JPH11277990A - Transfer foil, its manufacture, and manufacture of molded product using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a transfer foil for giving a protective layer having a chemi cal resistance and a wear resistance without generating a crack at the time of transferring, a method for transferring it, and a method for manufacturing a molded product using it. SOLUTION: The transfer foil is formed by coating a base material sheet 1 with a liquid-like or sticky material-like protective layer 2 composition containing a reactive polymer A having 10, 000 to 100, 000 of a weight-average molecular weight and in which an average of 15 or more of (meth)acryloyl groups are added to one molecule and a monomer or oligomer B having 3 or more of functional groups at a ratio of A:B=20 to 80:80 to 20, and 0 to 15 wt.% of a photopolymerization initiator, preliminarily emitting an electron beam 3 of 0.05 to 2 Mrad to a printable and windable state, and forming a design layer and an adhesive layer. The foil is stuck on a molding, the sheet 1 is removed, or before the sheet 1 is removed, an ultraviolet ray 7 of 50 mJ/cm<2> or more or an electron beam 6 of 1 Mrad or more is emitted onto the sheet 1, and it is finally crosslinked.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a general transfer foil and a transfer foil for in-molding which are excellent in abrasion resistance and chemical resistance and do not cause cracks at corners or curved surfaces of a molded article. The present invention relates to a method for producing a molded article having excellent wear resistance and chemical resistance.

[0002]

2. Description of the Related Art Conventionally, as a method for forming a protective layer on the surface of a molded article, a transfer foil having a protective layer formed on a substrate sheet having releasability is bonded and cured to the surface of the molded article by some means. Then, a transfer method of peeling the base sheet is known. This is performed at a different time between the production of the molded article and the transfer by the transfer foil.

Further, a transfer foil is sandwiched in a molding die, a resin is injected and filled in a cavity, and a resin molded product is obtained by cooling. At the same time, the transfer foil is adhered to the surface of the resin molded product. There is an in-mold transfer method. The transfer foil used for this is called an in-mold transfer foil.

[0004] The present invention addresses the protective layer of the transfer foil. As the protective layer of the transfer foil, (1) thermosetting resin (2) active energy ray-curable resin (3) two-step active energy ray-curable resin is generally used. Thermosetting resins are the most commonly used. It is applied to the base sheet in a liquid state and cured by heat to obtain a protective layer. Large scale equipment is unnecessary and easy to use. The term “active energy ray-curable resin” is a term that encompasses an ultraviolet ray-curable resin and an electron beam-curable resin. The UV-curable resin protective layer is applied in a liquid state to the base sheet and cured by applying ultraviolet rays. An electron beam-curable resin protective layer is applied in a liquid state to a substrate sheet and cured by applying an electron beam. The term active energy rays, including both, is not a mature term.

[0005]

[Problems to be solved by the invention]

(1) Disadvantages of the thermosetting resin protective layer The transfer foil of the thermosetting resin protective layer uses a thermosetting resin that has been crosslinked and cured by heating as the protective layer, and the transfer foil is transferred to an object. The thermosetting transfer foil protective layer has poor chemical resistance and abrasion resistance on the surface of the protective layer. It cannot be used as a protective film for molded products that require strong chemical and abrasion resistance.

(2) Disadvantages of the active energy ray-curable resin protective layer The transfer foil of the active energy ray-curable resin protective layer uses an active energy ray-curable resin cross-linked and cured by applying an active energy ray as a protective layer. Then, the transfer foil is transferred to the object. The active energy ray transfer foil protective layer can improve chemical resistance and abrasion resistance by increasing the amount of energy ray irradiation and increasing the crosslinking density of the resin. However, when the crosslinking density is increased, the protective layer becomes too hard and brittle. Since there is not sufficient flexibility, cracks occur in the protective layer located at the curved surface and the corner of the molded product during transfer.

(3) Disadvantages of the two-step active energy ray-curable resin protective layer Another method of using an active energy ray (ultraviolet ray, electron beam) curable resin as the protective layer is as follows. There has also been proposed a method of irradiating an active energy ray in a first step to partially cross-link and cure a solid-state resin, and after the transfer, irradiating an active energy ray again in a second step to completely cure the active energy ray-curable resin. In the first stage, the solid-state resin is irradiated with active energy rays to be cured in the middle. If the flexibility is maintained well, cracks should not occur during transfer.

JP-A-63-126797, JP-A-63-126797
JP-A-132095 and JP-A-63-153200 show a method of half-curing a thermoplastic ultraviolet-curable or electron-beam-curable resin which is solid at room temperature in an uncured state and is thermoplastic. However, since the protective layer composition is solid before preliminary ultraviolet or electron beam crosslinking, there is very little molecular movement. Irrespective of the amount of ultraviolet rays or electron beams irradiated in the final cross-linking, the radical reaction hardly proceeds, so that sufficient surface hardness cannot be obtained.

[0009] The two-stage irradiation has the following disadvantages. If the amount of active energy ray irradiation is insufficient in the first stage irradiation, the solidity of the active energy ray resin is small in the number of cross-linking points, so the thermoplasticity is large, and it flows due to heat during transfer or in-mold and deforms or flows with the picture. Or cause a phenomenon. On the other hand, if the irradiation amount of energy rays in the first stage is excessive, cracks are likely to occur in the protective layer at the position of the curved surface of the molded product during transfer. In addition, peeling is likely to occur between the ink and the protective layer.

[0010]

Means for Solving the Problems As a result of repeated studies on a daily basis, the inventors have wound up a special liquid adhesive protective layer composition, pre-crosslinked with an electron beam until a printable state is obtained, and printed an adhesive layer. It has been found that the above problem can be solved by transferring or in-molding and then again performing final crosslinking with ultraviolet rays or electron beams.

The method for producing a molded article according to the present invention comprises the steps of: A: a reactive polymer having a weight-average molecular weight of 10,000 to 100,000, and an average of 15 or more (meth) acryloyl groups added per molecule; B: a monomer or oligomer having 3 or more functional groups, wherein the ratio of A to B is 20 to 80:80 to 20; C: protection of a liquid or sticky substance containing 0 to 15% by weight of a photopolymerization initiator Apply layer composition and apply 0.05Mrad to 2M
Pre-irradiation of rad electron beam to make it printable and windable, form a pattern layer, an adhesive layer to form a transfer sheet, paste it on the molded product, remove the base sheet, or before removing the base sheet This is a method of irradiating an ultraviolet ray of 50 mJ / cm ² or more or an electron beam of 1 Mrad or more from the top of the base sheet to perform final crosslinking. This is a method of transferring a protective layer to a molded article.

