JP2001260596A - Partial matte hard coat transfer material and method for manufacturing partial matte hard coat molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a partial matte hard coat transfer material capable of certainly performing decoration having matte partially and excellent in surface strength even if the transfer material is manufactured by in-line printing, and a method for manufacturing a partial matte hard coat molded article. SOLUTION: At least, a partial matte layer having fine unevenness comprising a water-soluble resin in which a matting agent is dispersed, a hard coat layer comprising an active energy beam curable resin and an adhesive resin are laminated on a substrate sheet having releasability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a partially matte hard coat transfer material and a method for producing a partially matte hard coat molded article which can partially obtain a molded article having a mat portion and a high surface strength.

[0002]

2. Description of the Related Art Conventionally, there has been a transfer method as a method of decorating the surface of home electric appliances, cosmetic containers, miscellaneous goods and the like. The transfer method uses a transfer material having a transfer layer composed of a release layer, a pattern layer, an adhesive layer, etc. formed on a base sheet, and heating and pressurizing the transfer layer to bring the transfer layer into close contact with an object to be transferred. This is a method in which decoration is performed by peeling and transferring only the transfer layer to the surface of the transfer object. As a transfer material for obtaining a decorative molded product having high surface strength, a hard coat layer made of an active energy ray-curable resin composition is formed on a base sheet having releasability, and a pattern layer and an adhesive are further formed thereon. Some of them had a layer or the like.

As a partial mat hard coat transfer material for obtaining a decorative molded article having a high surface strength and a partially mat-like surface, a partial mat layer is formed on a base sheet and cured. Thereafter, a hard coat layer made of an active energy ray-curable resin composition was formed, and a pattern layer, an adhesive layer, and the like were further formed thereon. As the partial mat layer, a resin in which a matting agent is dispersed in a curable resin having good adhesion to the base sheet, for example, an aminoalkyd-based resin or a urea-melamine-based resin is often used.

When such a transfer material is adhered to an object to be transferred and the partial mat layer is peeled off together with the base sheet, the surface of the partial mat layer has fine irregularities. Can be partially expressed, and a hard coat layer can be formed.

[0005]

However, in the case of so-called in-line printing, in which printing from the partial mat layer to the hard coat layer and the picture layer is performed by a series of printing machines, the time from printing of the partial mat layer to printing of the hard coat layer is reduced. Can not secure sufficient drying time. As a result, before the resin constituting the partial mat layer is sufficiently cured, the hard coat layer must be formed by overlapping, and the resin constituting the partial mat layer is hardened by the active energy ray curing constituting the hard coat layer. When the base sheet is peeled off after the transfer material is adhered to the molded product, it peels between the partial mat layer and the hard coat layer because the adhesive property between the partial mat layer and the hard coat layer is increased by reacting with the reactive resin. However, there is a problem in that the hard coat layer causes peeling in the layer or the base sheet is torn without peeling, resulting in poor appearance of the partially matte hard coat molded product.

In the case of so-called off-line printing, in which after the mat layer is printed, the mat layer is sufficiently heated and dried, the mat layer is sufficiently hardened, and then attached to a printing machine again to print the hard coat layer and thereafter. Since the curing of the mat layer proceeds sufficiently, the reactive group in the resin constituting the partial mat layer disappears, so that it does not react with the active energy ray-curable resin constituting the hard coat layer, and the partial mat layer and the hard coat layer Has low adhesion, but has the following problems.

That is, since printing of the partial mat layer and printing of the hard coat layer and thereafter must be performed in separate steps, it is not economical to manufacture a partial mat hard coat transfer material. In addition, since more heat and longer time are required between the time of printing the partial mat layer and the time of printing the hard coat layer than in the case of in-line printing, the base sheet shrinks, and the previously printed partial mat layer is printed. It is difficult to match the pattern with the pattern after the hard coat layer to be printed later, especially the pattern on the picture layer.

