JP3955599B2 - Transfer sheet for mat hard coat and method for producing mat hard coat molded product - Google Patents

Description

  Conventionally, there is a transfer method as a method for decorating the surface of home appliances, cosmetic containers, miscellaneous goods and the like. The transfer method uses a transfer sheet in which a transfer layer composed of a release layer, a decorative layer, an adhesive layer, and the like is formed on a base sheet. After the heat and pressure are applied to the transfer layer, the base sheet is It is a method of peeling and transferring only the transfer layer to the surface of the molded product for decoration. As a transfer sheet for obtaining a decorative molded product having high surface strength, a hard coat layer made of an ionizing radiation curable resin composition is formed on a substrate sheet having releasability, and further a decorative layer and an adhesive are formed thereon. Some formed layers.

  Furthermore, as a transfer sheet for a partial mat hard coat for obtaining a decorative molded product having a high surface strength and a partially mat-like surface, a partial mat layer made of a curable resin has been conventionally formed on a base sheet. Has been proposed in which a hard coat layer made of an ionizing radiation curable resin composition is formed, and a decorative layer, an adhesive layer, and the like are further formed thereon. When such a transfer sheet is adhered to a molded product and the partial mat layer is peeled off together with the base sheet, the surface of the partial mat layer has fine irregularities, so the irregularities are copied to the transfer layer, and the mat shape is partially And a hard coat layer is expected to be formed.

Conventionally, as the partial mat layer, a curable resin having good adhesion to the base sheet, for example, amino alkyd resin or urea melamine resin in which resin fine particles are dispersed is used, and a specific glass transition is used as the hard coat layer. A transfer sheet for partial mat hard coat using a resin in a temperature zone has been proposed (see, for example, Patent Document 1).
These transfer sheets are expected to be used not only for forming a partial mat hard coat layer but also for forming a full mat hard coat layer.

JP 2000-85299 A

  However, in the case of so-called inline printing in which a series of printing machines is used to print from the partial mat layer to the hard coat layer, and in some cases, the decorative layer, a sufficient drying time is required between the printing of the partial mat layer and the hard coat layer. It cannot be secured. As a result, before the resin constituting the partial mat layer is sufficiently cured, the hard coat layer is inevitably formed, and the resin constituting the partial mat layer is ionizing radiation curable constituting the hard coat layer. The adhesiveness between the partial mat layer and the hard coat layer is increased by reacting with the resin. For this reason, when the base sheet is peeled off after the transfer sheet is adhered to the molded product, the hard coat layer does not peel off between the partial mat layer and the hard coat layer, or the base sheet peels off. There is a problem that the appearance of the partially matted hard coat molded product is poor.

  In the case of the transfer sheet for a partial mat hard coat having a hard coat layer made of a specific material described in Patent Document 1, the problems caused when the base sheet is peeled off after the transfer sheet is bonded are improved to some extent. However, the problem was not completely overcome.

  In addition, 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 cured, and then attached to the printing machine again to print the hard coat layer and the subsequent layers, Since the reactive group in the resin constituting the partial mat layer disappears when the curing proceeds sufficiently, it does not react with the ionizing radiation curable resin constituting the hard coat layer, and the adhesion between the partial mat layer and the hard coat layer is Although lower, there are the following problems. That is, since printing of the partial mat layer and printing after the hard coat layer must be performed in separate steps, it is not economical in the production of the transfer sheet for the partial mat hard coat. In addition, since the printing process of the partial mat layer and the hard coat layer takes more heat and longer time than in the case of inline printing, the base sheet contracts and the previously printed partial mat layer It is difficult to make this pattern coincide with the pattern of the decorative layer, in particular, after the hard coat layer to be printed later.

