is preferable. preferable. As the ionizing radiation, electron beams, ultraviolet rays, gamma rays, etc. can be used, and in the case of electron beams and gamma rays, it is preferably about 1 to 20 Mrad, and in the case of ultraviolet irradiation, benzoquinone, as a sensitizer,
It is preferable to use benzoin ethers such as benzoin and benzoin methyl ether, halogenated acetophenones, and biacyl which generate radicals when irradiated with ultraviolet rays. In addition, in the method using a radical polymerization initiator, a polymerization initiator such as various peroxides such as benzoyl peroxide or α,α′-azobisisobutyronyl-IJ is added to the derivative (B). It is sufficient to add about 0.1 to 1% by weight and heat above the decomposition temperature, but as a whole, the releasable layer composed of a polymer crosslinked by thermosetting is formed after the transfer is completed. Since the peeling force when peeling the transfer layer and the base sheet becomes heavy, it is preferable to have a crosslinked structure introduced by irradiation with ionizing radiation. A vinyl polymer [A] in which siloxane units are bonded in a block or graft form, or a modified derivative of the polymer [A] [B], or both of these polymers [A], (B) The removable layer substantially composed of a vinyl polymer [A] or a derivative obtained by modifying the polymer [A] [B], or a derivative thereof obtained by modifying the polymer [A], is applied to at least one side of the base sheet. The above polymer [
It can be easily obtained by coating with a coating agent containing components that produce A] and the like, followed by drying or, if necessary, post-treatment such as heating. The above-mentioned coating agent for forming the releasable layer has a solvent added to it as necessary to adjust the coating suitability, but the coating agent obtained when obtaining the polymer [A] or the derivative (B) In some cases, the reaction product solution is used as it is as a coating agent. Further, in order to improve storage stability, it is preferable to add a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether to this coating agent. In addition, the coating agent contains each component capable of producing the above-mentioned polymer [A] and derivative [B], or polymer [A] and derivative CB), and if necessary, a radically polymerizable monomer and a sensitizer. Of course, it is a homogeneous solution containing additives such as.

Of course, in the transfer painting sheet of the present invention, the releasable layer is made of the vinyl polymer [A] or the polymer [A].
] e-modified derivative [B] or a mixture thereof [A], CB), so the above-mentioned coating agent may contain, if necessary, e.g. In addition to polymers such as cellulosic resins such as ethyl cellulose and nitrocellulose, polyester resins, polyurethane resins, rosin ester resins, rubber resins such as cyclized rubber, and chlorinated polyolefin resins, colorants such as pigments and dyes, etc. It can be added as appropriate.

The method of forming a release layer on the upper surface of the base sheet using the coating agent is the same as the conventional coating method of a general coating agent, such as a roll coating method or a gravure coating method.

A base sheet, such as a polyester film, polyamide film, cellophane film, acetate film, polypropylene film, paper, or metal foil, can be used alone or if necessary, two or more types can be laminated using a coating method such as a screen coating method or a fountain coating method. It is coated on the surface of a base sheet such as a sheet to a solid content of about 0.1 to 42, and dried to form a releasable layer.

In addition, as the base sheet, for example, polyester resin,
An ink composition made by adding an extender pigment to a vehicle in which polyurethane resin, cellulose resin, or polyether resin is dissolved in a solvent, and further adding a water repellent such as silicone, an oil repellent, etc. as necessary, and a sheet. 0.5 to 0.5 on the surface
A matte sheet with micrometer-sized unevenness, or a sheet with a convex pattern layer of 5 micrometers or more on the surface of the sheet, etc. is fully utilized, and a release layer is applied to the surface of the unevenness or convex pattern layer of the base sheet. By forming the transfer pattern, the protective layer, which is the surface layer of the transferred pattern, becomes an uneven or concave pattern layer, and the transfer layer allows for easier peeling between the base sheet and the release layer. It can be used as a sheet for painting.

The most typical example of the transfer painting sheet of the present invention, which is provided with a release layer having the above-described structure, is a base sheet; - a coloring agent is contained on the surface of the release layer formed on A picture layer is printed with printing ink and dried to form a picture pattern layer which is a coloring agent layer, and then the picture pattern layer obtained in the above step is applied to the surface of the release layer. A coating agent containing a thermoplastic resin as a main component is applied so as to cover the surface of the mold releasable layer and the surface of the mold releasable layer, and is dried to form an adhesive layer. Incidentally, the irradiation of ionizing radiation applied to the mold release layer as necessary may be performed subsequent to the application and drying of the coating agent for forming the mold release layer, or may be performed after the formation of the adhesive layer. Later, it may be carried out through the adhesive layer.

In the above description, a picture pattern layer is used as the coloring agent layer, but the adhesive layer may of course be a plain coloring agent layer formed uniformly over the entire surface.

