JPH0263824A - Specular transfer material and production of transferred molded article - Google Patents

Abstract

PURPOSE:To represent extremely smooth metallic luster by forming a combined peeling and primer layer made of specified substance on a substrate. CONSTITUTION:A combined peeling and primer layer 2, a metallic thin layer 3 and an adhesive layer 4 are laminated on a substrate sheet 1. The combined peeling and primer layer 2 formed between the substrate sheet 1 and the metallic thin layer 3 has a function for enhancing adhesion of the peeling layer, a pattern layer and the metallic thin layer. Therefore such the need that several layers are provided before the metallic thin layer 3 is provided is eliminated and a transfer material which has the metallic thin layer 3 free from an unevenness and is excellent in luster is obtained. Further the combined peeling and primer layer 2 consists of a prepolymer having a reactive double bond or reaction epoxy group and a reactive diluent and a photoinitiator added in accordance with necessity. Therefore the surface of a transfer medium turns to a cured layer and excellent in resistance to wear and resistance to chemicals by thermally transferring this specular transfer material on the transfer medium.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a transfer material that can express an extremely smooth metallic luster and has excellent surface strength, and a method for producing a transfer molded product using this transfer material.

[Conventional technology]

Conventionally, in order to express a metallic luster on the entire or partial surface of a plastic molded product, there has been a method of using a transfer material used for stamping, roll transfer, etc. The transfer material is placed on a base sheet made of plastic film, etc.
It was manufactured by sequentially printing several layers such as a release layer and a primer layer using a gravure printing method, then forming a metal thin film layer, and finally providing an adhesive layer using a printing method. [Problems to be Solved by the Invention] However, the above transfer material has several layers formed by a gravure printing process before forming the metal thin film layer.
Although efforts have been made to adjust the depth, number of lines, and angle of the gravure plate pattern, unevenness called gravure eyes caused by the gravure plate pattern occurs on each layer. The plate used for gravure printing is composed of a wall and cells.
The cell portions on the surface of the printed matter are raised and the wall portions are flat. Due to the unevenness formed in this way, the smoothness of the layer formed by gravure printing is lost, and the metal thin film layer formed on top of it also has unevenness, which diffuses light and reduces the gloss of the metal thin film layer. It was lowering it. Furthermore, thermoplastic resins are often used as the release layer, which is insufficient in terms of chemical resistance, solvent resistance, and abrasion resistance. In order to improve chemical resistance, solvent resistance, and abrasion resistance, some products use thermosetting resin as a release layer, but the heat treatment process requires a long furnace length, takes time, and has insufficient abrasion resistance. I haven't gotten anything. The present invention solves these problems and provides a transfer material that can express extremely smooth metallic luster and has excellent surface strength, and a method for manufacturing transfer molded products using this transfer material. It's about doing.

[Means to solve the problem]