Therefore, the present invention provides a mat hard coat transfer sheet used for decorating with a matte feel and excellent surface strength, and reliably between the base sheet and the hard coat layer when the base sheet is peeled off after transfer. It is an object of the present invention to obtain a mat hard coat transfer sheet to be peeled off. Another object of the present invention is to obtain a mat hard coat transfer sheet that can be manufactured by performing inline printing with mat type printing and printing after the hard coat layer. Furthermore, the present invention provides a mat hard coat transfer sheet that allows easy positioning of the decorative layer even when a partial mat layer and a decorative layer combined therewith are formed. Make things a challenge.
Moreover, this invention makes it a subject to provide the manufacturing method of the mat | matte hard-coat molded product which has a mat feeling and can attach the decoration excellent in surface strength.
Other problems of the present invention will become apparent from the following description of the present invention.

In order to solve the above-described problem, the transfer sheet for mat hard coat of the present invention has a transfer layer including an ionizing radiation curable hard coat layer at least in an uncured or semi-cured state formed on one surface of a base sheet, A mat mold including resin fine particles having an average particle diameter of 5 to 25 μm is formed on the other surface of the base sheet.
In the transfer sheet for mat hard coat of the present invention, the hard coat layer and the mat mold are disposed on both sides of the base sheet, so that the hard coat layer and the mat mold are not fixed. Since the mat mold is used for forming the hard coat layer via the deformation of the base sheet, such a mat mold is optimized. That is, the mat type includes resin fine particles having an average particle diameter of 5 to 25 μm. Further, since the hard coat layer is in an uncured or semi-cured state in the state of the transfer sheet, the hard coat layer is easily deformed into a mat-molded state following the deformation of the base sheet.

The transfer sheet for mat hard coat of the present invention does not have to wait for the mat mold to be specially dried in the production process, and can be easily produced by so-called in-line printing which is printed with a series of printing machines together with a decorative layer and the like. However, the transfer sheet for mat hard coat of the present invention does not necessarily have to be manufactured by in-line printing, and may be manufactured by off-line printing.
The transfer sheet for mat hard coat of the present invention may be used for a transfer product having a mat shape on the entire surface (that is, the above-mentioned mat mold may be formed on almost the entire surface of the transfer sheet). In particular, it may be used for a transfer product having a mat shape (that is, the above-mentioned mat mold may be formed on a part of a transfer sheet). In another molding method, the present invention is preferably used for a transfer product partially having a mat shape because it is difficult to produce a product having a partial mat hard coat.

In the transfer sheet for mat hard coat according to a preferred embodiment of the present invention, the average thickness of the base sheet is t (μm), and the weight average particle diameter of the resin fine particles obtained by the Coulter counter method is d ( (μm), equation (1) may hold.
0.06 ≦ t / d ² ≦ 1.9 (1)
(However, 12 ≦ t ≦ 50)
Regarding the formula (1), when it is difficult to measure the weight average particle diameter of the resin fine particles obtained by the Coulter counter method, the equivalent spherical diameter obtained using an image processing apparatus is used.
As described above, the mat mold is used for forming the hard coat layer via the deformation of the base sheet. In order to satisfactorily perform this deformation and molding, it is preferable that the thickness of the base sheet and the particle diameter of the resin fine particles contained in the mat mold satisfy the relationship of the formula (1). The transfer sheet for mat hard coat according to this preferred embodiment makes it easier to form a hard coat layer and provides a more preferable mat-shaped hard coat layer.

The manufacturing method of the partial mat | matte hard coat molded article of this invention consists of the following processes.
Step of preparing the mat hard coat transfer sheet according to the present invention (b) The transfer layer side of the mat hard coat transfer sheet is the molded product side, the mart hard coat transfer sheet is positioned on the surface of the molded product, And applying a pressure from the mat mold side to transfer the transfer layer to the molded product and to form a mat shape on the uncured or semi-cured hard coat layer, and to integrate the mat hard coat transfer sheet and the molded product. (C) a step of peeling off the base sheet from the monolith to obtain a molded product with a hard coat in a mat-molded state; d) irradiating the molded product with a hard coat in the mat-molded state with ionizing radiation; Process to harden hard coat layer and obtain mat hard coat molded product

In another method for producing a mat hard coat molded article according to the present invention, the mat hard coat transfer sheet according to the present invention is installed in an injection mold, and after molding resin is injected into the mold and cooled and solidified. The mold is opened, the molded product is taken out and the base sheet is peeled off, and then the ionized radiation curable hard coat layer in an uncured or semi-cured state is cured by irradiating the molded product with ionizing radiation. .
One embodiment of the present invention described above, preferred embodiments of the present invention, and components included in these embodiments can be implemented in combination as much as possible.

