JPH0253885A - Transfer foil - Google Patents

Abstract

PURPOSE:To obtain a transfer foil excellent in physical properties, such as scuff resistance, pencil hardness, RCA abrasion, chemical resistance, etc., by containing a crosslinkable resin and also a thermoplastic resin in a primer and adhesive layers. CONSTITUTION:The objective transfer foil obtained by laminating a protective layer 3 constituted of a crosslinkable curable resin selected from ionizing radiation curing type resins, two-pack reaction curing type resins and thermosetting resins to the surface of a mold release sheet 2 consisting of a synthetic resin, such as polyester, PP or PE, or paper and successively laminating a primer layer 4 constituted of a thermoplastic resin, such as polymethyl methacrylate, PS or ethyl cellulose, and an adhesive layer 5 constituted of an acrylic, vinyl chloride and/or vinyl acetate copolymer, cyclized rubber, etc. The above- mentioned primer layer or adhesive layer or both contain a crosslinkable curable resin.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a transfer foil.

[Prior Art and Problems to be Solved by the Invention] Transfer foils are known in which a protective layer, a pattern layer, an adhesive layer, etc. are laminated on the surface of a base sheet. It has also been practiced to use an ionizing radiation curable resin in the protective layer of such a transfer foil to protect the surface of the transfer body after transfer.

The present invention has improved pencil hardness and
The object of the present invention is to provide a transfer foil with further improved physical properties such as RCA abrasion and scratch resistance.

[Means for Solving the Problems] In order to solve the above problems, the transfer foil of the present invention has the configuration shown below.

That is, the present invention provides: ``(1) A transfer foil having at least a release sheet, a protective layer made of a cross-linked curable resin, a primer layer containing a thermoplastic resin, and an adhesive layer; A transfer foil characterized in that at least one of the adhesive layers contains a crosslinked curable resin.

(2) The transfer foil according to claim 1, wherein at least one layer of a transparent resin layer, a colored resin layer, a pattern layer, and a metal vapor deposition layer is laminated.

(3) At least one of a transparent resin layer, a colored resin layer, and a pattern layer
The transfer foil according to claim 2, wherein the layer contains a crosslinked curable resin.

(4) The transfer foil according to claim 1 or 3, wherein the crosslinked curable resin has already been cured.

(5) The transfer foil according to claim 1 or 3, wherein the crosslinked curable resin is solid at room temperature in an uncured state and is thermoplastic.

(6) The transfer foil according to any one of claims 1 to 5, wherein the crosslinked curable resin contained in the primer layer and the adhesive layer is 20 to 70% by weight.

(7) The transfer foil according to any one of claims 1 to 6, wherein an uneven shape is formed on the protective layer side of the release sheet.

(8) The transfer foil according to any one of claims 1 to 6, wherein a moldable sheet is used as the releasable sheet.

(9) The transfer foil according to any one of claims 1 to 9, wherein an ionizing radiation-curable resin is used as the crosslinked curable resin, and a heat-sensitive adhesive made of a thermoplastic resin is used in the adhesive layer. ” is the gist.

(10) Transfer according to any one of claims 1 to 9, in which the content of the crosslinked curable resin decreases in order from the protective layer side [Example] Examples of the present invention will be described in detail below with reference to the drawings. explain.

In FIG. 1, l indicates a transfer foil, and the transfer foil 1 has a protective layer 3, a primer layer 4, and an adhesive layer 5 on the surface of a release sheet 2.
are sequentially stacked.

In principle, the material of the release sheet 2 may be one that is used for this type of transfer foil (its thickness is usually 5 to 2 μm (preferably 10 μm, more preferably 12 μm).
~50 μm.

Specific examples include polyester typified by polyethylene terephthalate, synthetic resin films such as polypropylene 1, polyethylene, and polyamide', paper, and synthetic paper. These materials can be laminated and used if necessary.

