JPH0248936A - transfer foil - 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 foil, and particularly to a transfer foil that provides a flexible transfer layer that is excellent in scratch resistance, impact resistance, and abrasion resistance. Furthermore, the present invention relates to a transfer foil that provides a matte transfer layer in addition to the above properties.

[Conventional technology and problems]

In recent years, plastic materials, including engineering plastics, have been widely used as substitutes for inorganic materials such as metal materials and glass, taking advantage of their properties such as toughness and workability. However, since the surface hardness and scratch resistance are poor, it is necessary to provide a surface releasable protective layer.

Conventional techniques for hardening plastic surfaces include:
Coatings have been carried out with organosiloxane-based, melamine-based thermosetting resins, and polyfunctional acrylic-based photocuring resins.

However, conventional scratch-resistant surface releasable protective layers using thermosetting resins or photocuring resins lack flexibility and are prone to cracking, which is a problem.

Therefore, when forming a surface releasable protective layer on a curved molded product or synthetic resin film, it may be difficult to process the surface into a curved shape, or cracking may occur due to bending. I was not satisfied with the layer. Furthermore, even when used as a surface releasable protective layer on a flat surface, there are problems in that once scratches occur, they do not recover or that the scratches are conspicuous.

Further, in ordinary decorative applications, it is often required that the surface after transfer be made matte. Conventionally, the transfer foil used to transfer a releasable protective layer with a matte surface is one in which the releasable protective layer is applied to a base film with fine irregularities and the irregularities are copied. So-called "mat materials" made of fine powder such as silica and polyethylene
There is a type in which a releasable protective layer containing added is applied to a base film. However, the method of copying the unevenness is not suitable for achieving a large matte effect. Furthermore, when adding a matte material made of fine powder such as silica or polyethylene, the elasticity of the releasable protective layer containing these materials decreases, the abrasion resistance of the surface decreases, and the There is also the problem that it is difficult to transfer, the matting effect is small, and depending on the viewing direction, the matting may not be achieved.

Therefore, an object of the present invention is to provide a transfer foil capable of providing a transfer layer having flexibility, scratch resistance, abrasion resistance, etc.

Another object of the present invention is to provide a transfer foil that has the above characteristics and can provide a transfer layer with a good matte surface.

[Means for solving problems]

In view of the above problems, as a result of intensive research, we have developed a urethane compound in which a diol having a specific molecular weight and a compound having a polymerizable unsaturated group are introduced into the skeleton as a flexible ionizing radiation-curable resin. It has been discovered that it is possible to obtain a transfer foil having a releasable protective layer that is ionizing radiation-curable and has good scratch resistance, abrasion resistance, and flexibility. In addition, paints containing so-called "bead pigments," which are fine pigment powder coated with synthetic resin on the outside as a coloring and matting agent, have recently been put into practical use. discovered that it is possible to form a suede-like coating film with good matting properties, no directionality in the matting effect, and a soft texture.

The present invention was completed based on the above findings.

That is, the transfer foil of the present invention is characterized in that a releasable protective layer made of a flexible ionizing radiation-curable resin is laminated on a base sheet.

Furthermore, in the present invention, by using a bead pigment dispersed in the ionizing radiation curable resin, the transfer foil can provide a releasable protective layer having a good matte surface in addition to the above properties. .

The invention will be explained in detail below.

In principle, the material of the base sheet may be any material used for this type of transfer sheet, and its thickness is usually preferably 5 to 200 μm, more preferably 12 to 5 μm.
It is 0 μm. Specific examples include films, papers, and synthetic papers made of polyesters such as polyethylene terephthalate, polyolefins such as polypropylene and polyethylene, polyamides such as nylon, and synthetic resins such as polyvinyl chloride, polyarylates, and polycarbonates. These can be laminated and used if necessary.

The unevenness on the surface of the base sheet determines the unevenness on the surface of the releasable protective layer when it is transferred.

If the surface after the transfer is desired to be a mirror surface, the surfaces of these base sheets must also be mirror surfaces. Furthermore, since a matte surface is often required in decorative applications, a matte film whose luster has been adjusted by kneading a matte material, sandblasting, or chemical etching may be used as the base sheet.