Therefore, the present invention solves the above-mentioned problems, and even if a transfer material is manufactured by in-line printing, it is possible to reliably perform decoration having a partial mat and excellent surface strength. It is an object of the present invention to provide a method for producing a partially matte hard coat transfer material and a partially matte hard coat molded product.

[0009]

In order to achieve the above object, a partial matte hard coat transfer material of the present invention comprises a fine base material having a releasable property and comprising a fine water-soluble resin having a matting agent dispersed therein. It was configured such that at least a partial mat layer having irregularities, a hard coat layer made of an active energy ray-curable resin, and an adhesive layer were laminated.

In the above structure, the water-soluble resin may be
It was configured to be one of sodium polyacrylate, polyvinylpyrrodrine or polyvinyl alcohol.
The partial mat hard coat transfer material according to claim 1.

In each of the above structures, a picture layer is provided between the hard coat layer and the adhesive layer.

The method for producing a partially matte hard coat molded article according to the present invention comprises the steps of: adhering the partial matte hard coat transfer material to the surface of the molded article; releasing the base sheet; irradiating active energy rays; The water-soluble resin of the partial mat layer remaining on the surface was washed and removed with water.

Further, according to the method for producing a partially matte hard coat molded product of the present invention, the above-mentioned partially matte hard coat transfer material is sandwiched in an injection mold and a molding resin is injected into a cavity to obtain an injection molded product. At the same time, the transfer material is adhered to the surface, the mold is opened, the molded product is taken out, the base sheet is peeled off, the active energy ray is irradiated, and then the water-soluble resin of the partial mat layer remaining on the hard coat layer surface Was configured to be washed away with water.

[0014]

Embodiments of the present invention will be described below in detail with reference to the drawings. 1 to 4 are cross-sectional views showing one embodiment of the partial matte hard coat transfer material of the present invention, and FIGS. 5 and 6 are cross-sectional views showing one embodiment of the process of the method for producing a partially matte hard coat molded product of the present invention. FIG. In the figure, 1 is a partial mat hard coat transfer material, 2 is a base sheet, 3 is a partial mat layer, 4 is a hard coat layer, 5
Is a picture layer, 6 is an adhesive layer, 7 is a release layer, 8 is an anchor layer,
9 denotes a metal thin film layer, and 10 denotes a molded product.

The partial matte hard coat transfer material 1 of the present invention
A partial mat layer 3 having fine irregularities made of a water-soluble resin in which a matting agent is dispersed, a hard coat layer 4 made of an active energy ray-curable resin, and an adhesive layer 6 on a base sheet 2 having releasability. They are at least stacked (see FIG. 1).

The base sheet 2 may be made of a polypropylene resin, a polyethylene resin, a polyamide resin,
Resin sheets such as polyester resin, acrylic resin and polyvinyl chloride resin, metal foil such as aluminum foil and copper foil, cellulosic sheets such as glassine paper, coated paper and cellophane, or composites of the above sheets ,
What is used as a base sheet of a usual transfer material can be used. Further, a release layer 7 may be formed on the base sheet 2 in order to enhance the releasability of the base sheet 2. As the release layer 7, an amino alkyd resin, an epoxy resin, a melamine resin, a urea resin, a polyurethane resin, a polyester resin, a phenol resin, a mixed resin thereof, or the like can be used. As a method for forming the release layer 7, there are a coating method such as a gravure coating method, a roll coating method, a comma coating method, and a lip coating method, and a printing method such as a gravure printing method and a screen printing method. When forming the release layer 7, the surface of the base sheet 2 may be subjected to a corona treatment or an easy adhesion treatment.