The transfer foil itself is also novel, and the emphasis of the present invention is rather on here. The transfer sheet according to the present invention has a base sheet and a base sheet coated thereon. A: weight average molecular weight of 10,000 to 100,000; (meth) acryloyl groups are added on average to 15 or more per molecule. B: a monomer or oligomer having 3 or more functional groups, wherein the ratio of A to B is 20 to 80:80 to 20; C: 0.05 Mra containing 0 to 15% by weight of a photopolymerization initiator
The protective layer is preliminarily irradiated with an electron beam of d to 2 Mrad, and an adhesive layer is formed on the protective layer. If a picture is required, a picture layer is further formed on the protective layer, and an adhesive layer is placed thereon.

The transfer foil of the present invention can also be used for in-mold transfer. In the in-mold transfer method of the present invention, a base sheet and a base material sheet are coated. A: weight average molecular weight of 10,000 to 100,000; (meth) acryloyl group is 15 or more per molecule on average B: a monomer or oligomer having 3 or more functional groups, the ratio of A to B is 20 to 80:80 to 20, C: 0 to 15% by weight including a photopolymerization initiator. 05Mra
a protective layer pre-irradiated with an electron beam of d to 2 Mrad, and an adhesive layer formed on the protective layer. If a pattern is required, a pattern layer is further formed on the protective layer, and an adhesive layer is formed thereon. The transfer foil of the structure on which is placed is placed in a mold in advance, and the resin is poured into the mold and cured to form a molded article. The molded article is taken out of the mold, and the base material sheet is peeled off or the base material is removed. Before removing the sheet, from the top of the base sheet, a protective layer of 50 mJ / cm
^The final cross-linking is performed by irradiating ^two or more ultraviolet rays or an electron beam of 1 Mrad or more.

In the present invention, a special resin composed of a reactive polymer, a monomer, and an oligomer is used for the protective layer composition, instead of a thermoplastic resin as in the conventional transfer foil, as shown below. It is necessary that the protective layer composition be liquid or sticky at room temperature. Do not be solid from the start. It is important that it be liquid or sticky at first. Irradiation with active energy rays in two stages is performed, and an electron beam of a certain range of energy (0.05 Mrad to 2 Mrad)
Is pre-irradiated first. After the pattern printing and transfer to the molded product, an electron beam (1 Mrad or more) or ultraviolet ray (50 mJ / cm ² or more) of a certain range of energy is finally irradiated.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION According to the present invention, a special protective layer composition described below is applied to a substrate sheet, pre-crosslinked by an electron beam, an adhesive layer is formed thereon, and transferred to a molded article. ,
Before the base sheet is removed or the base sheet is removed, the base sheet is finally crosslinked by ultraviolet rays or electron beams.

FIG. 2 shows the process. FIG. 2A shows a state in which the protective layer composition is applied to the base sheet 1. At this time, the composition is in a liquid or sticky state. In FIG. 2 (2), preliminary cross-linking is performed by an electron beam. Thereby, printing and winding are possible. After forming the protective layer as shown in FIG. 1, the protective layer can be once wound around a roll. Following the formation of the protective layer and the preliminary irradiation of the electron beam, a pattern layer and an adhesive layer may be formed and then wound around a roll. When the protective layer, the picture layer, and the adhesive layer are formed at different places, they can be wound into a roll immediately after covering the protective layer, and then transported and stored.

As shown in FIG. 2 (3), if necessary, a picture layer 8 is formed on the protective layer 2, and an adhesive layer 9 is further formed thereon. The picture layer 8 may be inserted in order to provide decorativeness. The adhesive layer 9 is essential, but the picture layer 8 may not be present. Thus, the transfer foil 5 was completed. In that state, it is wound up in a roll and stored and transported. FIG. 3 shows a cross section of a transfer foil 5 having a base sheet 1, a protective layer 2, a picture layer 8, and an adhesive layer 9. FIG. 4 shows a cross section of the transfer foil 5 which is composed of only the base sheet 1, the protective layer 2 and the adhesive layer 9 and has no picture layer 8.

When coating a plastic molded product, a metal molded product, or the like, the molded product is covered by applying an adhesive layer of a transfer foil to the surface of the molded product. FIG. 5 shows the transfer situation. The adhesive layer 9 of the transfer foil 5 is applied to the surface of the
Press strongly while heating. The transfer foil 5 adheres to the object 4 by the action of the adhesive layer 9. Only the base sheet 1 is peeled off. The protective layer 2 comes out on the outermost surface. As shown in FIG. 1 (3) or FIG. 2 (4), 50 mJ / cm ²
The above ultraviolet ray 7 or the electron beam 6 of 1 Mrad or more is applied for final crosslinking. The above is the process of manufacturing the transfer foil and attaching the transfer foil to the molded product.

(1) The protective layer of the present invention is characterized by its material. The protective layer composition according to the present invention includes: A: a reactive polymer having a weight average molecular weight of 10,000 to 100,000, and an average of 15 or more (meth) acryloyl groups added to one molecule; B: a monomer having 3 or more functional groups; Oligomers, wherein the ratio of A to B is 20 to 80:80 to 20, and C is a composition containing 0 to 15% by weight of a photopolymerization initiator.

[A. Conditions for Reactive Polymer A] The reactive polymer A has a weight average molecular weight of 10,000 to 100,000. 1
If it is less than 10,000, even when copolymerized with a monomer or oligomer, the molecular weight is too small and the dissolution rate of the ink in the solvent is faster than the evaporation rate of the solvent, so that dissolution, swelling, and cracks occur during printing, which is not preferable. . Conversely, if the weight average molecular weight is more than 100,000, the solubility in a solvent is remarkably reduced, it is difficult to add an acryloyl group, and the viscosity of the solution is high, and handling such as coating is difficult.

The average of the number of (meth) acryloyl groups added to the reactive polymer is preferably 15 or more per molecule. 1
If the number is less than 5, it becomes difficult to obtain a sufficient hardness by final crosslinking even when copolymerized with a monomer or oligomer. Since the reactive polymer in this state has a large molecular weight after evaporating the solvent, it is often in a solid state.

[A. Ratio of Reactive Polymer A] In the present invention, the weight ratio of the reactive polymer A to the monomer / oligomer B is A: B = 20 to 80:80 to 20. That is, 0.2 ≦ A / (A + B) ≦ 0.8 or 0.2 ≦ B /
(A + B) ≦ 0.8. 0.25 ≦ A
/ B ≦ 4. If the reactive polymer component is less than this range (less than 20%), even if it is copolymerized with a monomer or oligomer, the apparent molecular weight is small and the dissolution rate in the solvent, which is the solvent of the ink, is faster than the evaporation of the solvent. And cracks and the like are generated, which is not preferable. Conversely, the reactive polymer component exceeds this range (80%
In the case of (excess), the protective layer composition is often a solid, the molecular movement is very small, and no radical reaction progresses even when irradiated with ultraviolet rays or electron beams in the final crosslinking, so that it is difficult to obtain a sufficient surface hardness.