Note that the base sheet may be made of materials other than those mentioned above, and may also be one having a releasable layer provided on the surface to make the surface releasable. This releasable layer contains a component that enables the cured resin layer to be peeled off from the base sheet during transfer, and specifically includes a suitable vehicle (examples of vehicles include those described below as vehicles for ordinary ink compositions). (same) Can be made alone or by adding a releasing substance such as wax or silicone if necessary.

The releasable protective layer uses an electron beam curable resin that remains flexible even after curing. Such electron beam curable resins are mainly composed of monomers having at least one radically polymerizable unsaturated group in one molecule of the urethane acrylate oligomer. The urethane acrylate oligomer functions as a soft segment, and the monofunctional or polyfunctional monomer functions as a hard segment. The urethane acrylate oligomer typically has a diisocyanate and a hydroxyl group at both ends, and has a weight average molecular weight of 200 to 5,000.
The diol is bonded to an acrylate compound having a hydroxyl group at the terminal and a radically polymerizable unsaturated group.

Moreover, instead of using the above-mentioned urethane acrylate oligomer alone, a monomer having at least one radically polymerizable unsaturated group can be contained in one molecule. In this case, the urethane acrylate oligomer functions as a soft segment, and the monofunctional or polyfunctional monomer functions as a hard segment.

The surface-releasable protective layer formed by curing such a resin composition with ionizing radiation is thought to have a phase-separated structure. By adjusting the mixing ratio of oligomer and monomer, the phase separation structure can be controlled, thereby controlling the scratch resistance, flexibility, and bendability.

The above electron beam curable resin composition will be explained in detail below.

The diisocyanate that can be used in the present invention is an aliphatic or aromatic diisocyanate compound having two isocyanate groups in one molecule, such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2.4-)lylene diisocyanate, etc. Ne), 2.6-)
lylene diisocyanate, 4,4-diphenylmethane diisocyanate), 1,5-naphthalene diisocyanate, 3,3-dimethyl-4,47-difnylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate), 1,3-bis (Methyl isocyanite) cyclohexane, trimethylhexamethylene diisocyanate, etc. can be used alone or in combination of two or more.

In particular, inphorone diisocyanate, hexamethylene diisocyanate, etc. are preferred in order to have weather resistance.

Examples of diols having hydroxyl groups at both ends include polyester brevolimers, polyether brevolimers, and polycarbonate prepolymers having hydroxyl groups at both ends.

Examples of polyester prepolymers having hydroxyl groups at both ends include (a) addition reaction products of a diol compound having an aromatic or spiro ring skeleton and a lactone compound or its derivative or an epoxy compound; (b) an addition reaction product of a polybasic acid and a polyol; and (c) a ring-opened polyester compound derived from a cyclic ester compound, and these may be used alone or in combination of two or more.

The diol compound having an aromatic or spiro ring skeleton used in the addition reaction product (a) is, for example, CH3 -0(C112Cl(20) nH).

etc.

Further, typical examples of epoxy compounds include ethylene oxide and propylene oxide.

Next, the polybasic acids used in the condensation product (b) include saturated polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, and sepacic acid, maleic acid, fumaric acid, and itaconic acid. acid, unsaturated polybasic acids such as citraconic acid, and polyols include ethylene glycol, diethylene glycol, 1.4-7'tanediol, 1. fli-hexane glycol and the like.

Examples of polyether prepolymers having hydroxyl groups at both ends include polytetramethylene ether glycol, polyethylene glycol, and polypropylene glycol.

Examples of polycarbonate prepolymers having hydroxyl groups at both ends include Plaxel CD-210 (molecular weight 1000), Plaxel CD-220 (molecular weight 2000) manufactured by Daicel Chemical Industries, Ltd., and DN-983 (molecular weight 2000) manufactured by Nippon Polyurethane Industries, Ltd. Molecule 11000)
Polycarbonate diols such as

The diol having hydroxyl groups at both ends preferably has a weight average molecular weight of 200 to 5,000. If the weight average molecular weight is less than 200, the abrasion resistance measured by the falling sand abrasion test and the taper abrasion test will be poor;
If it exceeds the hardness, the hardening machine will not be able to obtain sufficient hardness. A more preferable range of weight average molecular weight is 500 to 3000, especially 5
00-1500.