In order to achieve the above object, the present invention is made as follows. That is, in the mirror transfer material of the present invention, a release/primer layer, a metal thin film layer, and an adhesive layer are sequentially laminated on a base sheet having release properties, and 7.11 the release/primer layer has reactive double bonds or A prepolymer having a reactive evoquine and a reactive diluent were added as necessary. The present invention will be explained in more detail with reference to the drawings. FIG. 1 is a sectional view showing an embodiment of the mirror transfer material of the present invention. (2) indicates a beneficial sheet, 2 indicates a peeling/primer layer, 3 indicates a metal thin film layer, and 4 indicates an adhesive layer. As the base sheet 1, polyethylene terephthalate,
A blasting film made of polypropylene, polyethylene, nylon, cellophane, etc., or a film obtained by subjecting the above film to a release treatment can be used. II, Tll and Primer 2 is composed of a prepolymer having a reactive double bond or a reactive epoxy group, a reactive diluent, and a photoinitiator added as necessary. The peeling/primer layer 2 is a layer that can be peeled off from the base sheet 1 and has properties as a primer that firmly adheres to the metal thin film layer 3 due to a prepolymer containing a functional group and a reactive diluent. Examples of prepolymers having reactive double bonds include unsaturated polyesters, alkyd acrylates, polyester acrylates, urethane acrylates, silicone acrylates, diene acrylates, melamine acrylates, and side chain functional groups of low molecular weight vinyl copolymers. Examples include products in which acryloyl groups are introduced using , or products in which these prepolymers are assembled with isocyanate compounds. Furthermore, examples of prepolymers having reactive epoxy groups include compositions in which reactive epoxy groups undergo ring-opening polymerization using a photopolymerization initiator that is a compound that decomposes with light to generate a Lewis acid. In particular, from the viewpoint of coachability and adhesion of the metal thin film layer 3, the molecular weight is the enemy, preferably 100, -C on the side chain of 10,000 to 50,000.
Preference is given to acrylic acrylate prepolymers incorporating groups such as OOI+. Examples of reactive diluents include monofunctional monomers such as 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate, and polyfunctional monomers such as 1-3 butadiol diacrylate, diethylene glycol diacrylate, trimethylolpropane triacrylate, and pentaerythritol triacrylate. Examples include functional monomers. Further, as the photoinitiator added if necessary, carbonyl compounds such as acetophenone and benzophenone, sulfur compounds such as tetramethyl-thiural monosulfite and thioxanthone, and azo compounds such as allyl azonium salts can be used. Before forming the metal thin film layer 3, the release/primer layer 2 is cured or semi-cured by irradiating ultraviolet rays if it contains a photoinitiator, or irradiating it with an electron beam if it does not contain a photoinitiator. The metal thin film layer 3 is preferably formed of metal such as aluminum, chromium, nickel, etc. by a vacuum evaporation method, an ion blasting method, a sputtering method, etc.
As a method of partially providing the metal thin film layer 3, a water-soluble resin layer is formed on the parts where the metal thin film layer 3 is not required, a metal layer is formed on the entire surface from above, and the unnecessary metal layer is removed together with the water-soluble resin by washing with water. There are ways to remove it. The adhesive layer 4 can be selected from various types depending on the type of object to be transferred. For example, resins such as vinyl chloride, acrylic, and rubber may be used. When a plastic molded article with metallic luster is produced by heat transfer using a transfer material, the unevenness of the adhesive layer 4 affects the surface smoothness when a transfer method using a normal roll is used. Therefore, when manufacturing items that require a mirror surface, such as mirrors, etc., in extrusion molding, after extruding the resin, before the resin has cooled, transfer the transfer material to the extruded resin and the nip. A molding simultaneous transfer method in which a transfer material is placed in an injection mold and transfer is performed at the same time as injection is advantageous for obtaining surface smoothness. This is because the transfer process is performed before the resin on the transferred object is cooled and solidified, so when pressure is applied during transfer, the unevenness of the adhesive layer 4 is absorbed by the elasticity of the resin on the transferred object. This is to be done. For example, in the conventional transfer method, the molded product is in a cooled state and heat pressure is applied through the base sheet by the silicone rubber, so it is not possible to fuse the base sheet adhesive layer, and the antistatic layer ~ The unevenness of the adhesive layer will not be absorbed by the transfer target and will appear on the transfer surface after transfer. These irregularities cause light to diffuse, resulting in an uneven surface with glare. In addition, even if the transferred object has elasticity, the unevenness of the formed metal thin film layer does not disappear during the transfer process because the extensibility of the metal is low. Therefore, in extrusion molding, press molding, or injection molding, since the object to be transferred has elasticity before being cooled and solidified, it is possible to eliminate irregularities in the adhesive layer. Also,
By employing the release/primer layer 2 instead of forming a release layer and a primer layer, it is possible to reduce the unevenness caused by overprinting and eliminate the unevenness of the metal thin film layer. Further, if overlapping is required, it is preferable to leave the peeling and primer layer 2 in a semi-cured state. In this way, the adhesion of the overlamp part becomes strong, and by irradiating ultraviolet rays or electron beams after transfer, a molded product with excellent surface strength can be obtained. This is also an advantageous method for suppressing the occurrence of cracks on the transfer surface.

[Effect]

In the transfer material of the present invention, the only layer formed between the base sheet 1 and the metal thin film layer 3 is the release/primer N2. The release/primer layer 2 has the function of a primer layer in a normal transfer material, that is, the function of increasing the adhesion between the release layer or pattern layer and the metal thin film layer, so several layers are provided before forming the metal thin film layer 3. There is no need for this, and a transfer material with excellent gloss of the metal thin film layer 3 without the occurrence of irregularities called gravure grains can be obtained. In addition, the peeling/primer layer 2 is composed of a prepolymer having a reactive double bond or a reactive epoxy group, a reactive diluent, and a photoinitiator added if necessary, so this mirror transfer material is thermally transferred to the object to be transferred. By carrying out this process, the surface of the object to be transferred becomes a hardened layer and has excellent abrasion resistance and chemical resistance. Thus, the painted object obtained using the above transfer material has excellent surface smoothness, metallic luster, and surface strength.