It is also possible to use a releasable sheet whose surface on the protective layer side has an uneven shape. The unevenness on the surface of the release sheet is
This determines the unevenness of the surface of the protective layer when it is transferred. If the surface after the transfer is desired to be a mirror surface, the surface of the release sheet must be a mirror surface. In addition, in decorative applications, a matte surface is often required, and in such cases, the ridges of the releasable surface can be improved by kneading a matting agent into a releasable sheet, sandblasting, mud coating, or chemical etching. It is better to use a so-called matte film whose condition has been adjusted. Furthermore, by embossing a suitable uneven pattern on the protective layer side of the release sheet, an uneven pattern can be formed on the surface of the protective layer.

The releasable sheet may be made of materials other than those mentioned above, and may also have a releasable layer provided on the surface to make the surface releasable.

This releasable layer contains a component that enables the protective layer to be peeled off from the base sheet of the releasable sheet during transfer. (same as those described later) may be made alone or by further adding a releasing substance such as wax or silicone as necessary.

It is also possible to use a moldable sheet as the releasable sheet I. Examples of such sheets include single-layer or multi-layer films such as polyvinyl chloride, polystyrene, polypropylene, polyethylene, EV OH, nylon, polyester with a low curing point, ABS, polyvinylidene fluoride, etc. A transfer foil using such a sheet I can be used for transfer during injection molding.

The protective layer 3 is made of a crosslinked curable resin and serves to prevent scratches on other layers when transferred. As the crosslinkable curable resin constituting the core layer 3, there are three types: (1) ionizing radiation curing resin (2) two-component reaction curing resin (2) thermosetting resin.

2. The ionizing radiation-curable resin has the property of being cured by irradiation with ionizing radiation. Ionizing radiation refers to electromagnetic waves or charged particle beams that have the ability to ionize substances.There are various types of radiation, but those that can be used industrially are ultraviolet rays and electron beams. Other gamma rays can also be used.

Prepolymer with ethylenically unsaturated bonds in the molecule,
Or oligomers, such as unsaturated polyesters, polyester acrylate, epoxy acrylate-1, various acrylates such as urethane acrylate, polyether acrylate, polyol acrylate, melamine acrylate, polyester methacrylate-1, polyether methacrylate-1, etc. -, one or more of various methacrylates such as polyol methacrylate, melamine methacrylate-1, etc., and a monomer having an ethylenically unsaturated bond in the molecule, such as a styrene monomer such as styrene and α-methylstyrene. methyl acrylate,
Acrylic acid esters such as 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, phenyl acrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, methacrylate ethoxymethyl methacrylate, phenyl methacrylate, methacrylic acid esters such as lauryl methacrylate, unsaturated carboxylic acid amides such as acrylamide and methacrylamide, 2-(NN-diethylamino)ethyl acrylate,
2(N,N-dimethylamino)ethyl methacrylate,
2-(N,N-diethylamino)ethyl acrylate,
W-converted amino alcohol esters of unsaturated acids such as (N,N-dimethylamino)methyl methacrylate and 1-(N,N-diethylamino)propyl acrylate, ethylene glycol diacrylate, propylene glycol diacrylate I. , neopentyl glycol diacrylate, 16-hexanethiol diacrylate 1, diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol acrylate, propylene glycol dimethacrylate, diethylene dimethacrylate 1
Mixtures of polyfunctional compounds such as ・and/or polythiol compounds having two or more thiol groups in the molecule, such as trimethylolpropane trithioglycolate, trimethylolpropanethiopropylate, pentaerythritol tetrathioglycol, etc. It is formed from a coating composition made of The coating composition is obtained by arbitrarily mixing the above-mentioned compounds, but in order to make the composition have normal coating suitability, 5% by weight or more of the prepolymer or oligomer is added. It is preferable that the monomer and/or polythiol be 95% by weight or less.

In addition, as an example of a two-component reaction-curing resin, polyurethane (
isocyanate curing agent), unsaturated polyester (isocyanate curing agent), or epoxy (amine curing agent) in a diluting solvent, and containing stabilizers and fillers as necessary. Can be mentioned. Further, examples of the thermosetting resin include known ones such as melamine resin type and polysiloxane type. Also, among the above-mentioned cross-linked curable resins, those that are solid at room temperature in an uncured state,
In addition, although it has thermoplasticity and solvent solubility, it is non-fluid (dry to the touch) and non-adhesive when painted and dried. Those which give a certain coating are preferably used.