[C. Kinds of Reactive Polymer A] Examples of reactive polymers include (meth) acryloyloxylethyl isocyanate adduct to styrene-2-hydroxyethyl (meth) acrylate polymer and mono-styrene to styrene-2-hydroxyethyl (meth) acrylate polymer. (Meth) acryloyloxyethyl urethanized tolylene monoisocyanate adduct, styrene-2-hydroxyethyl (meth) acrylate polymer mono (meth) acryloyloxyethyl urethanized isophorone monoisocyanate adduct, styrene-glycidyl (meta ) Acrylate polymers to (meth) acrylic acid adducts and the like. Styrene is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, (meth) Hexyl acrylate may be replaced with (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl vinyl acetate, vinyl toluene, one or more of α- methyl styrene.

In place of 2-hydroxylethyl (meth) acrylate, ethylene glycol (meth) acrylate, diethylene glycol mono (meth) acrylate and the like can be mentioned. In place of glycidyl (meth) acrylate, bisphenol A-diglycyl ether (meth) And acrylic acid monoadducts.

[D. Ratio of monomer / oligomer B] 0.2 or less B / (A + B) ≦
Add in the range of 0.8. The meaning of this range is also described in the section on polymers. If the polymer alone or the polymer exceeds 80%, it becomes solid at room temperature. By the addition of the monomer / oligomer, the state at normal temperature before the preliminary cross-linking with the electron beam becomes a liquid state and a sticky state instead of a solid state. 0.2 to make the initial state liquid / adhesive
Addition of 0.8 monomer / oligomer B is essential.
The presence of the monomer / oligomer leads to an increase in the crosslink density in the final crosslink and is necessary for obtaining a sufficient surface hardness in the final crosslink. Conversely, if the proportion of the monomer / oligomer B is too large, the apparent molecular weight is too small when copolymerized with the polymer, and the dissolution rate in the solvent is faster than the evaporation of the solvent,
Dissolution, swelling, cracking, etc. occur during printing. Therefore, the ratio of monomer / oligomer is 0.2 ≦ B / (A + B) ≦
0.8.

The number of functional groups of the monomer or oligomer to be copolymerized is preferably 3 or more. If the number of functional groups is less than 3, it will be difficult to obtain sufficient hardness when copolymerized.

[E. Types of Monomers and Oligomers] Examples of monomers or oligomers having 3 or more functional groups include the following. Dipentaerythritol hexa (meth) acrylate, dipentaerythritol dipenta (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropanetri (meth) A) Acrylate, tris (methacryloxyethyl) isocyanurate and modified products thereof, urethane (meth) acrylate oligomer having 3 or more functional groups, epoxy (meth) acrylate oligomer having 3 or more functional groups, polyester (meth) having 3 or more functional groups Acrylate oligomers and the like can be mentioned.

[F. Addition of Photopolymerization Initiator] When the final crosslinking is ultraviolet light, it is preferable to add up to 15% by weight of a photopolymerization initiator C to the present composition from the viewpoint of radical generation. 0
≦ C / (A + B + C) ≦ 0.15. No photopolymerization initiator is required for those that are finally cross-linked by an electron beam (C =
0).

[G. Types of Photopolymerization Initiator] As photopolymerization initiators, diethoxyacetophenone, 2-hydroxy-
2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-
Acetophenone-based initiators such as 1- [4- (methylthio) phenyl] -2-morpholinopropane-1, benzoin-based initiators such as benzoin, benzyldimethyl ketal and benzoin isopropyl ether; benzophenone;
Benzophenone-based initiators such as methyl benzoylbenzoate and 4-benzoyl-4'-methyldiphenylsulfide, thioxanthone, isopropylthioxanthone,
Thioxanthone-based initiators such as 2,4-diethylthioxanthone can be mentioned.

[K. Photopolymerization Initiating Aid] In the case of final crosslinking by ultraviolet rays, triethanolamine, 4-dimethylaminobenzoic acid (n-butoxy) is used for the purpose of accelerating crosslinking.
Photoinitiating aids such as ethyl and 4,4'-dimethylaminobenzophenone can be used in combination. When the present composition is finally crosslinked by an electron beam, it is not necessary to add a photopolymerization initiator and a photopolymerization initiation auxiliary.

[K. Addition of anti-blocking agent] A general anti-blocking agent can be added to the composition for the purpose of preventing blocking during winding and preventing winding marks.
However, the use of a large amount is not preferred because it impairs the gloss and transparency of the protective layer. Examples of the inorganic blocking inhibitor include silica, kaolin, talc, calcium carbonate and the like. Examples of the organic blocking inhibitor include polyethylene fine particles, PMMA fine particles, styrene fine particles, and benzoguanamine fine particles.

[K. Addition of thermal polymerization inhibitor] An appropriate amount is used for the purpose of storage stability of the coating solution of the present composition, prevention of dark reaction of the protective layer composition after foil formation, and prevention of progress of crosslinking by heat during in-mold processing. Although a thermal polymerization inhibitor can be added, addition of a large amount is not preferable when final crosslinking is carried out by ultraviolet rays or electron beams, because it inhibits curing during irradiation. Examples of the thermal polymerization inhibitor include hydroquinone, 2,6-t-butyl-p-cresol, anthraquinone, p-benzoquinone, methoquinone and the like.

[S. Addition of a modifier] In addition, silicone oil, a high boiling point solvent, a leveling agent such as an acrylic polymer, etc., which improve the smoothness of the coating film, and various modifiers which improve adhesion, defoaming, and yuzu skin It can be added within a range that does not lower the performance of the protective layer.

[S. Addition of Solvent] Further, an appropriate amount may be diluted with a solvent generally used for the purpose of improving coating properties. In the case of dilution with a solvent, the solvent is evaporated and dried by a dryer and then irradiated with an electron beam until it can be wound and printed. When a solvent is not added, preliminary irradiation with an electron beam is performed immediately after coating.

(2) Application of Protective Layer Composition to Base Sheet FIGS. 1 (1) and 2 (1) show the first stage of the present invention. In order to prepare a transfer sheet, the above-mentioned protective layer composition in the form of a liquid or an adhesive is applied to the base sheet 1. The base sheet is, for example, a PET film subjected to a release treatment.
In this case, as a method of applying the composition to the substrate sheet, there are a general gravure coating method, a roll coating method, a coating method such as a comma coating method, and a printing method such as a gravure printing method and a screen printing method. The initial state shown in FIG. At this time, the protective layer on the base sheet is a liquid or an adhesive.