【Example】

Back coating ↓ A polyester film coated with melamine on one side was used as the base sheet, and a release/primer layer having the composition below was coated on it using a reverse roll coater to a thickness of 4 μm. . Composition l: 70 parts of acrylic acrylate prepolymer with a molecular weight of 30,000 and having a reactive double bond in the side chain. 30 parts of trimethylolpropane triacrylate. 5 parts of benzophenone. 160 W/C after coating! A peeling/primer layer was formed by irradiating with ultraviolet light at 15 m/min using 2 lamps. On top of that, vacuum the aluminum! A metal thin film layer is formed to a thickness of 60 parts m by a 4-layer method, and then vinyl chloride ink is applied to a thickness of la by a gravure coating method.
A mirror transfer material was completed by coating the adhesive layer on the mirror surface. This mirror transfer material was transferred to an AS molded product to obtain a molded product with a thin film on the entire surface. This molded product has excellent surface smoothness and metallic luster, and its surface hardness is RCA abrasion 1000 times or more, pencil hardness is 311, and it will not be scratched even when rubbed with 1l1000 steel wool. there were. Tip 1 A polyester film coated with melamine on one side is used as a base sheet, and 21 consisting of the following composition 2 is placed on top of the polyester film coated with melamine on one side.
One layer of primer was coated with a reverse roll coater to a thickness of 4 μm. Composition 2 After coating 70 parts of acrylic acrylate prepolymer with a molecular weight of 30,000 and having a reactive double bond in the side chain and 1 to 30 parts of trimethylolpropane triacrylate, an acceleration voltage of 175 ν and an electron beam current of 6 m were applied.
After irradiating the electron beam with a throughput of 5 Mrad, Example 1
In the same manner as above, three metal layers and an adhesive layer were formed to complete a mirror transfer material. This mirror transfer material was transferred to an AS molded product to obtain a molded product having metallic luster on the entire surface. This molded product has excellent surface smoothness and metallic luster, and its surface hardness is R.
It was CA abraded more than 1,000 times, had a pencil hardness of 311, and was not scratched even when rubbed with steel wool of 111,000. EXAMPLE A polyester film coated with melamine on one side was used as a base sheet, and a release/primer layer having composition 3 below was coated on the base sheet to a thickness of 4 μm using a reverse roll coater. Composition 3: 70 parts of acrylic acrylate prepolymer with a molecular weight of 30,000 and having a reactive double bond in the side chain. 30 parts of trimethylolpropane triacrylate. 5 parts of benzophenone. After coating, irradiate with ultraviolet light at 80 W/cm, 1 lamp, 30 m, 7 minutes. A peeling and primer layer was formed in a semi-cured state. Thereon, a metal thin film layer and an adhesive layer were formed in the same manner as in Example 1 to obtain a mirror transfer material. This mirror transfer material was transferred onto an AS molded product to obtain a molded product with a thin film on the entire surface. 80W/cm, 2 lights, 5
When UV irradiation was performed at a rate of m/min, a molded product having surface smoothness, metallic luster, and surface strength similar to those of Examples I and 2 was obtained. A polyester film was used as a base sheet, and a release/primer layer having the following composition 4 was coated thereon to a thickness of 3 μm using a reverse roll coater. Composition 4 Acrylic acrylate prepolymer with a molecular weight of 30,000
50 parts trimethylolpropane triacrylate 48 parts benzoin ethyl ether 2 parts After coating, 80 W/cm, line speed 1 with high pressure mercury lamp.
The peeling and primer layer was cured at 5 m/1 inch. Thereafter, aluminum was formed to a thickness of 80n+s by vacuum evaporation, and then coated to a thickness of 1 μm using a vinyl chloride adhesive ink by gravure printing. Before the acrylic material extruded using an extrusion molding machine was cooled, the extruded resin and the mirror transfer material were nipped with a rolling roll to obtain a resin plate with the mirror transfer material transferred thereon. The resin plate had no image distortion and could be used as a mirror. In addition, the surface of this mirror is not attacked by organic solvents or chemicals, and is made of steel wool.
It did not get scratched even if rubbed with oooo. A polyester film was used as a base sheet, and a release/primer layer having composition 5 below was coated on the base sheet to a thickness of 3 μm using a reverse roll coater. Composition 5 Acrylic acrylate prepolymer with molecular N30,000
35 parts urethane acrylate prepolymer 15 parts trimethylolpropane triacrylate 30 parts tetramethylolmethane tetraacrylate
After 2o part coating, acceleration voltage 175KV, electron beam current 9...A
The peeling and primer layer was cured by irradiation with an electron beam at a treatment amount of 5 Mrad. Thereafter, aluminum was formed to a thickness of 80 nm by vacuum evaporation, and then vinyl chloride adhesive ink was coated to a thickness of 1 um by gravure printing. Before the acrylic extruded from the above specular transfer material with an extrusion molding machine was cooled, the extruded resin and the specular transfer material were nipped with a rolling roll to obtain a resin plate on which the specular transfer material was transferred. The resin plate had no image distortion and could be used as a mirror. In addition, the surface of this mirror is not attacked by organic solvents or chemicals, and is made of steel wool.
It did not get scratched even if rubbed with oooo. 1. The mirror transfer material of Example 4 was inserted into an injection mold, and after the mold was clamped, acrylonitrile molding resin was injected to obtain a molded product to which the mirror transfer material of Example 1 was transferred. The mirror transfer material had no image distortion and could be used as a mirror. Further, the surface of this mirror was not attacked by organic solvents or chemicals, and was not scratched even when rubbed with steel wool.