Further, in order to show excellent wear resistance properties in the sand drop abrasion test and the taper abrasion test, polytetramethylene ether glycol, polybutylene adipate, polycarbonate diol, etc. are particularly preferred. Further, in order to provide a cured product having good flexibility, it is preferable to use a linear aliphatic diol.

Acrylate compounds that have a hydroxyl group at the end and a radically polymerizable unsaturated group bond to the isocyanate group of a urethane compound, and easily generate radicals when irradiated with ionizing radiation, resulting in a so-called unsaturated group that causes a crosslinking reaction. It is a radically polymerizable compound.

Such radically polymerizable acrylate compounds having a hydroxyl group at the end are ester compounds of acrylic acid or methacrylic acid or derivatives thereof and have a hydroxyl group at the end, such as hydroxyethyl acrylate, hydroxypropyl acrylate, Hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate 4-hydroxycyclohexyl acrylate, 5-hydroxycyclooctyl acrylate.

Polymerization represented by formula 0(:H2CH20)1 including (meth)acrylic acid ester compounds having one polymerizable unsaturated group such as 5-hydroxycyclooctyl acrylate and 2-hydroxy-3-phenyloxypropyl acrylate. Ester compounds having two sexually unsaturated groups can be used.

Next, a method for producing the above urethane acrylate oligomer will be explained.

The first step using a diisocyanate and a diol having hydroxyl groups at both ends can typically be represented by the following reaction formula.

20CN-R, -NCO+ 1Io-R2-OH→0C
N-R, -NHCO-R2-OCNH-R, -NCO・
- (1) However, R1 is a hydrocarbon group having 4 to 14 carbon atoms, and R2 is a diol residue.

The reaction temperature in the first step is 40-60℃ and the reaction time is 1-4
It's time. Although the reaction may be carried out without a solvent, it is preferably carried out in a solvent such as a ketone that has no reactivity with incyanate groups.

The second step is to react the reaction product of the first step with an acrylate compound having a hydroxyl group at the end and a radically polymerizable unsaturated group, and can typically be represented by the following formula.

However, Ro is an acrylate residue (acrylic acid ester group or methacrylic acid ester group).

Note that instead of reacting all of the incyanate residues with the radically polymerizable compound, one end is reacted with a triol such as trimethylolpropane so that three residues of the radically polymerizable compound are contained in one molecule. You can also do that.

The reaction temperature in the second step is 40-60℃ and the reaction time is 2-6
It's time. Although it may be carried out without a solvent as in the first step, it is preferably carried out in a solvent such as a ketone.

In addition, in the reaction system of the second step, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, 2.6-
Di-t-butyl-p-cresol etc. from 100 to 1100
It is preferable to add about 0 pp. In addition, triethylamine, piperazine, triethanolamine, dibutyltin dilaurate,
Stannath octoate, stannath slaurate, dioctyltin dilaurate, etc. can be added.

Monofunctional monomers that can be mixed with the urethane acrylate oligomer include acrylic acid esters such as methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, and phenyl acrylate: methyl methacrylate, Methacrylic acid esters such as ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, phenyl acrylate, and lauryl methacrylate; unsaturated carboxylic acid amides of acrylamide and methacrylamide; 2(N,N-dimethylamino)ethyl acrylate); 2-(N,N-dimethylamino>ethyl acrylate, 2-(N,N-dibenzylamino)ethyl acrylate, (N,N-dimethylamino)methyl methacrylate, 2-(N,N-dimethylamino)propyl acrylate Substituted amino alcohol esters of unsaturated acids such as N-methylcarbamoyloxyethyl acrylate, N-ethylcarbamoyloxyethyl acrylate, N-butylcarbamoyloxyethyl acrylate, N-phenylcarbamoyloxyethyl acrylate, 2 -(N-methylcarbamoyloxy)ethyl acrylate, 2-carbamoyloxyalkyl acrylate, and other carbamoyloxyalkyl acrylates.