(3) Preliminary cross-linking by electron beam Before irradiation with an electron beam, the protective layer composition 2 which is a liquid or a sticky substance is wound at room temperature with an electron beam 3 and cross-linked to a printable state. This is pre-crosslinking. It is called pre-crosslinking to distinguish it from final crosslinking. This is preliminarily cross-linked by irradiation with an electron beam 3 until it can be wound up.

In order to crosslink the composition to a state where it can be wound up and printed, electron beam irradiation of from 0.05 to 2 Mrad, more preferably from 0.1 to 1 Mrad is suitable, though it depends on the composition of the protective layer. Irradiation with an electron beam less than 0.05 Mrad has too few cross-linking points and dissolves and swells with the ink during printing.
Cracks and the like occur. Further, depending on the composition, the tackiness of the protective layer composition remains, which is not preferable because blocking, winding marks and the like occur during winding. Further, a phenomenon occurs in which the protective layer composition abnormally deforms or flows due to the heat during the in-mold processing.

Conversely, when the electron beam irradiation exceeds 2 Mrad, the crosslinking progresses too much and the adhesiveness between the ink and the protective layer composition cannot be obtained.
In addition, cracks are generated in the radius portion of the base material during the in-mold processing, which is not preferable. In addition, at the stage where the crosslinking has progressed excessively, even if an attempt is made to finally crosslink with ultraviolet rays or electron beams, the protective layer composition is completely solid, so that the radical reaction hardly proceeds, and sufficient surface hardness cannot be obtained.

In the above-mentioned JP-A-63-126797, JP-A-63-132095 and JP-A-63-153200, a thermoplastic resin which is a solid at ordinary temperature and which is hardened by an ultraviolet curable or electron beam curable resin is used. A method of curing is shown. This is because the starting material is solid and the final crosslinking is incomplete. The present invention uses a special resin which is liquid at room temperature and sticky.

Preliminary cross-linking of the protective layer composition, which is a liquid or sticky substance, with an electron beam at room temperature before electron beam irradiation makes it possible to control a delicate cross-linking density and to maintain the cross-linking density until ultraviolet rays or electron beams are irradiated again. This is an effective means because a radical reaction does not proceed, and is a method in which a sufficient surface hardness can be easily obtained by final crosslinking.

The electron beam irradiator has an acceleration voltage of 100 to 300.
0 kV, dose is 0.05 to 2.0 Mrad, more preferably, acceleration voltage is 150 to 300 kV, and dose is 0.1 to 1
Mrad range. The irradiation atmosphere is an inert gas atmosphere such as nitrogen, and the residual oxygen concentration is preferably 500 ppm or less.

(4) Formation of a Picture Layer In some cases, there is no picture layer, but a picture layer is sometimes sandwiched in order to provide decorativeness. The picture layer 8 is provided next to the protective layer 2 of the base sheet, and is usually formed as a printing layer. As the material of the printing layer, polyvinyl resin, polyamide resin,
A resin such as a polyester resin, a polyacrylic resin, a polyurethane resin, a polyvinyl acetal resin, a polyester urethane resin, a cellulose ester resin, or an alkyd resin is used as a binder, and a colored ink containing a pigment or a dye may be used. . As a method for forming the print layer, an offset printing method, a gravure printing method, or a screen printing method may be used. Further, the picture layer may be composed of a metal thin film layer or a combination of a printing layer and a metal thin film layer.

(5) Formation of Adhesive Layer The adhesive layer 9 is for adhering the above layers to the surface of the molded product. The adhesive layer 9 is appropriately used according to the material of the molded article, and may be made of a polyacrylic resin, a polystyrene resin, a polyamide resin, a chlorinated polyolefin resin, a rubber resin, or the like. As a method for forming the adhesive layer, there are a gravure coating method, a roll coating method, a coating method such as a comma coating method, a gravure printing method, and a printing method such as a screen printing method. The configuration of the transfer layer is not limited to the above-described embodiment.For example, in the case of a transfer foil for the sole purpose of protecting the surface, taking advantage of the ground pattern and transparency of the molded product, the pattern layer may be omitted. it can.

(6) Formation of anchor layer An anchor layer may be provided between each layer. The anchor layer is a resin layer for improving the adhesion between the layers and improving the chemical resistance, for example, a thermosetting resin such as a urethane resin, a melamine resin, an epoxy resin, and a chlorinated vinyl copolymer resin. Etc. can be used. Examples of the method for forming the anchor layer include a gravure coating method, a roll coating method, a coating method such as a comma coating method, a gravure printing method, and a screen printing method. The transfer foil 5 is completed by the above steps.

(7) Step of Transferring Transfer Foil to Molded Product Next, a method for producing a molded product having excellent abrasion resistance and chemical resistance according to the present invention using the transfer foil having the above-described layer structure will be described. FIG. 5 is a schematic diagram. First, a transfer foil is placed on a molded product with the adhesive layer side down. Next, a heat transfer rubber-like elastic body, for example, a roll transfer machine equipped with silicone rubber,
Using up-down transfer machine, rubber surface temperature about 120 ~
At a temperature of 200 ° C. and a pressure of about 200 kg / m ² , heat pressure is applied from the base sheet side of the transfer foil via the heat-resistant rubber elastic body. When the adhesive layer adheres to the surface of the molded article and peels off the base sheet, it is peeled off at the interface between the base sheet and the protective layer. When a release layer is provided on a base sheet, peeling occurs at the interface between the release layer and the protective layer.

(8) Final cross-linking by ultraviolet ray or electron beam Finally, the protective layer is cross-linked by irradiating with ultraviolet or electron beam active energy ray. Note that the step of irradiating with the active energy ray may be performed before the step of peeling the base sheet. In the case of ultraviolet irradiation, it is preferable to add a photopolymerization initiator to the protective layer composition, but in the case of electron beam irradiation, it is not necessary. In the case of ultraviolet irradiation, a high-pressure mercury lamp, a metal halide lamp, or the like can be used as a light source. The irradiation amount of the ultraviolet ray is preferably 50 mJ / cm ² or more, more preferably 100 mJ / c, with an illuminometer having a peak near 360 nm.
m ² or more is appropriate. In the case of electron beam irradiation, the accelerating voltage is 100 to 500 kV, and the irradiation amount is suitably 1 Mrad or more, more preferably 3 Mrad or more. The irradiation atmosphere may be air, but an inert atmosphere such as nitrogen is more preferable. This completes the step of covering the molded product with the transfer foil.