The partial mat layer 3 is formed on the base sheet 2 or the release layer 7. The mat layer 3 is a layer for partially matting the surface of the object to be transferred.
Is a layer that is removed by washing with water after peeling. As the partial mat layer 3, a layer obtained by dispersing a matting agent in a water-soluble resin such as sodium polyacrylate, polyvinylpyrrolidone, and polyvinyl alcohol is used. As a matting agent,
An inorganic pigment containing silicon oxide, titanium oxide, carbon black, precipitated barium, calcium carbonate, calcium oxide, talc, or the like, or an organic pigment such as phthalocyanine, dioxazine, or anthraquinone is used. The partial mat layer 3 is adjusted to have a gloss value of less than 175 by adjusting the amount and particle size of the matting agent in accordance with the mat feeling to be expressed. Gross value is 17
If it is 5 or more, it looks glossy visually and does not show a matte feeling.

As a method for forming the partial mat layer 3, there are printing methods such as a gravure printing method, a screen printing method and an offset printing method. The thickness of the partial mat layer is 0.5 μm to 3
0 μm. If it is less than 0.5 μm, the base sheet 2 is stretched when transferring to a two-dimensional or three-dimensional shape or transferring simultaneously to molding, and the partial mat layer may be sheared at that part, The mat feeling may be lost. On the other hand, if the thickness exceeds 30 μm, when transferring to a two-dimensional or three-dimensional shape or transferring simultaneously with molding, it is impossible to follow the elongation of the base sheet 2 and cracks occur in the partial mat layer itself. Also, since a large amount of matting agent may be used depending on the thickness of the partial mat layer 3,
As the thickness of the film increases, the cost increases. The more preferable thickness of the partial mat layer 3 is 1 to 5 μm. .

The hard coat layer 4 is a layer which is peeled off from the base sheet 2 and becomes the uppermost layer of the transfer layer when the base sheet 2 is peeled off after the transfer. As the hard coat layer 4,
An active energy ray-curable resin that is cured by ultraviolet rays or electron beams is used. Examples of the method for forming the hard coat layer 4 include a coating method such as a gravure coating method, a roll coating method, a comma coating method, and a lip coating method, and a printing method such as a gravure printing method and a screen printing method.

With this configuration, when the transfer sheet is adhered to the molded article, when the base sheet 2 is separated, the partial mat layer 3 and the base sheet 2 are separated, and then the hard coat layer 4 is washed with water. Since the partial mat layer 3 can be removed from the surface, it is necessary to secure a sufficient drying time between the printing of the partial mat layer and the printing of the hard coat layer in order to prevent appearance defects in the partial mat hard coat molded product. Absent. That is, the partial matte hard coat transfer material of the present invention can be manufactured continuously by inline printing.

If necessary, a picture layer 5 may be formed between the hard coat layer 4 and the adhesive layer 6 (see FIG. 2). The picture layer 5 is usually formed on the hard coat layer 4 as a printing layer. As the material of the printing layer, polyvinyl resin, polyamide resin, polyacrylic resin, polyurethane resin, polyvinyl acetal resin, polyester urethane resin, cellulose ester resin,
It is preferable to use a coloring ink containing a resin such as an alkyd resin as a binder and a pigment or dye of an appropriate color as a coloring agent. In the case of coloring a metal, a pearl pigment obtained by coating titanium oxide on metal particles such as aluminum, titanium, and bronze, or mica can also be used. Offset printing method,
A normal printing method such as a gravure printing method or a screen printing method may be used. In particular, an offset printing method or a gravure printing method is suitable for performing multicolor printing and gradation expression. In the case of a single color, a coating method such as a gravure coating method, a roll coating method, and a comma coating method can be adopted. The print layer may be formed to a thickness of 0.5 to 50 μm. The printing layer may be provided entirely or partially depending on the picture to be expressed. Further, an anchor layer may be provided between the printing layer and the hard coat layer in order to improve the adhesion to the hard coat layer. As the material of the anchor layer, a two-component curable urethane resin, a thermosetting urethane resin, a thermosetting resin such as a melamine resin or an epoxy resin, or a thermoplastic resin such as a vinyl chloride copolymer resin may be used. . Examples of the method for forming the anchor layer include a coating method such as a gravure coating method, a roll coating method, and a comma coating method, and a printing method such as a gravure printing method and a screen printing method.