Furthermore, an intermediate layer such as a metal vapor deposited layer may be provided between the colored pattern layer and the adhesive layer.

- [Example] Hereinafter, the specific structure of the transfer decoration sheet of the present invention will be explained using manufacturing examples, and the properties of the obtained transfer decoration sheet will also be explained.

Example 1 The following composition (1) was completely sealed in a reaction vessel equipped with a heating and stirring device, and refluxed for 10 hours to perform a polymerization reaction to obtain coating material [A].

Composition (1) Methyl methacrylate 500 parts by weight Dimethylpolysiloxane (*1) 50 parts by weight Methyl ethyl ketone 500 parts by weight Toluene
500 parts by weight, then the coating material [A]'
r, one side of a base sheet made of a 25 μm thick polyester film (Nilmirror, manufactured by Toshi ■), with a 40 μm thick film
It was applied uniformly over the entire surface using a gravure solid plate, the solvent was evaporated by passing it through a drying hood at 80° C., and the entire applied coating layer was dried to the touch to obtain a releasable layer.

On the surface of the obtained releasable layer, a coating agent of the following composition (2) was printed and applied in a wood grain pattern using a halftone gravure plate, and the solvent was evaporated by passing it through a drying hood at 80°C, and then applied. The entire coating layer was dried to the touch to form a patterned layer as a coloring agent layer.

Composition (2) Polymethyl methacrylate 10 parts by weight Sepia pigment 10 parts by weight Toluene
40 parts by weight methyl ethyl ketone
40 parts by weight Next 1.1 The coating agent of the following composition (3) is applied on the releasable layer including the picture pattern layer and dried to form an adhesive layer. A transfer painting sheet [a], which is an example product, was obtained.

Composition (3) Chlorinated polyzolopyrene (manufactured by Dezumi Kokusaku Pulp) 10 parts by weight sepia pigment
10 parts by weight carbon black
1 part by weight Toluene 40 parts by weight Methyl ethyl ketone 40 parts by weight Obtained transfer painting sheet (a)'! r. The adhesive layer of sheet (a) was brought into close contact with a separately manufactured polypropylene resin plate, and the surface temperature was 200'.
Pressure 6.5kg/Crn with C silicon im roller
Pressurize and heat at a running speed of 15 m/sec, then peel off the polyester film that is the base sheet in the transfer painting sheet (a), and release the adhesive layer containing the pattern layer on the surface of the polyzolopyrene resin plate. When the release layer was transferred, the peeling between the base sheet and the release layer was smooth.
And it was done reliably.

The coefficient of dynamic friction between the surfaces of the grain pattern transfer layers of the obtained polypropylene resin plate was 0.13. In addition, the surface of the transfer layer was tested with a friction tester [manufactured by Gas Tester ■: Model FR-2].
When a reciprocating friction test was performed 1000 times with cotton cloth (Kanakin No. 3) under a load of 0.001, there was no change in the surface of the transfer layer.

For comparison, the surface of the transfer layer of a transfer sheet in which the releasable layer was formed using a coating material made of a polymethacrylic acid solution in accordance with Example 1 was tested in the same manner as described above. Many fine streaks occurred.

Example 2 0.5 parts by weight of hydroquinone, 75 parts by weight of acrylic acid and 5 parts by weight of pyridine were added to a reaction product solution obtained by refluxing the following composition (4) for io hours in a reaction vessel, and 4 parts by weight of pyridine were added at a temperature of 80°C. A coating material (B) was obtained by reacting for a period of time.

Composition (4) Methyl methacrylate 200 parts by weight Glycidyl methacrylate 142 parts by weight Dimethylpolysiloxane (*1) 20 parts by weight Toluene
300 parts by weight methyl ethyl ketone
300 parts by weight of benzoyl peroxide 1 part by weight The obtained coating material CB) was applied uniformly over the entire surface on one side of a base sheet made of a 25 μm thick polyester film (manufactured by Diafoil ■) using a gravure plate of 40 ItrIL. , and dried to obtain a releasable layer.

Thereafter, a picture pattern layer, which is a coloring agent layer with a wood grain pattern, was formed in the same manner as in the recipe for obtaining the transfer painting sheet [a] of Example 1. ◇Next, a mold release layer containing the picture pattern layer was formed. A coating agent of the following composition (5) is applied on the sexual layer,
It was coated uniformly with a gravure solid plate with a 60μ film quality, and after drying, it was rolled up into a roll.
By irradiating the sheet, a sheet for transfer painting [b], which is an example of the present invention, was obtained.