(9) In the case of the in-mold transfer method (simultaneous transfer of molding) In the present invention, not only the transfer foil is attached to the preformed object, but also the molding and the transfer of the molded product can be performed simultaneously.
This is called in-mold transfer. Next, a method for imparting abrasion resistance and chemical resistance to the surface of a resin molded product using an in-mold transfer method by injection molding using the transfer foil of the present invention will be described. FIG. 6 shows the in-mold transfer method. As shown in FIG. 3 and FIG. 4, the transfer foil has a base sheet 1, a protective layer 2,
It has a picture layer 8 and the like.

The transfer foil 5 is fed into a molding die composed of the movable die 13 and the fixed die 14. At this time, the transfer foil 5
May be sent one by one, or a long transfer foil may be sent intermittently.

When a long transfer foil is used, it is preferable to use a feeder having a mechanism for determining the position so that the register of the pattern layer of the transfer foil matches the registration of the molding die. First, the position of the transfer foil is detected by a sensor and sent into the mold.
After the mold is closed, the molten resin 11 is injected and filled into the mold 12 from the fixed mold 14. A transfer foil is adhered to the surface of the molded article at the same time as the molded article is formed. After cooling the resin molded product, the mold is opened and the resin molded product with the picture is taken out. Finally, the base sheet 1 is peeled off. Thereafter, the protective layer is cured by irradiation with an active energy ray. After the irradiation with the active energy ray, the base sheet may be peeled off.

In the case of ultraviolet irradiation, a high-pressure mercury lamp, a metal halide lamp, or the like can be used as a light source. The amount of ultraviolet irradiation is preferably 50 mJ / cm ² or more, more preferably 10 mJ / cm ² or more, with an illuminometer having a peak near 360 nm.
0 mJ / cm ² or more is appropriate. For electron beam irradiation,
The acceleration voltage is 100-500 kV, and the irradiation amount is 1 Mr.
ad or more, more preferably 3 Mrad or more is appropriate. The irradiation atmosphere may be air, but an inert atmosphere such as nitrogen is more preferable.

[0052]

EXAMPLES Examples 1 to 4 of the present invention and Comparative Examples 1 to 4 will be described below.
8 is shown. However, the present invention is not limited to Examples 1-4.

[0053]

[Table 1]

Example 1 (Table 1, FIG. 7) "Synthesis Example 1" In a 1 liter flask equipped with a condenser equipped with a stirrer, 200 g of methyl ethyl ketone as a solvent, 160 g (1.54 mol) of styrene as a raw material, glycidyl meta 40 g (0.256 mol) of acrylate and 6 g of azobisisobutyronitrile were charged and polymerized at 65 ° C. for 6 hours while blowing nitrogen, and further 6 g of azobisisobutyronitrile was added and polymerized for 16 hours.
Next, nitrogen was stopped and heat treatment was performed for 8 hours under the boiling point of the solvent. To this reaction solution were added 19.3 g (0.268 mol) of acrylic acid, 2 g of dimethylbenzylamine as a catalyst and 0.4 g of P-methoxyphenol as a polymerization inhibitor.
When the esterification reaction was performed for 4 hours, the acid value was 6.4 mg.
A reactive polymer solution having a KOH / g (dry) solid content of 67.5% was obtained. The molecular weight of this reactive polymer is determined by gel permeation chromatography (polystyrene conversion).
Was found to have a weight average molecular weight of 20,000. That is, the present reactive polymer has an average of 23 per molecule.
There are calculated to be acryloyl groups.

With respect to 29.6 g of this reactive polymer solution (20 g as a reactive polymer component), 80 g of PE4
A (pentaerythritol tetraacrylate (manufactured by Kyoeisha Yushi Co., Ltd.)), 5 g of Darocure 1173 (2-
Hydroxy-2-methyl-1-phenylpropane-1-
ON (manufactured by Merck)) and 20 g of butyl acetate were added thereto, stirred and dissolved to obtain a protective layer composition solution.

After being applied on the PET film subjected to the mold release treatment using a wire bar # 5, the solvent was evaporated by allowing to stand for 10 minutes. This was treated with an electron beam irradiator (area beam type curetron EBC200-20-15 (manufactured by Nissin High Voltage Co., Ltd.)) at an accelerating voltage of 200 kV.
Irradiation with 5 Mrad of electron beam was performed to perform pre-crosslinking.

The surface of the protective layer composition was pressed against a finger and a PET surface, but had no tackiness. The pencil hardness is HB
Met. A gravure ink was applied on this protective layer composition with a wire bar # 3, but no cracking, swelling or the like occurred.

After transferring to the surface of a molded article by using the transfer foil by an in-mold transfer method, the base sheet is peeled off.
Using a UV irradiator (UB032 I-Graphics) and a high-pressure mercury lamp, the integrated light amount (UV L) of 100 mJ / cm ²
IGHT MEASURE UV350 (manufactured by Oak Manufacturing Co., Ltd.) and irradiated with ultraviolet rays to form a final protective layer.
The molding conditions for the in-mold transfer method are a resin temperature of 240
° C, a mold temperature of 50 ° C, and a resin pressure of 300 kg / cm ² . The molded article is made of acrylic resin (Mitsubishi Rayon Acrypet VH), 95 mm long, 65 mm wide, 5 height
It was formed into a tray shape of 2.5 mm and R2.5 mm at the corners.

The surface of the protective layer was cut in a grid with a cutter knife, and a tape test (Cellotape 24 mm (manufactured by Nichiban Co., Ltd.)) was performed. No peeling of the protective layer was observed. The measurement result of the pencil hardness was 5H. The steel wool # 000 was rubbed vigorously but hardly scratched. No cracks were found in the corners.

Using a dropper, cyclohexane and xylene were dropped on the surface of the protective layer and left for 10 minutes. After wiping, the surface was observed, but no change was observed. Table 1 and FIG. 7 show the parameters and performance of the first embodiment.
FIG. 7 shows the polymer molecular weight, the PMA component ratio, and the PMA of the example.
The number of functional groups, the number of monomer oligomer functional groups, the amount of electron beam for pre-crosslinking, and the amount of ultraviolet irradiation are shown. The inner circle indicates the lower limit of the appropriate value, and the outer arc indicates the upper limit of the appropriate value.

Example 2 (Table 1, FIG. 8) "Synthesis Example 2"
The reactivity was the same except that 300 g of toluene (1/1 weight ratio), 50 g of styrene, 50 g of glycidyl methacrylate, and 1 g of azobisisobutyronitrile twice as raw materials, a polymerization temperature of 60 ° C., and 9.6 g of acrylic acid were used. A polymer solution was obtained. It has a solids content of 64.1% and a weight average molecular weight of 70,000. It was calculated that there were 180 acryloyl groups per molecule. A protective layer composition solution was prepared in the same manner as in Example 1. However, 93.6 g of a reactive polymer solution (60 g as a reactive polymer component), and an oligomer component ebicryl 1290K (product of Daicel UCB 6
Functional urethane acrylate) 40 g, photopolymerization initiator Darocur 1173 g, viscosity adjusting solvent butyl acetate 20
g. Table 1 shows the result of the same test as in Example 1.
As a protective layer.