【Effect of the invention】

In the mirror transfer material of the present invention, a release/primer layer, a metal thin film layer, and an adhesive layer are sequentially laminated on a base sheet having release properties, and the release/primer layer has a reactive double bond or a reactive epoxy group. It is composed of a prepolymer, a reactive diluent, and a photoinitiator added if necessary. Therefore, the peeling and primer layer also serves as a metal thin film primer, and there is no need for overprinting as in the past, and a mirror transfer material with excellent surface smoothness and metallic luster can be obtained. In addition, since the release/primer layer uses ultraviolet or electron beam curable resin, the molded product obtained by using this mirror transfer material has a smooth surface, metallic luster, surface hardness, and chemical resistance. It has excellent toughness and solvent resistance.

[Brief explanation of the drawing]

FIG. 1 is a sectional view showing an embodiment of the mirror transfer material of the present invention. 1...Base film, 2...Peeling and primer layer,
3... Metal thin film layer, 4... Adhesive layer. Patent applicant: Nissha Printing Co., Ltd. Base film... Peeling and primer layer... Metal thin film layer... Adhesive layer

Claims (1)

[Claims] 1. A release/primer layer (2), a metal thin film layer (3), and an adhesive layer (4) are sequentially laminated on a base sheet (1) having release properties, and the release/primer layer ( 2) A mirror transfer material comprising a prepolymer having a reactive double bond or a reactive epoxy group, a reactive diluent, and a photoinitiator added as necessary. 2. The specular transfer material according to claim 1, wherein the peeling and primer layer (2) is cured by being irradiated with ultraviolet rays when it contains a photoinitiator, or with an electron beam when it is not. 3. The mirror transfer material according to claim 1, wherein the peeling and primer layer (2) is semi-cured by being irradiated with ultraviolet rays when it contains a photoinitiator, or with an electron beam when it is not. 4. The mirror transfer material according to any one of claims 1 to 3, wherein the metal thin film layer (3) is formed in a pattern. 5. A release/primer layer (2), a metal thin film layer (3), and an adhesive layer (4) are sequentially laminated on a base sheet (1) having release properties, and the release/primer layer (2) has a reactive secondary layer. Transfer is performed simultaneously with extrusion molding, press molding, or injection molding using a mirror transfer material consisting of a prepolymer having a double bond or reactive epoxy group, a reactive diluent, and a photoinitiator added if necessary. A method for manufacturing a transfer molded product characterized by the following. 6. A release/primer layer (2), a metal thin film layer (3), and an adhesive layer (4) are sequentially laminated on a base sheet (1) having release properties, and the release/primer layer (2) has a reactive secondary layer. A transfer molded product characterized in that it is subjected to bending after being transferred using a mirror transfer material consisting of a prepolymer having a double bond or a reactive epoxy group, a reactive diluent, and a photoinitiator added if necessary. Production method.