The pattern layer 5 may be composed of a metal thin film layer 9 or a combination of a printing layer and a metal thin film layer (see FIGS. 3 and 4). Metal thin film layer 9
Is for expressing metallic luster as the picture layer 5, and is formed by a vacuum evaporation method, a sputtering method, an ion plating method, a plating method, or the like. Further, a metal foil may be used. Metals such as aluminum, nickel, gold, platinum, chromium, iron, copper, tin, indium, silver, titanium, lead, and zinc, and alloys or compounds thereof are used according to the metallic luster color to be expressed.

When the metal thin film layer 9 is provided, an anchor layer 8 such as a front anchor layer or a rear anchor layer may be provided in order to improve the adhesion between another transfer layer and the metal thin film layer 9. . As a material of the anchor layer 8, a two-component curable urethane resin, a thermosetting urethane resin, a thermosetting resin such as a melamine resin or an epoxy resin, or a thermoplastic resin such as a vinyl chloride copolymer resin is used. Good. Anchor layer 8
As a method of forming, a gravure coating method, a roll coating method, a coating method such as a comma coating method, a gravure printing method,
There are printing methods such as a screen printing method.

The adhesive layer 6 is for bonding the above layers to the surface of the molded product. The adhesive layer 6 is formed on a portion to be bonded. That is, if the portion to be bonded is the entire surface, the adhesive layer 6 is formed entirely on the picture layer 5. If the portion to be bonded is partial, the adhesive layer 6 is partially formed on the picture layer 5. As the adhesive layer 6, a resin having heat-sensitive and pressure-sensitive adhesive properties suitable for the material of the molded product is appropriately used. For example, when the material of the molded article or the molding resin is an acrylic resin, an acrylic resin may be used. When the material of the molded product or the molding resin is a polyphenylene oxide / polystyrene resin, a polycarbonate resin, a styrene copolymer resin, or a polystyrene blend resin, an acrylic resin or a polystyrene resin having an affinity for these resins. , A polyamide resin or the like may be used. Furthermore, when the material of the molded article or the molding resin is a polyethylene resin or a polypropylene resin, a chlorinated polyolefin resin, a chlorinated ethylene-vinyl acetate copolymer resin, a cyclized rubber, and a coumarone indene resin can be used. is there. As a method for forming the adhesive layer 6, a gravure coating method,
There are coating methods such as a roll coating method and a comma coating method, and printing methods such as a gravure printing method, a screen printing method, and an offset printing method.

The structure of the transfer layer is not limited to the above-described embodiment. For example, when a material having excellent adhesion to a molded product is used as the material of the picture layer 5, the adhesive layer 6 is omitted. can do.

In order to obtain a transfer product having a matte feeling while making use of the ground pattern and transparency of the molded product, the hard coat layer 4 and the adhesive layer are formed on the base sheet 2 on which the partial mat layer is printed. It is also possible to form a layer and omit the picture layer and the like.

As molded products, resin molded products, rubber products,
Examples include metal products, wood products, glass products, ceramic products, and composite products made of various materials. The molded article may be transparent, translucent, or opaque. Further, the molded article may be colored or uncolored. Examples of the resin include general-purpose resins such as a polystyrene resin, a polyolefin resin, an ABS resin, an AS resin, and an AN resin. Also, general-purpose engineering resins and polysulfone resins such as polyphenylene oxide / polystyrene resin, polycarbonate resin, polyacetal resin, acrylic resin, polycarbonate-modified polyphenylene ether resin, polyethylene terephthalate resin, polybutylene terephthalate resin, ultra-high molecular weight polyethylene resin, Super engineering resins such as polyphenylene sulfide resin, polyphenylene oxide resin, polyarylate resin, polyetherimide resin, polyimide resin, liquid crystal polyester resin, and polyallyl heat-resistant resin can also be used. Further, a composite resin to which a reinforcing material such as glass fiber or inorganic filler is added can be used.