Further, the polyfunctional monomer has two or more radically polymerizable unsaturated groups, and particularly preferred is a polyfunctional (meth)acrylate having two or more (meth)acryloyl groups. Specific examples include ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tetra (meth)acrylate, pentaerythritol tri (meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, polyethylene glycol diglycidyl ether di(meth)acrylate, propylene glycol diglycidyl ether di (meth)acrylate, polypropylene glycol diglycidyl ether di(meth)acrylate, sorbitol tetraglycidyl ether tetra(
Examples include polyfunctional (meth)acrylates such as meth)acrylate and melamine (meth)acrylate.

In order to obtain good scratch resistance, among the monofunctional or polyfunctional (meth)acrylates mentioned above, the (meth)acrylic equivalent (molecular weight/number of functional groups) is from 90 to 200, especially 1.
00 or less is preferable.

Addition of monofunctional or polyfunctional monomers changes the surface properties (hardness, etc.) after curing, but in order to obtain a coating film (soft coat) with sufficient flexibility and high resilience against scratches, It is necessary to reduce the amount of the above-mentioned monofunctional or polyfunctional (meth)acrylate added. In that case, the appropriate amount to add will vary depending on each (meth)acrylate compound.
Generally, in the case of a compound having a large number of functional groups, the amount added may be small; if it is too large, sufficient flexibility cannot be obtained. Furthermore, when the monofunctional acrylate compound has a low glass transition point, if the amount added is large, the cured product of the composition obtained by irradiation with ionizing radiation will remain tacky and will have stickiness.

Specifically, when the monomer blending amount is 30 parts by weight or less with respect to 100 parts by weight of urethane acrylate oricomer,
A soft coat can be obtained that has sufficient flexibility and flexibility, as well as abrasion resistance, and has a large resilience against scratches. In particular, when the monofunctional or polyfunctional monomer is contained in an amount of 5 to 20 parts by weight, the resulting composition cured by irradiation with ionizing radiation is rich in scratch resistance, flexibility, resilience against scratches, and flexibility.

In the present invention, a releasable protective layer having a good matte surface can be provided by dispersing bead pigments in the above-mentioned ionizing radiation curable resin composition.

The bead pigments include Fe2C0, , TiO2,
The surface of fine powder of commonly used pigments such as CaC0* and quinacridone can be coated with polyurethane, acrylic resin, epoxy resin, polyester resin, nylon, fluororesin, vinyl chloride, etc.
A material coated with an elastic resin such as vinyl acetate copolymer can be used.

The particle size of the bead pigment varies depending on the thickness of the coating film to be formed, but is in the range of 5 to 80 μm.
Particularly preferred are those in which the distribution maximum is in the range of 10 to 35 μm. If the particle size is less than 5 μm, the matting effect on the surface of the protective layer will be insufficient, and if it exceeds 80 μm, the scratch resistance and impact resistance of the protective layer will be insufficient.

The color of the bead pigment is not particularly limited and may be selected as desired. For example, if you use colorless and transparent bead pigments, you can create a deep matte coating, and by combining two or more colored bead pigments, you can create a variety of matte surfaces.

The bead pigment is added in an amount of 20 to 200 parts by weight, preferably 50 to 150 parts by weight, per 100 parts by weight of the resin component. If the amount added is too small, a sufficient matting effect cannot be obtained, and if the amount is too large, the bending resistance etc. of the protective layer will deteriorate.

Bead pigments have a larger particle size than fine silica powder.

The large-diameter particles protrude from the surface of the releasable protective layer to form irregularities, thereby producing a remarkable matting effect. Moreover, since the unevenness is large and deep, the degree of matteness is sufficient.

Furthermore, since the pigment particles are covered with an elastic resin, even if an external force is applied to the releasable protective layer, the particles will deform and absorb it, and once the external force is removed, the shape of the particles will change. Restore. Therefore, the matte appearance of the resulting coating film does not change. Moreover, since the resulting coating film has a soft feel, it is possible to impart a high-grade suede-like feel to the transfer body both in appearance and feel.