Example 3 (Table 1, FIG. 9) "Synthesis Example 3"
A reactive polymer solution was obtained in the same manner except that 16 g, 200 g of styrene, 16 g of glycidyl methacrylate, 10 g of azobisisobutyronitrile, and 9 g of acrylic acid were used. It has a solids content of 53.0% and an acid value of 3.1 mg KOH /
g (dry), weight average molecular weight 30,000,
It was calculated that there were 15 acryloyl groups per molecule.

A protective layer composition solution was prepared in the same manner as in Example 1. However, 151 g of a polymer solution (80 g as a reactive polymer component), 20 g of a monomer component TMPT-A (trimethylolpropane triacrylate (manufactured by Kyoeisha Yushi Co., Ltd.)), and a photopolymerization initiator Darocure 1173
5 g and a solvent for adjusting viscosity, butyl acetate, were 20 g. As a result of performing the same test as in Example 1, as shown in Table 1, the protective layer was good.

Comparative Example 1 (Table 1, FIG. 10) A protective layer composition solution was prepared using the reactive polymer of Synthesis Example 2. However, 23.4 g of the present polymer solution (15 g as a reactive polymer component) and the oligomer component Evicryl 1290K
(Daicel UCB 6-functional urethane acrylate) 85
g, photopolymerization initiator Darocure 1135 g, and a viscosity adjusting solvent butyl acetate 30 g. As a result of performing the same test as in Example 1, the surface preliminarily irradiated with an electron beam as shown in Table 1 remained tacky, and blocking occurred when the surface was wound up in a roll. In addition, swelling and cracking occurred in the portion where the gravure ink was printed, and the intended protective layer could not be obtained.

[0065]

[Table 2]

Comparative Example 2 (Table 2, FIG. 11) A protective layer composition solution was prepared using the reactive polymer of Synthesis Example 1. However, 125.9 g of the present polymer solution (85 g as a reactive polymer component), 15 g of a monomer component PE4A (pentaerythritol tetraacrylate (manufactured by Kyoeisha Yushi Co., Ltd.)), and 1355 g of a photopolymerization initiator Darocure 1173 g
And As a result of performing the same test as in Example 1, as shown in Table 2, thermal deformation of the protective layer was observed during in-mold transfer. When irradiation with ultraviolet rays was performed at 100 mJ / cm ^2, sufficient hardness was not obtained. Under these conditions, irradiation with ultraviolet rays was repeated four times in the same manner, but no significant improvement in hardness was observed.

Comparative Example 3 (Table 2, FIG. 12) "Synthesis Example 4"
A reactive polymer solution was obtained in the same manner except that 14 g, styrene 200 g, glycidyl methacrylate 13.6 g, azobisisobutyronitrile 10 g, and acrylic acid 7.5 g were used. This has a solid content of 52.0% and an acid value of 4.0 mg.
KOH / g (dry), weight average molecular weight 30,000
0 and was calculated to be 13 acryloyl groups per molecule.

A protective layer composition solution was prepared in the same manner as in Example 1. However, 115.4 g of the polymer solution (60 g as a reactive polymer component), 40 g of an oligomer component ebicryl 1290K (6-functional urethane acrylate manufactured by Daicel UCB), and a photopolymerization initiator Darocure 1173
g and a solvent for adjusting viscosity, butyl acetate, were 20 g. Example 1
As a result of the same test as in
When irradiated with mJ / cm ^2, sufficient hardness could not be obtained.

Comparative Example 4 (Table 2, FIG. 13) Using the reactive polymer of Synthesis Example 1, a protective layer composition solution was prepared. However, 88.9 g of the present polymer melt wave (60 g as a reactive polymer component), 40 g of a monomer component TPGD-A (tripropylene glycol diacrylate (manufactured by Kyoeisha Yushi Co., Ltd.)), and 1355 g of a photopolymerization initiator Darocure 1173 g
And As a result of performing the same test as in Example 1, as shown in Table 1, when irradiated with 100 mJ / cm ^{2 of} ultraviolet rays, sufficient hardness could not be obtained.

Comparative Example 5 (Table 2, FIG. 14) "Synthesis Example 5"
00 g, styrene 100 g, glycidyl methacrylate 134 g, and azobisisobutyronitrile were added at the initial stage and at the third and sixth hours, 6 g each in a total of 18 g. The polymerization temperature was 75 ° C., and 69 g of acrylic acid was used. Thus, a reactive polymer solution was obtained. It has a solids content of 55.0.
%, The acid value was 5.2 mg KOH / g (dry), the weight average molecular weight was 8,000, and it was calculated that there were 25 acryloyl groups per molecule.

A protective layer composition solution was prepared in the same manner as in Example 1. However, 109 g of the present polymer solution (60 g as a reactive polymer component) and the oligomer component ebicryl 1
290K (Daicel UCB 6-functional urethane acrylate) 40 g, photopolymerization initiator Darocur 1173 5 g,
The viscosity adjusting solvent butyl acetate was 20 g. As a result of performing the same test as in Example 1, as shown in Table 2, swelling and cracking occurred in the portion where the gravure ink was printed, and the intended protective layer was not obtained.

[0072]

[Table 3]

Comparative Example 6 (Table 3, FIG. 15) A protective layer composition solution was prepared using the reactive polymer of Synthesis Example 2. However, 93.6 g of the present polymer solution (60 g as a reactive polymer component), and the oligomer component ebicryl 1290K
(Daicel UCB 6-functional urethane acrylate) 40
g, 5 g of a photopolymerization initiator Darocur 1173, and 20 g of a viscosity adjusting solvent butyl acetate. The pre-irradiation condition of the electron beam was 0.04 Mrad. As a result of performing the same test as in Example 1, as shown in Table 3, the surface remained tacky, and blocking occurred when wound up in a roll. In addition, swelling and cracking occurred in the portion where the gravure ink was printed, and the intended protective layer could not be obtained. Furthermore, the thermal deformation of the protective layer during in-mold transfer was remarkable.