A method of decorating the surface of a molded product by using a transfer method using a partial matte hard coat transfer material having the above-described layer structure will be described.

First, the adhesive layer 6 side of the transfer material is brought into close contact with the surface of the molded article. Next, using a transfer machine such as a roll transfer machine equipped with a heat-resistant rubber-like elastic body such as silicon rubber, an up-down transfer machine, and a vacuum press transfer machine, the temperature is 80 to 260.
Heat and pressure are applied from the base sheet 2 side of the transfer material through a heat-resistant rubber-like elastic body set to a condition of about ° C. By doing so, the adhesive layer 6 adheres to the molded product surface 10.

Next, when the base sheet 2 is peeled off after cooling, separation occurs at the boundary surface between the base sheet 2 or the partial mat layer 3 and the hard coat layer 4, and transfer is completed (see FIG. 5).

Next, the hard coat layer 4 is cross-linked and hardened by irradiation with active energy rays. As the active energy ray, ultraviolet rays or the like are used, and 400 to 4000 mJ / cm.
Irradiation may be performed under about ^two conditions.

Finally, the water-soluble resin of the partial mat layer remaining on the surface of the hard coat layer is washed away with water to obtain a partially mat hard coat molded product. In water washing, after spraying or shower washing with water having a water temperature of 20 to 40 ° C., rubbing is performed by impregnating a soft washing tool such as a sponge (see FIG. 6). After washing with water, the molded article may be dried in a drying oven at 40 to 60 ° C. to evaporate the moisture on the surface of the molded article. The drying time at this time is 30 seconds to 3 seconds.
0 minutes. Considering work efficiency, 30 to 60 seconds is desirable.

When the transfer target is a resin molded product, there is a simultaneous molding transfer method as a method for performing the transfer method more rationally. Next, a method of decorating the surface of a resin molded article as an object to be transferred by using the above-described transfer material and using a simultaneous molding transfer method will be described.

First, the transfer material is fed into a molding die 7 composed of a movable die and a fixed die. At this time, the sheet transfer material may be fed one by one, or a necessary portion of a long transfer material may be sent intermittently.

After the molding die 7 is closed, the molten resin is injected and filled into the die 7 from the gate, and a transfer material is adhered to the surface of the molded product while forming the molded product. After cooling and solidification, the molding die 7 is opened and the molded product is taken out.

Next, when the base sheet 2 is peeled off after cooling, peeling occurs at the interface between the base sheet 2 or the partial mat layer 3 and the hard coat layer 4, and the transfer is completed.

Next, the hard coat layer 4 is cross-linked and cured by irradiation with active energy rays.

Finally, a partially matte hard coat molded product can be obtained by rinsing and removing the water-soluble resin of the partial matte layer remaining on the hard coat layer surface.

[0039]

EXAMPLE A polyethylene terephthalate film having a thickness of 38 μm, which was subjected to a release treatment, was used as a base sheet, and the following layers were continuously formed by in-line printing to form a partial matte hardware for a window panel of a mobile phone. A coat transfer material was produced.

That is, gravure printing was partially performed using an ink obtained by adding silica particles to a sodium acrylate resin, and the resulting product was touch-dried through a drying hood at 80 ° C. to form a partial mat layer.

Subsequently, a urethane acrylate type ultraviolet curable ink was subjected to gravure printing, and a hard coat layer was formed through a drying hood at 80 ° C.

Subsequently, an ink composed of an acrylic resin and a vinyl resin containing a colorant was subjected to gravure printing, and a picture layer was formed through a drying hood at 80 ° C.

Finally, an ink composed of a vinyl chloride-vinyl acetate copolymer resin was gravure-printed, and an adhesive layer was formed through a drying hood at 80 ° C.