  ADVANTAGE OF THE INVENTION According to this invention, the transfer sheet for mat | matte hard-coats which has a mat feeling and can perform the decoration excellent in surface strength reliably can be obtained. Further, when used in the transfer step, a mat hard coat transfer sheet from which the base sheet and the hard coat layer can be easily peeled is obtained. Furthermore, according to the present invention, the mat-type printing and the printing after the hard coat layer can be produced by in-line printing, and a mat hard coat transfer sheet that can be produced economically is obtained. Moreover, according to the present invention, even when a partial mat layer and a decorative layer combined therewith are formed, the mat hard coat transfer sheet can easily align the decorative layer. Is obtained.

In addition, according to the present invention, a method for producing a mat hard coat molded product that can reliably produce a transfer product having a matte feeling and excellent surface strength can be obtained.
Furthermore, according to the present invention, a method for producing a mat hard coat injection molded article that can reliably produce an injection molded article having a mat feeling and excellent surface strength can be obtained.
The transfer sheet for mat hard coat and the method for producing a mat hard coat molded product according to the present invention are particularly suitable for the production of a partial mat hard coat product.

  With reference to the drawings, the mat hard coat transfer sheet and the method for producing a mat hard coat molded product according to the present invention will be further described below. The dimensions, materials, shapes, relative positions, etc. of the members and parts described in the embodiments of the present invention are not intended to limit the scope of the present invention to those unless otherwise specified. It is merely an illustrative example.

FIG. 1 is a cross-sectional explanatory view showing the structure of one embodiment of a transfer sheet 1a for mat hard coat according to the present invention.
On one surface of the base sheet 11, an uncured or semi-cured hard coat layer 13a and an adhesive layer 14 are sequentially formed. The transfer layer 16a of the mat hard coat transfer sheet 1a includes an uncured or semi-cured hard coat layer 13a, an adhesive layer 14, and other layers formed as necessary. A mat die 12 is partially formed on the other surface of the base sheet 11. The mat mold may be formed on the entire surface of the base sheet 11 as necessary.

FIGS. 2A to 2D are cross-sectional explanatory views showing a method of decorating a molded product by a transfer method using the mat hard coat transfer sheet 1a.
As shown in FIG. 2 (a), the transfer layer 14 of the mat hard coat transfer sheet 1 a faces the molded product 6, and the mat hard coat transfer sheet 1 a is adhered to the surface of the molded product 6. Then, using a transfer machine such as a roll transfer machine, an up-down transfer machine, and a vacuum press transfer machine provided with a pressure heat roller 31 made of a heat-resistant elastic body (for example, silicon rubber), the temperature is set to about 80 to 260 ° C. The pressure and heat roller 31 applies heat and pressure from the mat mold 12 side of the mat hard coat transfer sheet 1a.

FIG. 2B is a view showing a state of the mat hard coat transfer sheet 1 a and the molded product 6 in an integrated state after the pressure heat is applied by the pressure heat roller 31. Since the mat mold 12 is pressed against the base sheet 11, the base sheet 11 is deformed so as to substantially match the shape of the mat mold 12. The deformation of the base sheet is reflected on the uncured or semi-cured hard coat layer, and the mat-molded hard coat layer 13b is formed. At the same time, the adhesive layer 14 adheres to the molded product 6.
After cooling, as shown in FIG. 2C, the base sheet 11 with the mat die 12 is peeled from the mat hard coat transfer sheet 1a and the molded product 6. In this step, peeling occurs at the boundary surface between the base sheet 11 and the mat-shaped hard coat layer 13b, and the transfer is completed.