= Generally, when a paint film is formed on a smooth base film, the surface obtained by transferring the paint film is as smooth and glossy as the base film surface. It was thought that the same would happen when a matte paint containing bead pigments was applied to the film.

However, the present inventors have discovered that even when a coating film of the above-mentioned paint is provided on an object to be transferred by a transfer method, a matting effect similar to that of a spray coating film can be obtained. Although the mechanism by which such an effect is obtained is not necessarily clear, the following two mechanisms are presumed.

One of them is that when a coating film is formed on a base film, an uneven surface is created by the bead pigment on the inner surface of the coating film, that is, the surface that will be on the transferee side when transferred. As a result of the surface coming into close contact with the smooth surface of the object to be transferred, the unevenness moves to the outer surface of the coating film, which was previously smooth.

The other is that when the solvent evaporates from the coating film on the base film, the vehicle shrinks and becomes thinner, and when it is cured by ionizing radiation, the vehicle of the coating shrinks and the bead pigments protrude. This means that unevenness is formed on the outer surface of the coating.

In any case, the use of bead pigments, which have a diameter that is relatively larger than the thickness of the coating film, makes it possible to achieve matting by transfer than conventional matte materials such as fine silica powder. .

The resin composition of the present invention may also contain an ultraviolet absorber or a light stabilizer, if necessary.

Examples of ultraviolet absorbers include benzo) IJ azoles, such as 1f2-(2-hydroxy-5methylphenyl)benzotriazonope2-(2-hydroxy-3,5 ditertiary-amylphenyl)benzotriazole, and polyethylene glycol. Examples include 3=[3(benzotriazol-2-yl-5-butyl-4-hydroxyphenyl)propionic acid ester. Also, as a light stabilizer, a hindered amine type, such as 2-(3,5-
di-t-butyl-4-hydroxybenzyl)-2'-n
-butylmalonate bis(1,2,2,6-inkmethyl-4-piperidyl), bis-(1,2°2.6.6-bentamethyl-4-piperidyl) sebacate, tetrakis-(2,2,6 , 6-tetramethyl-4-piperidyl)
-1,2,3,4-butanetetracarboxylate and the like.

A significant improvement in weather resistance can be obtained by using a UV absorber and a light stabilizer together. Addition of only a UV absorber has no effect of reducing deterioration and hardly improves weather resistance. Further, although the addition of only a light stabilizer has an effect in lowering the deterioration range, it is not sufficient to improve weather resistance. The amount of the ultraviolet absorber added and the amount of the light stabilizer added are 0.01 to 10 parts by weight, respectively, per 100 parts by weight of the resin composition, particularly 0.1 to 2 parts by weight of the ultraviolet absorber and the light stabilizer. It is desirable to add 0.5 to 4 parts by weight at the same time. If the amount added is too small, there will be no effect of improving weather resistance, and if it is too large, adverse effects such as a decrease in curability and adhesion will appear.

The ionizing radiation-curable resin composition thus obtained has tackiness before curing. It is important to have tackiness because the physical properties (abrasion resistance, etc.) of the resulting coating film will not be sufficient if there is no tackiness before curing.

Next, a method of coating a releasable protective layer using the above resin composition will be explained. First, a solvent or a reactive diluent is added to the resin composition as necessary to give an appropriate viscosity, and then the resin composition is coated on a suitable substrate using a conventional coating method, such as a roll coating method, a gravure coating method, or the like.
Apply by fountain coating method, curtain flow coating method, wire bar code method, etc. The film thickness is about 3 to 40 μm. At this stage, the coating film remains tacky even when dry.

The releasable protective layer is cured by irradiation with ionizing radiation. Preferably, electron beams or ultraviolet radiation are used as the ionizing radiation.

In the case of electron beam irradiation, 100 to 300 KeV is emitted from various electron beam accelerators such as Cockroft-Walton type, bumpgraph type, resonant transformer type, insulated core transformer type, linear type, dynamidron type, and high frequency type.

Preferably, an electron beam having an energy in the range of 150 to 200 KeV is used, and the irradiation dose is 2 to 10 Mrad.