As such, it has a radically polymerizable unsaturated group,
There are two types of thermoplastic resins:

(1) A polymer having a glass transition temperature of 0 to 250°C and having a radically polymerizable unsaturated group. More specifically, compounds obtained by polymerizing or copolymerizing the following compounds 1 to 2 and introducing radically polymerizable unsaturated groups by methods (a) to (d) described below can be used.

■ Monomers with hydroxyl groups 2N-methylol (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, 2-human 1-cogiciprobyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3- Phenoxyprovir (meth)acrylate etc.

■ Monomers with carboxyl groups - (meth)acrylic acid, (meth)acryloyloxyethyl monosuccinate, etc.

■ Monomer nigrindyl (meth)acrylate, etc. having an epoxy group.

(2) Monomers having an aziridinyl group: 2-allydinylethyl (meth)acrylate, allyl 2-aziridinylpropionate, etc.

■ Monomers having amino groups: (meth)acrylamide, diacetone (meth)acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, etc.

(2) Monomers having a sulfone group: 2-(meth)acrylamide 1'-2-methylpropanesulfonic acid, etc.

■ Monomer having an incyanate group: Diisocyanate-1 such as a 1 mole to 1 mole adduct of 2,4 toluene diisocyanate and 2-hydroxyethyl (meth)acrylate
・Adducts of radically polymerizable monomers with active hydrogen, etc.

■Furthermore, in order to adjust the glass transition point of the copolymer described in "-" and to adjust the physical properties of the cured film, the above compound and the following monomers that can be copolymerized with this compound are added. It can be copolymerized with.

Examples of such copolymerizable monomers include methyl (meth)acrylate, ethyl (meth)acrylate,
Propyl (meth)acrylate, Butyl (meth)acrylate, Isobutyl (meth)acrylate, t-Butyl (meth)acrylate, Isoamyl (meth)acrylate, Schiffr:1 Hegotosyl (meth)acrylate, 2
-Ethylhexyl (meth)acrylate and the like.

Next, the polymer obtained as described above is reacted by the methods (a) to (d) described below, and a radically polymerizable unsaturated group is introduced, thereby obtaining an ultraviolet or electron beam curable resin. .

(a) In the case of a polymer or copolymer of a monomer having a hydroxyl group, a monomer having a carboxyl group such as (meth)acrylic acid is subjected to a condensation reaction.

(b) In the case of a polymer or copolymer of a monomer having a carboxyl group or a sulfone group, the aforementioned monomers having a hydroxyl group are subjected to a condensation reaction.

(C) In the case of a polymer or copolymer of a monomer having an epoxy group, an incyanate group, or an aziridinyl group, the above-mentioned monomer having a hydroxyl group or a monomer having a carboxyl group is added in several units. .

(d) In the case of a polymer or copolymer of a monomer having a hydroxyl group or a carboxyl group, a monomer having an epoxy group or a monomer having an aziridinyl group or a diisocyanate compound and a hydroxyl group-containing acrylic acid ester monomer 1 to 1 mole of adducts are subjected to an addition reaction.

In order to carry out the above reaction, it is desirable to add a trace amount of a polymerization inhibitor such as hydroquinone and carry out the reaction while blowing dry air.