Next, as shown in FIG. 2 (d), the ionizing radiation 36 is irradiated to crosslink and cure the uncured or semi-cured ionizing radiation curable hard coat layer 13b, which is a mat-molded state. A hard coat layer 13c is obtained. As the ionizing radiation 36, ultraviolet rays or electron beams may be used, and irradiation may be performed under conditions of about 400 to 4000 mJ / cm ² .
As described above, a molded product decorated with the mat hard coat layer can be manufactured.

  The mat mold 12 requires a certain thickness in order to mat-mold the hard coat layer through deformation of the base sheet 11. In order to provide this thickness and to form appropriate irregularities, the mat mold 12 is formed of resin fine particles having an average particle diameter of 5 μm to 25 μm. Specifically, the mat mold 12 can be formed, for example, by printing with an ink in which the resin fine particles and a binder are mixed.

FIG. 3 is a schematic cross-sectional view of the mat mold 12 formed using ink composed of resin fine particles and a binder.
The mat mold 12 is formed by printing the mat mold forming ink 21 on the surface of the base sheet 11. The mat-type forming ink 21 is considered to be fixed to the surface of the base sheet 11 by a thin layer binder 23 surrounding the surface of the resin fine particles 22. Although FIG. 3 illustrates the case where the resin fine particles are arranged in a single layer on the surface of the base sheet 11, the resin fine particles may be arranged in two layers or three layers.

The resin fine particles having an average particle diameter of 5 μm to 25 μm are used to secure the thickness of the mat mold 12 necessary for making the hard coat layer mat-like through deformation of the base sheet, and at the same time, in the mat-molded state, This is to form moderate irregularities necessary to make the surface of the coat layer matte. In particular, when resin fine particles having an average particle diameter of 8 μm to 15 μm are used, a very beautiful mat feeling can be obtained.
If the average particle diameter is less than 5 μm, the required thickness of the mat mold 12 cannot be ensured. If the average particle diameter is larger than 25 μm, the surface of the molded product is inconvenient because it feels more rugged than matte.

Furthermore, as described above, the mat mold is used for forming the hard coat layer via the deformation of the base sheet. In order to satisfactorily perform this deformation and molding, the relationship between the thickness of the base sheet and the particle size of the resin fine particles contained in the mat mold was tested.
Matte feeling when changing the average thickness t (μm) of the base sheet and the weight average particle diameter d (μm) of the resin fine particles to prepare a transfer sheet for mat hard coat and using this to produce a molded product The results of measuring are shown in Table 1.

マット感は、目視の結果を以下の３段階で評価したものである。
○ 良好
△ やや良
× 不可
樹脂微粒子の重量平均粒子径は、コールターカウンター法により求めた。

The matte feeling is obtained by evaluating the visual result in the following three stages.
○ Good △ Somewhat good × Weight average particle size of resin fine particles was determined by a Coulter counter method.

From the above experiment, in the mat hard coat transfer sheet according to the present invention, the average thickness of the base sheet is t (μm), and the weight average particle diameter of the resin fine particles obtained by the Coulter counter method is d ( (μm), it has become clear that the formula (1) is preferably satisfied.
0.06 ≦ t / d ² ≦ 1.9 (1)
(However, 12 ≦ t ≦ 50)
The numerical range of the thickness t (μm) of the base sheet was determined based on the experimental results shown in Table 1 and factors such as handleability when the transfer sheet is used in the transfer process.

  Regarding the formula (1), when it is difficult to measure the weight average particle diameter of the resin fine particles obtained by the Coulter counter method, a sphere equivalent diameter obtained using an image processing apparatus can be used.

In forming the mat 12, an ink composed of resin fine particles and a binder can be used.
In creating a transfer sheet used in the transfer method described with reference to FIG. 2, the mat mold 12 is made of a curable resin such as an epoxy resin, a cyanoacrylate resin, a urethane acrylate resin, or a melamine resin as a binder, What disperse | distributed resin fine particles with an average particle diameter of 5-25 micrometers is preferable.
On the other hand, when preparing a transfer sheet used in the simultaneous molding transfer method described later, an average particle diameter is obtained by using a thermoplastic resin such as a polyvinyl resin, a thermoplastic polyacrylic resin, a thermoplastic polyurethane resin, or a polyester resin as a binder. What disperse | distributed 5-25 micrometer resin fine particles is preferable.