Further, in the case of ultraviolet irradiation, ultraviolet rays emitted from an ultraviolet source using a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc metal halide lamp, etc. are used.

The transfer foil of the present invention also has an adhesive layer.

As the adhesive for the adhesive layer, known adhesives can be used, such as rubber resins such as polyisoprene rubber, polyisobutyl rubber, styrene butadiene rubber, phthadiene acrylonitrile rubber, (meth)acrylic acid ester resins,
Use any adhesive such as polyvinyl ether resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, polystyrene resin, polyester resin, polyamide resin, polychlorinated olefin resin, polyvinyl butyral resin, etc. Can be done.

These resins are diluted as necessary to obtain a viscosity suitable for coating, and then coated by known coating methods such as Eververse Roll Coach Ink, roll coating, gravure coating, kiss coating, blade coating, smooth coating, etc. .

The structure of the transfer foil is basically as described above, but a pattern layer can be further provided if necessary.

Since the pattern layer is for imparting a pattern to the object to be transferred by transfer, it is always necessary in a pattern transfer foil whose purpose is to transfer a pattern. An example of a transfer foil that does not require a pattern layer is a releasable protective layer transfer foil that transfers substantially only a releasable protective layer, and in this case, it can be used as a substitute for painting.

The pattern layer is usually provided directly on the releasable protective layer or indirectly through another layer. The type of ink may be determined in consideration of the application, the structure of the transfer foil, etc.

Ordinary inks are prepared by kneading a vehicle with colorants such as pigments or dyes, plasticizers, stabilizers, other additives, or solvents or diluents.

Among the components of the ink, binders related to adhesion include, for example, ethyl cellulose, ethyl hydroxypropoxycellulose, cellulose acetate propionate, cellulose acetate derivatives, polystyrene, and poly(α-methylstyrene).
Styrene resins and styrene copolymer resins such as /N, single or copolymer resins of acrylic or methacrylic resins such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, rosin, rosin-modified phenol resin, rosin ester resin such as polymerized rosin, polyvinyl acetate resin, coumaron resin, vinyl toluene resin, vinyl chloride resin, polyester resin, polyurethane resin, butyral resin, shellac, gum arabic, acaroid, mastic, etc. One or more kinds can be selected and used.

Transfer methods include, for example, a thermal transfer method in which the object to be transferred is thermocompressed by heating and transferred together with an uncured resin layer, and an activation method in which a solvent or a solvent solution of resin is used between the transfer foil and the object to be transferred. There is a solvent-activated transfer method that uses a liquid as an intermediary.

Other interesting transfer methods include press molding, vacuum forming,
Among molding methods such as air pressure forming, vacuum pressure forming, simultaneous injection molding, extrusion molding, and calendar molding, there is a method in which transfer is performed simultaneously with molding. Furthermore, press molding, vacuum forming, pressure forming, vacuum pressure forming, etc. may be performed so as to obtain a predetermined shape after transfer.

When molding is performed after transfer, there is no need to mold into the final shape at the time of transfer. In such a case, it is better to form the layer into a simple shape such as a flat plate and focus on making sure that the layer to be transferred is in sufficient contact with the layer.

Various objects can be used as objects to be transferred when performing transfer using the transfer foil of the present invention, and examples include the following.

Papers used as base materials for decorative materials, such as bleached kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, etc.
Plastic films, such as polyethylene films, polypropylene films, polyvinyl chloride films,
Polyvinylidene chloride film, polyvinyl alcohol film, polyethylene terephthalate film, polycarbonate film, nylon film, polystyrene film, ethylene/vinyl acetate copolymer film, ethylene/vinyl alcohol copolymer film, ionomer, etc. ■Wood base materials, e.g. Wood, plywood, verticle board, etc., ■Gypsum base materials, such as gypsum board, gypsum slag board, etc., ■Fibre cement board, such as valve cement board, asbestos cement board, wood chip cement board, etc., ■Other GRC and concrete, Metal foils or sheets of iron, aluminum, copper, etc., as well as composites of each of the above-mentioned materials (1) to (2) can be used.

Furthermore, various molded products can also be used as transfer objects.