Comparative Example 7 (Table 3, FIG. 16) A protective layer composition solution was prepared using the reactive polymer of Synthesis Example 2. However, 93.6 g of the present polymer solution (60 g as a reactive polymer component), and the oligomer component ebicryl 1290K
(Daicel UCB 6-functional urethane acrylate) 40
g, 5 g of a photopolymerization initiator Darocur 1173, and 20 g of a viscosity adjusting solvent butyl acetate. The pre-irradiation condition of the electron beam was 2.1 Mrad. During the in-mold transfer, cracks occurred at the rounded portions of the protective layer. In addition, when irradiation with ultraviolet rays was performed at 100 mJ / cm ^2, sufficient hardness was not obtained. Irradiation was again performed under these conditions, but no significant improvement in hardness was observed.

[0075]

[Table 4]

Example 4 (Table 4, FIG. 17) Using the reactive polymer of Synthesis Example 2, a protective layer composition solution was prepared. However, 93.6 g of the present polymer solution (60 g as a reactive polymer component), and the oligomer component ebicryl 1290K
(Daicel UCB 6-functional urethane acrylate) 40
g and a solvent for adjusting viscosity, butyl acetate, were 20 g. The pre-irradiation condition of the electron beam was 0.5 Mrad. The same test as in Example 1 was performed for this. However, the final crosslinking was changed to ultraviolet rays, and irradiation with an electron beam of 3.0 Mrad was performed. The test results showed that the protective layer was good as shown in Table 4.

Comparative Example 8 (Table 4, FIG. 18) A protective layer composition solution was prepared using the reactive polymer of Synthesis Example 2. However, 93.6 g of a polymer solution (60 g as a reactive polymer component), 40 g of an oligomer component ebicryl 1290K (6-functional urethane acrylate manufactured by Daicel UCB),
The viscosity adjusting solvent butyl acetate was 20 g. The pre-irradiation condition of the electron beam was 0.5 Mrad. The same test as in Example 1 was performed for this. However, the final cross-linking was changed to ultraviolet light, and irradiation with an electron beam of 0.8 Mrad was performed. As a result of the test, as shown in Table 4, sufficient hardness was not obtained for the protective layer.

[0078]

According to the transfer foil of the present invention, a protective layer preliminarily cross-linked with an electron beam is formed on a base material sheet to such an extent that cracks do not occur at the time of transfer to a molded article, and an adhesive layer is further provided thereon. Therefore, by performing final cross-linking with an ultraviolet ray or an electron beam after transferring to a molded article, a protective layer having excellent chemical resistance and abrasion resistance can be provided without causing cracks during transfer. The method for producing a transfer foil of the present invention comprises applying a liquid or sticky protective layer composition to a substrate sheet, preliminarily crosslinking with an electron beam to such an extent that cracks do not occur during transfer to a molded article, and forming an adhesive layer. Is provided to obtain a transfer foil, so that after being transferred to a molded product, it is finally cross-linked by ultraviolet rays or an electron beam, whereby a crack does not occur at the time of transfer, and a protective layer having excellent chemical resistance and abrasion resistance can be provided. . The method for producing a molded article using the transfer foil of the present invention is to apply a liquid or sticky protective layer composition to a base sheet,
Pre-crosslinking with an electron beam to the extent that cracks do not occur at the time of transfer to the molded article, and the transfer foil provided with the adhesive layer is finally crosslinked by ultraviolet rays or electron beams after being transferred to the molded article, so that no cracks occur at the time of transfer A protective layer having excellent chemical resistance and abrasion resistance can be provided.

[Brief description of the drawings]

FIG. 1 (1) shows a method of applying a protective layer composition to a base sheet,
The figure which shows the state which preliminarily bridge | crosslinks by an electron beam and winds up on a roll, (2) The figure which shows the state which sticks a transfer foil to an object and peels a base material sheet. (3) is a diagram showing a state in which the protective layer is finally cross-linked by irradiating the protective layer with an electron beam or ultraviolet light after removing the base sheet.

FIG. 2 is a cross-sectional view showing a state where a protective layer composition is applied to a base sheet. (2) Sectional drawing which shows the process which preliminarily irradiates an electron beam to a protective layer, and sets it in the state which can be wound up and printed.
(3) is a sectional view of a state in which a picture layer and an adhesive layer are formed on the protective layer. (4) is sectional drawing which shows the process of sticking to an object and performing the final bridge | crosslinking by an electron beam.

FIG. 3 is a cross-sectional view of the transfer foil of the present invention comprising a base sheet, a protective layer, a picture layer, and an adhesive layer.

FIG. 4 is a cross-sectional view of the transfer foil of the present invention comprising a base sheet, a protective layer, and an adhesive layer.

FIG. 5 is an explanatory view showing a step of transferring the transfer foil of the present invention to an object.

FIG. 6 is a cross-sectional view for explaining a molding simultaneous transfer method.

FIG. 7 is a graph of the polymer molecular weight, the polymer component ratio, the number of functional groups of the polymer component, the number of monomer-oligomer functional groups, the pre-crosslinking dose of electron beam, and the final cross-linking dose of ultraviolet ray in Example 1 of the present invention. The inner circle indicates the lower limit of the optimal value. The outer arc indicates the upper limit of the optimal value. All values are in the appropriate range.

FIG. 8 is a graph of the polymer molecular weight, polymer component ratio, number of functional groups of polymer component, number of functional groups of monomer oligomer, pre-crosslinking dose of electron beam, and final cross-linking dose of ultraviolet ray in Example 2 of the present invention. The inner circle indicates the lower limit of the optimal value. The outer arc indicates the upper limit of the optimal value. All values are in the appropriate range.

FIG. 9 is a graph showing the molecular weight of the polymer, the ratio of the polymer components, the number of functional groups of the polymer component, the number of monomer-oligomer functional groups, the pre-crosslinking dose of electron beam, and the final cross-linking dose of ultraviolet ray in Example 3 of the present invention. The inner circle indicates the lower limit of the optimal value. The outer arc indicates the upper limit of the optimal value. All values are in the appropriate range.

10 is a graph of the polymer molecular weight, polymer component ratio, number of polymer component functional groups, number of monomer oligomer functional groups, electron beam preliminary crosslinking dose, and ultraviolet final crosslinking dose of Comparative Example 1. FIG. The inner circle indicates the lower limit of the optimal value. The outer arc indicates the upper limit of the optimal value. The polymer component ratio is 15%, which is lower than the lower limit of 20%, which is an appropriate value. All other values are in the appropriate range.

FIG. 11 is a graph of the polymer molecular weight, polymer component ratio, polymer component functional group number, monomer-oligomer functional group number, electron beam pre-crosslinking dose, and ultraviolet final crosslinking dose of Comparative Example 2. The inner circle indicates the lower limit of the optimum value. The outer arc indicates the upper limit of the optimal value. The value of the polymer component is 85%, which deviates from an appropriate value. All other values are in the appropriate range.