(2) has a melting point of room temperature (20°C) to 250'C,
A compound having a radically polymerizable unsaturated group. Specifically, stearyl acrylate-1~, stearyl (meth)acrylate, triacrylisocyanurate, cyclo\xanethiolcy(meth)acrylate, sylpyl:I glycol cyacrylate-1, biroglini, etc. Examples include 1-l(meth)acrylate. Further, in the present invention, the above (1) and (2) can be used as a mixture, and a radically polymerizable unsaturated monomer can also be added to them. This radically polymerizable unsaturated monomer improves the crosslinking density and heat resistance during electric radiation irradiation 1.1. Ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hex→nondiol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythryl-1-lutet( meth)acryle-I, pentaerythritol trintaerythritol hexa(meth)acryle-1-, ethylene glycol diglycidyl ether di(meth)acrylate, polyethylene glycol siglycidyl ether di(meth)acrylate, propylene glycol diglycidyl] -- Tercy(meth)acrylate, polybutylene glycol glycidyl ether di(meth)acrylate, sorbitol tetraglycidyl ether di(meth)acrylate, etc. can be used, and the ultraviolet curable resin or electron beam of Curable resin 1 (1
It is preferable to use 0.1 to 1 (10 parts by weight) per 0 parts by weight.The above materials can be sufficiently cured by electron beams, but when curing by ultraviolet irradiation, a sensitizer is used. Also usable are henzogynone, henzine, henzine ethers such as henzine methyl ether, halogenated acetophenones, biacetyls, and the like which generate radicals when irradiated with ultraviolet rays.

In order to apply the above two components to the releasable surface of the releasable sheet, known methods such as roll coating method, curtain flow coating method, wire barcoding method, gravure coating method, air knife coating method can be used. , a reverse coating method, a kiss coating method, a blade coating method, a smooth coating method, a silk screen printing method, etc., and the coating amount is about 1 μm to 10 μm when dry.

The primer layer 4 contains a thermoplastic resin and is composed of a thermoplastic resin in consideration of the adhesion between the protective layer 3 and the adhesive layer 5 or other pattern layer, and stress relaxation during friction. However, a blend of a thermoplastic resin and a cross-linked curable resin is preferred. Examples of thermoplastic resins include homocopolymers of acrylic or methacrylic monomers such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, and polybutyl acrylate, or copolymers containing these monomers, and polystyrene. , Sunalene resins such as poly α-methylstyrene and styrenic copolymer resins, ethyl cellulose,
Cellulose derivatives such as ethyl hydroxyethyl cellulose and cellulose acetate propionate, rosin, rosin-modified maleic acid resin, rosin-modified phenol resin, rosin ester resin such as polymerized rosin, polyhinyl acetate resin 1]L, hinyl chloride resin, hinyl chloride and hinyl acetate One or more of copolymers, coumaron resins, hinyltoluene resins, butyral resins, polyurethane resins, polycosdel resins, shellac, ashhia gum, Akaroy 1, mastic, etc. are used.

Further, as the crosslinked curable resin, those mentioned above can be used. The blend ratio of the crosslinked curable resin is preferably about 20 to 70%. If it exceeds this range, the adhesion will decrease, and if it is less than this range, there is no point in adding the crosslinked curable resin.

The adhesive layer 5 is involved in adhesion between the transfer layer and the transfer stopper when the transfer foil 1 is transferred, and its material may be any of those conventionally used for the adhesive layer of this type of transfer foil. It can also be used for various things.

Examples include acrylic, acrylic-styrene copolymer, vinyl chloride vinyl acetate copolymer, polyurethane chlorinated olefin, chlorinated rubber, and cyclized rubber.

In the present invention, it is preferable to blend a cross-linked curable resin into the adhesive layer 5, and it is necessary to blend a cross-linked curable resin into at least one of the pliers layer 4 and the adhesive layer 5. By blending cross-linked curable resin,
Due to the synergistic effect of increasing the total thickness of the hard film and stress relaxation by the thermoplastic resin, physical properties such as scratch resistance, pencil hardness, RCA abrasion, and chemical resistance of the transfer foil are significantly improved. In order to effectively exhibit such an effect, it is preferable to provide a layer containing a large amount of flexible thermoplastic resin between the highly hard protective layer and the adhesive layer, and more preferably, a layer containing a large amount of flexible thermoplastic resin ( It is preferable to lower the crosslinked curable resin content in order from the protective layer to the adhesive layer as in 10).

When blending the cross-linked curable resin into the adhesive layer 5, the blending ratio is preferably from 0 to 70% by weight, as in the case of the primer layer 4.