Although the material for molded products overlaps with the above-mentioned cosmetic material base material,
Examples include the following:

AAS resin, ABS resin, AC3 resin, amine resin, cellulose resin such as cellulose acetate, cellulose butyrate, ethyl cellulose, allyl resin, ethylene/α-olefin copolymer, ethylene/vinyl acetate copolymer, ethylene/vinyl chloride copolymer Coalescence, ionomer resin, MBS resin, methacrylic/styrene copolymer, nitrile resin, phenolic resin, polyamide resin, polyarylate resin,
Polycarbonate resin, polybutadiene resin, polybutylene terephthalate resin, polyethylene resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polypropylene resin, polyphenylene oxide resin, polystyrene resin, AS resin, polyurethane resin, polyvinyl chloride resin, acrylic modified polyvinyl chloride resin ,
Plastic molded products such as unsaturated polyester resin.

Extruded products of metals such as iron, aluminum, copper, and stainless steel.

If necessary, the transfer surface of these transfer objects may be subjected to pretreatment depending on the material of the transfer object surface, such as pretreatment to improve adhesion such as brimer treatment and corona treatment, painting, etc. These include adjusting the base color by using chlorine, sealing, and preventing alkali leaching from alkaline base materials such as cement.

〔Example〕

The invention will be explained in more detail with reference to the accompanying drawings and the following examples.

FIG. 1 shows a transfer foil according to an embodiment of the present invention, in which 1 is a base sheet, 2 is a protective layer made of an ionizing radiation-curable resin,
3 is a brimer layer, 4 is a pattern layer, and 5 is an adhesive layer.

Example 1 Using a 2β separable flask with heating stirring and a separable cover, inholon diison ane) 16
! 1 g of the mixture was placed in a flask, 0.2 g of di-n-butyltin dilaurate was added dropwise as a catalyst, and the mixture was heated and stirred at 40°C. Polytetramethylene ether glycol (PTG-650SN manufactured by Hodogaya Chemical, molecular weight 650) 24
5 g was gradually added so that the temperature within the system did not rise rapidly to advance the reaction. After 2 hours, 90 g of hydroxyethyl acrylate was added, the reaction temperature was raised to 60° C., and stirring was continued until the peak due to the isocyanate group at 2330 car′ in the ①R spectrum disappeared. In this way, urethane acrylate was produced with a yield of almost 100%.

On the other hand, a polyester film (manufactured by Diafoil) with a thickness of 25 μm was used as a base sheet, and one side thereof was gravure coated with a melamine resin varnish (manufactured by Dainichiseika Industries) to form a releasable layer with a thickness of 1 μm. Next, a 70% by weight solution of the urethane acrylate in isopropyl alcohol was applied onto the releasable layer by gravure coating, and dried with hot air at 100°C to form a releasable layer with a thickness of 30 lJm. formed a layer.

A scanning type electron beam irradiation machine (acceleration voltage 18
The sample was irradiated with an electron beam of 5 Mrad at V).

Furthermore, a pattern layer with a thickness of 1 μm was formed using acrylic ink [GG manufactured by Showa Ink] using a gravure printing method, and an acrylic adhesive [HS-32 manufactured by Showa Ink] was applied to the entire surface with a thickness of 3 μm using a gravure printing method. I applied it.

Using the transfer foil thus obtained, it was transferred onto the surface of an acrylic resin plate using a hot roll (surface temperature: 200°C), and after the transfer, the polyester film base sheet was peeled off.

The surface releasable protective layer of the transfer body thus obtained had a soft and moist feel.

Next, in order to evaluate the performance of the surface releasable protective layer of the obtained transfer body, the following test was conducted.

(1) RCA abrasion - Using an RCA abrasion tester, measure the number of times of friction until a change in gloss of the surface releasable protective layer occurs.

(2) Taper wear = Using a taper wear tester (wearing wheel C3-10, 1 kg load), the amount of wear reduction at 1500 revolutions was measured according to ASTM D-1044.

(3) Nail latch: Rub it with the nail of your index finger and evaluate the presence or absence of scratches on the surface releasable protective layer and changes in gloss.