FIG. 12 is a graph of the polymer molecular weight, polymer component ratio, polymer component functional group number, monomer-oligomer functional group number, electron beam pre-crosslinking dose, and ultraviolet ray final crosslinking dose of Comparative Example 3. The inner circle indicates the lower limit of the optimal value. The outer arc indicates the upper limit of the optimal value. The number of polymer functional groups is 13 and deviates from an appropriate value (15 or more). All other values are in the appropriate range.

FIG. 13 is a graph of the polymer molecular weight, polymer component ratio, polymer component functional group number, monomer-oligomer functional group number, electron beam preliminary crosslinking dose, and ultraviolet final crosslinking dose of Comparative Example 4. The inner circle indicates the lower limit of the optimal value. The outer arc indicates the upper limit of the optimal value. The number of functional groups in the monomer oligomer is 2
And deviated from an appropriate value (3 or more). All other values are in the appropriate range.

FIG. 14 is a graph of the polymer molecular weight, polymer component ratio, number of polymer component functional groups, number of monomer-oligomer functional groups, electron beam preliminary crosslinking dose, and ultraviolet final crosslinking dose of Comparative Example 5. The inner circle indicates the lower limit of the optimal value. The outer arc indicates the upper limit of the optimal value. The molecular weight of the polymer is 8,000, which is less than the lower limit of 10,000 which is an appropriate value. All other values are in the appropriate range.

FIG. 15 is a graph of the polymer molecular weight, polymer component ratio, polymer component functional group number, monomer-oligomer functional group number, electron beam pre-crosslinking dose, and ultraviolet final crosslinking dose of Comparative Example 6. The inner circle indicates the lower limit of the optimal value. The outer arc indicates the upper limit of the optimal value. 0.04M dose of electron beam pre-crosslinking
rad, which is lower than the appropriate lower limit of 0.05 Mrad.
All other values are in the appropriate range.

FIG. 16 is a graph of the polymer molecular weight, polymer component ratio, number of functional groups of polymer component, number of functional groups of monomer-oligomer, electron beam preliminary crosslinking dose, and ultraviolet final crosslinking dose of Comparative Example 7. The inner circle indicates the lower limit of the optimal value. The outer arc indicates the upper limit of the optimal value. The dose of electron beam pre-crosslinking is 2.1 Mr
ad, which is higher than the appropriate upper limit of 2 Mrad. All other values are in the appropriate range.

FIG. 17 is a graph of a polymer molecular weight, a polymer component ratio, the number of polymer component functional groups, the number of monomer-oligomer functional groups, an electron beam preliminary crosslinking dose, and an electron beam final crosslinking dose of Example 4 of the present invention. The inner circle indicates the lower limit of the optimal value. The outer arc indicates the upper limit of the optimal value. These values are all within the appropriate range.

FIG. 18 is a graph of the polymer molecular weight, polymer component ratio, polymer component functional group number, monomer-oligomer functional group number, electron beam preliminary crosslinking dose, and electron beam final crosslinking dose of Comparative Example 9. The inner circle indicates the lower limit of the optimal value. The outer arc indicates the upper limit of the optimal value. 0.8M electron beam irradiation for final crosslinking
rad, which is less than the lower limit of 1 Mrad. All other values are in the appropriate range.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base sheet 2 Protective layer 3 Electron beam for pre-crosslinking 4 Object (molded article) 5 Transfer foil 6 Electron beam for final crosslinking 7 Ultraviolet ray for final crosslinking 8 Picture layer 9 Adhesive layer 11 Molten resin 12 cavity

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yuzo Nakamura 3, Mibuhanai-cho, Nakagyo-ku, Kyoto, Japan Photographic Printing Co., Ltd. Inside the corporation

Claims (4)

[Claims] Claims: 1. A substrate sheet having a weight average molecular weight of 10,000 to
A reactive polymer A having an average of 15 or more (meth) acryloyl groups added to 100,000 molecules per molecule;
The above monomer or oligomer B is contained such that the ratio of A to B is 20 to 80:80 to 20, and (A +
A protective layer containing 0 to 15% by weight of the photopolymerization initiator C with respect to B) is formed, and the protective layer has a thickness of 0.05 Mrad to 2 Mrad.
A transfer foil characterized in that it is preliminarily irradiated with an electron beam to make it printable and windable, and further has an adhesive layer formed thereon. 2. The method according to claim 1, wherein the weight-average molecular weight is 10,000 to
A reactive polymer A having an average of 15 or more (meth) acryloyl groups added to 100,000 molecules per molecule;
The above monomer or oligomer B is contained such that the ratio of A to B is 20 to 80:80 to 20, and (A +
A liquid or sticky protective layer composition containing 0 to 15% by weight of a photopolymerization initiator C is applied to B), and 0.05 Mra is applied.
A method for producing a transfer foil, characterized in that a pre-irradiation of an electron beam of d to 2 Mrad is made to enable printing and winding, and an adhesive layer is formed thereon. 3. The method according to claim 1, wherein the weight average molecular weight is 10,000 to
A reactive polymer A having an average of 15 or more (meth) acryloyl groups added to 100,000 molecules per molecule;
The above monomer or oligomer B is contained such that the ratio of A to B is 20 to 80:80 to 20, and (A +
A liquid or sticky protective layer composition containing 0 to 15% by weight of a photopolymerization initiator C is applied to B), and 0.05 Mrad
Pre-irradiation of ~ 2 Mrad of electron beam to make it printable and windable, then form an adhesive layer on it to form a transfer foil, attach the transfer foil to the molded product, remove the base sheet or base sheet A method for producing a molded article using a transfer foil, comprising irradiating an ultraviolet ray of 50 mJ / cm ² or more or an electron beam of 1 Mrad or more from above the sheet substrate before removing the sheet substrate to perform final crosslinking. 4. The substrate sheet has a weight average molecular weight of 10,000 to 1
(Meth) acryloyl groups average 1 to 100,000 molecules
(A + B) containing 5 or more reactive polymer A and a monomer or oligomer B having 3 or more functional groups so that the ratio of A to B is 20 to 80:80 to 20;
Of a liquid or sticky protective layer composition containing 0 to 15% by weight of a photopolymerization initiator C,
Pre-irradiate Mrad electron beam to make it printable and windable, then form an adhesive layer on it to form a transfer foil, put the transfer foil in a mold, inject molten resin into the mold and solidify The molded product is opened, and the mold is opened to remove the base sheet, or the protective layer is irradiated with ultraviolet rays of 50 mJ / cm ² or more or electron beams of 1 Mrad or more from above the base sheet before removing the base sheet. A method for producing a molded article using a transfer foil, which is characterized by final crosslinking.