  In the case of the transfer method, it is preferable to use a curable resin as a binder. If a thermoplastic resin or the like is used, the mat mold 12 may adhere to a part of the transfer machine when the heat and pressure are changed. Because there is. On the other hand, in the case of the simultaneous molding transfer method, it is preferable to use a thermoplastic resin as a binder. When a curable resin is used, unreacted oligomers and additives are released and the surface of the molding die is contaminated. This is because there is a case where it ends up.

  In addition to resin particles such as silicon, benzoguanamine, acrylic, styrene, urethane, and melamine, the resin fine particles referred to in the present invention include inorganic pigments and components such as carbon black, precipitated barium, calcium carbonate, calcium oxide, and talc. It shall contain organic pigments such as Russian, dioxazine and anthraquinone. The amount of the resin fine particles is preferably adjusted to about 10 to 30% that does not cause cohesive failure with respect to the binder.

  As a method for forming the mat mold 12, there are printing methods such as a gravure printing method, a screen printing method, and an offset printing method. The thickness of the mat mold 12 is 5 μm to 200 μm at the thickest part. By setting the thickness within this range, the uncured or semi-cured ionizing radiation curable hard coat layer 13a can be brought into a mat-molded state. In addition, when a plurality of transfer sheet portions are formed on a belt-like base sheet and wound in a roll shape, it is possible to prevent the transfer sheet portion from becoming a bumpy shape. Considering the stability in production, a more preferable thickness is 10 to 50 μm.

The uncured or semi-cured ionizing radiation curable hard coat layer 13a is a layer that becomes the uppermost layer of the transfer layer 16a after the substrate sheet 11 is peeled off after the transfer. As the ionizing radiation curable hard coat layer 13a in an uncured or semi-cured state, an ionizing radiation curable resin that is cured by ultraviolet rays or electron beams is used. By setting the uncured or semi-cured state, the unevenness of the mat mold 12 is reflected on the surface portion of the hard coat layer 13a at the time of transfer.
As the ionizing radiation curable hard coat layer 13a in an uncured or semi-cured state, a urethane acrylate resin, a cyanoacrylate resin, or the like can be used. As a method of making it a semi-cured state, there is a method of crosslinking a part of the monomer or oligomer by adding an additive such as isocyanate and applying heat. Examples of the method of forming the uncured or semi-cured ionizing radiation curable hard coat layer 13a include a gravure coating method, a roll coating method, a comma coating method, a lip coating method, a gravure printing method, a screen printing method, and the like. There is a printing method.

  As a material of the base sheet 11, those used as a base sheet of a normal transfer sheet, such as a resin sheet such as a polypropylene resin, a polyethylene resin, a polyamide resin, a polyester resin, an acrylic resin, and a polyvinyl chloride resin, are used. Can be used. The thickness of the base sheet 2 reflects the unevenness of the mat mold 12 on the surface of the ionizing radiation curable hard coat layer 4 in an uncured or semi-cured state, and there are defects such as wrinkle marks on the surface of the mat hard coat molded article. 12-50 micrometers which do not generate | occur | produce is preferable.

  In order to improve the peelability of the base sheet 11, a release layer may be formed on the transfer layer side surface of the base sheet 11. As the release layer, aminoalkyd resins, epoxy resins, melamine resins, urea resins, polyurethane resins, polyester resins, phenol resins, or a mixed resin thereof can be used. As a method for forming the release layer, there are a coating method such as a gravure coating method, a roll coating method, a comma coating method and a lip coating method, a printing method such as a gravure printing method and a screen printing method. Further, when forming the release layer, the surface of the base sheet 11 can be subjected to corona treatment or easy adhesion treatment.