The transfer foil 1 shown in FIG. 2 has a structure in which a decorative layer 6 is provided between a primer layer 4 and an adhesive layer 5.

The decorative layer in the present invention refers to a transparent resin layer, a colored resin layer, a pattern layer, a metal vapor deposited layer, etc. alone or in combination.

For forming the transparent resin layer, the same resin as the resin constituting the primer layer described in - can be used. The colored layer is the transparent resin layer containing a coloring agent such as a pigment, and the pattern layer is formed by applying a pattern, design, pattern, etc. using ink. In addition, the metal vapor deposition layer is formed by forming metals such as aluminum, tin, silver, copper, chromium, etc. by vacuum vapor deposition, etc.
The thickness is 40 to 6 (preferably 10).It is preferable that these decorative layers are usually provided between the primer layer and the adhesive layer, but in addition, it is preferable to provide the decorative layer between the protective layer and the primer layer, between the Al layer and the release sheet. It can be provided on the surface of the adhesive layer, etc., and it is also possible to provide not only one layer but two or more layers simultaneously.

In the present invention, it is preferable to blend a crosslinked curable resin into each decorative layer except for the metal vapor deposited layer described in 2. In this case, the blending ratio of the crosslinked curable resin is preferably 3 to 30% by weight.

It is preferable to cure the crosslinked curable resin of each layer after each layer has been formed into a releasable sheet, since the curing can be carried out efficiently all at once.

Further, when using an ionizing radiation-curable resin that is solid at room temperature in an uncured state and is thermoplastic, it can be cured after being transferred to a transfer stopper.

Hereinafter, the present invention will be explained in more detail by giving specific examples.

Specific Example 1 Polyester film with a thickness of 38 μm (Toshi Lumirror)
T-70) was gravure coated with melamine resin (manufactured by Dainichiseika) to form a release layer with a thickness of 0.5 μm. After coating the treated surface of this film with 5 μm thick urethane acrylate-based ultraviolet curable resin (Moroboshi Ink Co., Ltd.), the above-mentioned ultraviolet curable resin (Moroboshi Ink Co., Ltd.)/acrylic resin-
A 1/2 blended resin was coated to a thickness of 2 μm to form a primer layer, and cross-linked and cured using a high-pressure mercury lamp.
Thereafter, an acrylic pattern ink layer was gravure coated to a thickness of 2 It'm, and then an acrylic heat-sensitive adhesive (manufactured by Showa Ink) was coated to a thickness of 2 μm. This transfer sheet was transferred to an acrylic plate (Mitsubishi rayon type) by Hiroll. Compared to the case where the primer layer is only acrylic resin, the transfer molded product created by the above method has a pencil hardness of 21
1 to 311, RCA wear value improved from 50 times to 1 (10 times).

Specific Example 2 Polyester film with a thickness of 38 μm (Toshi Lumira-T)
-70) was coated with melamine resin (manufactured by Dainichiseika Chemical Co., Ltd.) in a gravure mold to form a release layer with a thickness of 0.5 μm. After coating the treated surface of this film with an ultraviolet curable resin (manufactured by Mitsubishi Yuka Fine Co., Ltd.) to a thickness of 5 μm using gravure coating,
It was dried with 0'CX1ml1n hot air. Next, a 1/4 blend resin of the above ultraviolet curable resin (manufactured by Mitsubishi Yuka Fine Co., Ltd.)/hibinyl chloride vinyl acetate ink was coated to a thickness of 2 μm to form a primer layer. Thereafter, an acrylic pattern ink layer was gravure coated to a thickness of 2 μm, and then an acrylic adhesive (manufactured by Showa Ink) was coated to a thickness of 2 μm.

This transfer sheet was roll-transferred onto an acrylic plate (manufactured by Mitsubishi Rayon), and then cross-linked and cured using a high-pressure mercury lamp.

Compared to the case where the primer layer is only vinyl chloride vinyl acetate ink, the transfer molded product created as described above has a pencil hardness of 3H to 41] and an RCA abrasion value of 2 (1
It went from 00 times to 4 (toward 100 times).