Composition (5) Chlorinated polypropylene (manufactured by Dezumi Kokusaku Valve) 10 parts by weight Titanium white 10 parts by weight Hydroquinone
1 part by weight toluene
40 parts by weight of methyl ethyl ketone 40 parts by weight The obtained transfer painting sheet (b) e was operated in the same manner as the transfer painting sheet h (a) in Example 1 to obtain a polyzolopyrene resin plate having a transfer layer. The separation between the base sheet and the releasable layer in transfer painting sheet 1-(b) was 120 V15 crn width.

The coefficient of dynamic friction between the surfaces of the transfer layers of the wood grain pattern of the obtained polyzolopyrene resin plate was 0.14, and the surface of the transfer layers was
Using the above-mentioned friction tester, under a load of 200 g, a cotton cloth impregnated with ethyl acetate, toluene, methyl ethyl ketone, and ethyl alcohol (Kanakin No. 3) was tested at 100 g.
A friction test in which the transfer layer was moved back and forth several times was conducted, and there was no change in the surface of the transfer layer.

Example 3 Instead of the 5 Mrad γ-ray irradiation during the process of obtaining the transfer painting sheet [b] in Example 2, an electron beam of 3 Mrad accelerated to 175 KV in a nitrogen gas atmosphere was used. The same steps as those in Example 2 were applied to produce transfer painting sheet 1, which is an example product of the present invention.
-(C)'lz obtained.

The transfer layer transferred using the obtained transfer painting sheet [C] is the same as the transfer painting sheet (b) in the above example.
It had properties equivalent to those of the transfer layer formed using 'r.

Example 4 1 part by weight of benzoquinone was added to a reaction product solution obtained by refluxing the following composition (5) for 10 hours in a reaction vessel to stop the reaction, and 2-hydroxyethyl acrylate and 2.
Equimolar adduct with 4-toluene diisocyanate 640
5 parts by weight and further 5 parts by weight of dibutyltin silaurylate.
0 parts by weight was added, and the reaction was carried out at 80° C. for 5 hours while blowing dry air.

Composition (5) Methyl methacrylate 400 parts by weight 2-hydroxyethyl methacrylate 260 parts by weight Dimethylpolysiloxane (*2) 24 parts by weight α, α'-
Azobisisobutyronitrile 5 parts by weight Ethyl acetate 4100 parts by weight Next, UV sensitizer [Irgacure 184° manufactured by Ciba Geigy ■] 100 parts by weight
Parts by weight and trimethylolpropane triacrylate 15
0 parts by weight were added to obtain an ultraviolet curable coating material CD)'e.

The obtained coating material CD) was uniformly applied to one side of a 25 μm thick polyester film at a ratio of 1 t (solid content)/rn', dried, and an output of 80 KW/Cm was applied in a nitrogen gas atmosphere. Running speed 10m below the ultraviolet lamp with
The mold releasable layer was completely formed by passing at a speed of n/min.

Next, a picture pattern layer with a wood grain pattern was formed on the surface of the release layer in the same manner as in the formation of the picture pattern layer in Example 1, and then the following composition was applied on the release layer including the picture pattern layer. A transfer painting sheet (d), which is an example of the present invention, was obtained by applying and drying the coating material (6) to form an adhesive layer over the entire surface.

Composition (6) Methyl methacrylate-butyl methacrylate (60mol
9J-40mo196) Copolymer 10 parts by weight Sepia pigment 5 parts by weight Titanium white 10 parts by weight Toluene
32 parts by weight methyl ethyl ketone
43 parts by weight of the obtained transfer painting sheet) (
The transfer painting operation using d) was carried out on the surface of the ABS resin board under the same conditions as the transfer painting conditions described in Example 1 to form a transfer layer with a wood grain pattern.

The resulting transfer layer on the surface of the ABS resin plate had excellent resistance to various solvents, similar to the transfer layer obtained in Example 2.

[Action and effect]

In the transfer painting sheet of the present invention, the releasable layer of the sheet is made of a vinyl polymer [A] in which organopolycloxane units are bonded in a block or graft form, or a modified polymer [A].・The transfer layer obtained by the transfer painting sheet of the present invention has the above-mentioned releasability. The layer acts as a protective layer.

However, in the transfer painting sheet of the present invention, the base sheet can be easily peeled off in the transfer process, and the resulting transfer layer has stain resistance and scratch resistance.

It exhibits excellent properties such as chemical resistance and solvent resistance.

Claims (2)

[Claims] (1) In a transfer painting sheet comprising a pattern layer, an adhesive layer, etc. via a release layer formed on one side of a base sheet, the release layer has organopolysiloxane units in block or Substantially composed of a vinyl polymer [A] bonded in a grafted manner, a modified derivative of the polymer [A] [B], or both of these polymers [A] and [B]. A transfer painting sheet characterized by: (2) Vinyl polymer [A], a modified derivative of the polymer [A] [B], or both of these polymers [
The transfer painting sheet according to claim 1, wherein A] and [B] are polymers having a crosslinked structure.