Such a partially matte hard coat transfer material was fixed in an injection molding die, clamped, and an acrylic resin was injected. After cooling, the mold was opened, the base sheet of the partial mat hard coat transfer material was peeled off, and a high pressure mercury lamp (1 kW / c) was applied to the transfer layer and the partial mat layer adhered to the surface of the molded product.
m) for 7 seconds at an irradiation distance of 3 cm using ultraviolet light,
The hard coat layer was cross-linked and cured.

After shower washing with water at a water temperature of 40 ° C., sponge is impregnated and rub-washed.
When dried in a drying oven at 60 ° C. for 1 minute, the partial mat layer remaining on the hard coat layer surface was removed cleanly,
The cell phone window panel was obtained.

The thus obtained partially matte hard coat molded product has a mat portion formed on the surface without fail.
In addition, the surface was excellent in scratch resistance, friction resistance, and solvent resistance.

[0047]

The method for producing a partially matte hard coat transfer material and a partially matte hard coat molded product according to the present invention has the following configuration, and therefore has the following excellent effects.

That is, the partial mat hard coat transfer material of the present invention comprises a partial mat layer having fine irregularities made of a water-soluble resin in which a matting agent is dispersed on a base sheet having releasability; A hard coat layer made of resin and an adhesive layer are laminated at least, and after transfer, the partial mat layer remaining on the hard coat layer surface is removed by washing with water, so that appearance defects do not occur in the partial mat hard coat molded product. It is not necessary to secure a sufficient drying time between the printing of the partial mat layer and the printing of the hard coat layer. Therefore, even when the transfer material is manufactured by in-line printing, decoration having a partial mat and excellent surface strength can be reliably performed.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an embodiment of a partial matte hard coat transfer material of the present invention.

FIG. 2 is a sectional view showing another embodiment of the partial matte hard coat transfer material of the present invention.

FIG. 3 is a sectional view showing another embodiment of the partial matte hard coat transfer material of the present invention.

FIG. 4 is a sectional view showing another embodiment of the partial matte hard coat transfer material of the present invention.

FIG. 5 is a sectional view showing one embodiment of the steps of the method for producing a partially matte hard coat molded product of the present invention.

FIG. 6 is a sectional view showing one embodiment of the steps of the method for producing a partially matte hard coat molded product of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Partial mat hard coat transfer material 2 Base sheet 3 Partial mat layer 4 Hard coat layer 5 Picture layer 6 Adhesive layer 7 Release layer 8 Anchor layer 9 Metal thin film layer 10 Molded article

Claims (5)

[Claims] 1. A partial mat layer having fine irregularities made of a water-soluble resin in which a matting agent is dispersed, a hard coat layer made of an active energy ray-curable resin, and an adhesive layer are provided on a base sheet having releasability. A partially matte hard coat transfer material characterized by being laminated. 2. The water-soluble resin is sodium polyacrylate,
2. The partial matte hard coat transfer material according to claim 1, wherein the material is one of polyvinylpyrrolidone and polyvinyl alcohol. 3. The partial matte hard coat transfer material according to claim 1, further comprising a picture layer between the hard coat layer and the adhesive layer. 4. The partial mat hard coat transfer material according to claim 1, which is adhered to the surface of a molded product, and after the base sheet is peeled off, the active material is irradiated with an active energy ray, and then the hard coat layer surface is applied. A method for producing a partial mat hard coat molded product, comprising washing and removing a water-soluble resin of a remaining partial mat layer with water. 5. The partial mat hard coat transfer material according to claim 1, which is sandwiched in an injection mold, a molding resin is injected into a cavity, and an injection molded product is obtained at the same time. The transfer material is adhered to the surface, the mold is opened, the molded product is taken out, the base sheet is peeled off, the active energy ray is irradiated, and then the water-soluble resin of the partial mat layer remaining on the hard coat layer surface is washed off with water. A method for producing a partially matte hard coat molded product.