(4) Bending = sudden bending at 180 °C,
Evaluation based on the presence or absence of changes such as cracking and whitening of the surface releasable protective layer.

(5) Restorability = applying a load of 1 kg/cI11 for 5 hours,
Evaluation was made based on the state of restoration 5 hours after the load was released.

In addition, similar tests were conducted to compare the performance when using a transfer foil with a surface releasable protective layer made of thermoplastic acrylic resin. The results obtained are shown in Table 1.

Table 1 A transfer foil was formed in the same manner as in Example 1 using a 25 μm thick sand mud polyethylene terephthalate film (manufactured by Toshi) as a matte base sheet. The obtained transfer foil was transferred to an acrylic resin plate in the same manner as in Example 1, and then the layered sheet was peeled off.

The surface releasable protective layer of the transfer body thus obtained has sufficient scratch resistance, abrasion resistance and flexibility, and
It also had a matte feel.

Example 3 Urethane acrylate produced in Example 1, a bead pigment made by coating a blue pigment with polyurethane and having a particle size distribution of 5 to 80 μm and a distribution maximum of about 30 μm, and a 1:1 mixture of ethyl acetate and toluene as solvents. The mixture was mixed in the following proportions to obtain a matte paint.

Bead pigment: 17 parts by weight Urethane acrylate: 13 parts by weight A 1:1 mixture of ethyl acetate and toluene: IO parts by weight A transfer foil was formed in the same manner as in Example 1, except that the above matte paint was used. After transferring the obtained transfer foil to an acrylic resin plate in the same manner as in Example 1, the base sheet was peeled off. The surface releasable protective layer of the transfer body thus obtained had sufficient scratch resistance, abrasion resistance, and flexibility, as well as sufficient matte effect and soft feel.

〔Effect of the invention〕

Since the transfer foil of the present invention has an ionizing radiation-curable releasable protective layer that has both hardness and flexibility, it is possible to provide a transfer body that has excellent scratch resistance and abrasion resistance as well as flexibility. can. Further, the obtained transfer body has a soft feel and a moist feeling. Furthermore, by making the laminated surface of the base sheet sharp or matte, a sharp or matte transfer body can be obtained. Further, by incorporating a bead pigment in the ionizing radiation-curable releasable protective layer, a suede-like transfer body having a sufficient matting effect and a soft feel can be obtained.

Moreover, since the transfer foil of the present invention is ionizing radiation-curable,
Irradiation can be performed either before or after transfer, and even if curing is performed by irradiation with ionizing radiation before transfer,
Since the releasable protective layer has sufficient flexibility, it has the advantage of not causing cracks or the like even when transferred to objects of various shapes.

[Brief explanation of the drawing]

FIG. 1 is a sectional view showing a transfer foil according to an embodiment of the present invention. 1...Base sheet 2...Release protection layer 3...Primer layer 4...Picture layer 5...Adhesive layer

Claims (5)

[Claims] (1) A transfer foil comprising a base sheet and a releasable protective layer made of a flexible ionizing radiation-curable resin laminated thereon. (2) The transfer foil according to claim 1, wherein a pattern layer and an adhesive layer are laminated on the releasable protective layer. (3) In the transfer foil according to claim 1 or 2, the flexible ionizing radiation curable resin has a diisocyanate and a hydroxyl group at both ends and has a weight average molecular weight of 200 to 5.
1. A transfer foil comprising a urethane acrylate oligomer formed by bonding a 000 diol and an acrylate compound having a hydroxyl group at the terminal and a radically polymerizable unsaturated group. (4) In the transfer foil according to claim 1 or 2, the flexible ionizing radiation-curable resin contains (a) diisocyanate and a hydroxyl group at both ends and has a weight average molecular weight of 20.
(b) a urethane acrylate oligomer formed by bonding a diol of 0 to 5,000 and an acrylate compound having a hydroxyl group at the terminal and a radically polymerizable unsaturated group; and (b) at least one radically polymerizable unsaturated group in one molecule. A transfer foil characterized by containing a monomer having a saturated group. (5) The transfer foil according to any one of claims 1 to 4, wherein the releasable protective layer contains a bead pigment.