Specific Example 3 Polyester film with a thickness of 38 μm (Toshi Lumira-T)
-70) was gravure coated with melamine resin (manufactured by Dainichiseika) to form a release layer with a thickness of 0.5 μm. Electron beam curable resin (urethane acrylate 1
Oligomer 1 (10 parts by weight, polyethylene glycol 2
0 parts by weight) by roll coating to a thickness of 6 μm, and then a brimer layer (the above electron beam curable resin; urethane resin)
11) was coated with a thickness of 3 μm, and electron beam irradiation was performed using a scanning type electron beam irradiation machine. Accelerating voltage 17
The electron beam was irradiated with a 5 KV beam and a current of 36 mA at an irradiation dose of 10 Mrad.

After that, a 2 μm thick acrylic pattern ink layer was gravure coated, and then 2 μm of acrylic adhesive (manufactured by Showa Ink) was applied.
The film was made with a thickness of μm. 5mm using this transfer sheet
Roll transfer was carried out onto a mm guacrylic plate (manufactured by Hishishi Rayon).

The transfer molded product created by the above method does not cause any problems in transfer to a pencil hardness transfer body compared to a case where the primer layer is made of only urethane resin.

Furthermore, by using a releasable seal 1 in which an uneven shape is formed on the protective layer side, the uneven shape can be easily imparted to the protective layer.

Furthermore, if a moldable sheet is used as the release sheet, it is possible to transfer the image onto the surface of the molded product during injection molding.

[Brief explanation of the drawing]

FIGS. 1 and 2 are longitudinal sectional views showing the transfer foil. ■... Transfer foil 2... Release sheet 3... Protective layer 4... Primer layer 5... Adhesive layer 6... Decorative layer 3 H to 4H, RAC abrasion 6 (10 times to 1 (100
The transfer foil of the present invention can be used without rubbing with steel wool, and with immersion in ethanol 1 (10%) for 24 hours. Because it contains a crosslinked curable resin and also a thermoplastic resin, it has excellent physical properties such as scratch resistance, pencil hardness, RCA abrasion, and chemical resistance.Also, it is transparent. Decorative properties can be further improved by providing decorative layers such as a resin layer, a colored resin layer, a pattern layer, a metal vapor deposition layer, etc. Also, by making at least IN of each decorative layer a layer containing a crosslinked curable resin. Decorative properties can be improved while maintaining the above physical properties.

Claims (10)

[Claims] (1) In a transfer foil having at least a release sheet, a protective layer made of a cross-linked curable resin, a primer layer containing a thermoplastic resin, and an adhesive layer, at least l of the primer layer and adhesive layer is A transfer foil characterized in that the layer contains a crosslinked curable resin. (2) The transfer foil according to claim 1, wherein at least one layer of a transparent resin layer, a colored resin layer, a pattern layer, and a metal vapor deposition layer is laminated. (3) At least one of a transparent resin layer, a colored resin layer, and a pattern layer
The transfer foil according to claim 2, wherein the layer contains a crosslinked curable resin. (4) The transfer foil according to claim 1 or 3, wherein the crosslinked curable resin has already been cured. (5) The transfer foil according to claim 1 or 3, wherein the crosslinked curable resin is solid at room temperature in an uncured state and is thermoplastic. (6) The transfer foil according to any one of claims 1 to 5, wherein the crosslinked curable resin contained in the primer layer and the adhesive layer is 20 to 70% by weight. (7) The transfer foil according to any one of claims 1 to 6, wherein an uneven shape is formed on the protective layer side of the release sheet. (8) The transfer foil according to any one of claims 1 to 6, wherein a moldable sheet is used as the releasable sheet. (9) The transfer foil according to any one of claims 1 to 9, wherein an ionizing radiation-curable resin is used as the crosslinked curable resin, and a heat-sensitive adhesive made of a thermoplastic resin is used in the adhesive layer. (10) The transfer foil according to any one of claims 1 to 9, wherein the content of the crosslinked curable resin decreases in order from the protective layer side.