If necessary, the mat hard coat transfer sheet according to the present invention may be provided with a decorative layer.
FIG. 4 is a cross-sectional explanatory view showing a configuration of the mat hard coat transfer sheet 1b including a decorative layer. Components that are the same as or similar to those in FIGS. 1 and 2 are denoted by the same reference numerals.
The decorative layer 15 is formed between the uncured or semi-cured ionizing radiation curable hard coat layer 13 a and the adhesive layer 14. In the case of the mat hard coat transfer sheet 1b including a decorative layer, the transfer layer 16b includes an uncured or semi-cured ionizing radiation curable hard coat layer 13a, a decorative layer 15 and an adhesive layer 14, and further if necessary. It is composed of other layers formed.

The decorative layer 15 is usually formed as a printed layer on the hard coat layer 13a. As the material of the printing layer, a resin such as polyvinyl resin, polyamide resin, polyacrylic resin, polyurethane resin, polyvinyl acetal resin, polyester urethane resin, cellulose ester resin, alkyd resin, etc. is used as a binder. Colored inks containing color pigments or dyes as colorants may be used. In the case of forming a metal color, a pearl pigment in which titanium oxide is coated on metal particles such as aluminum, titanium, bronze, or mica can be used.
As a method for forming the decorative layer 15, a normal printing method such as an offset printing method, a gravure printing method, or a screen printing method may be used. In particular, the offset printing method and the gravure printing method are suitable for performing multicolor printing and gradation expression.

A cross-shaped or square phototube mark is formed in a blank portion on the base sheet 11 of the mat hard coat transfer sheet 1b including the decorating layer, and printing of the decorating layer and mat type are performed while detecting the phototube mark. When printing is performed, the registration of the decorative layer and the mat type can be easily matched. Since the base sheet is usually transparent or translucent, the above-described registration can be easily performed by attaching a photoelectric tube mark only to one surface of the base sheet. The registration using the photoelectric tube mark can be used for inline printing or off-line printing of a transfer layer and a mat mold each including a decoration layer on the front and back surfaces of the base sheet.
When the decoration layer 15 is a single color, a coating method such as a gravure coating method, a roll coating method, or a comma coating method may be employed for forming the decoration layer 15. The decorative layer 15 is preferably formed to a thickness of 0.5 to 50 μm.

  The decoration layer 15 may be provided entirely or partially depending on a decoration pattern to be expressed. In order to improve the adhesion between the uncured or semi-cured ionizing radiation curable hard coat layer 13a, an anchor is provided between the decorative layer 15 and the uncured or semi-cured ionizing radiation curable hard coat layer 13a. A layer may be provided. 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, a printing method such as a gravure printing method, and a screen printing method.

  The decorative layer 15 may be composed of a metal thin film layer or a combination of a printed layer and a metal thin film layer. The metal thin film layer is formed by a vacuum deposition method, a sputtering method, an ion plating method, a plating method, or the like. Moreover, you may use metal foil. Metals such as aluminum, nickel, gold, platinum, chromium, iron, copper, tin, indium, silver, titanium, lead, and zinc, and alloys or compounds thereof are used depending on the metallic luster color to be expressed.

  When providing the metal thin film layer, an anchor layer such as a front anchor layer or a rear anchor layer may be provided in order to improve the adhesion between the other transfer layer and the metal thin film 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, a printing method such as a gravure printing method, and a screen printing method.

  The adhesive layer 14 adheres the transfer layer 16a or 16b to the surface of the molded product. As the adhesive layer 14, a resin having heat and pressure adhesiveness suitable for the material of the molded product or the molded resin is appropriately used. For example, when the material of the molded product or the molded resin is an acrylic resin, an acrylic resin may be used. If the material of the molded product or molded resin is polyphenylene oxide / polystyrene resin, polycarbonate resin, styrene copolymer resin, or polystyrene blend resin, acrylic resin, polystyrene resin, polyamide that has an affinity for these resins A series resin or the like may be used. When the material of the molded product or the molded resin is a polyethylene resin or a polypropylene resin, a chlorinated polyolefin resin, a chlorinated ethylene-vinyl acetate copolymer resin, a cyclized rubber, or a coumarone indene resin can be used. Examples of the method for forming the adhesive layer 14 include coating methods such as gravure coating, roll coating, and comma coating, printing methods such as gravure printing, screen printing, and offset printing.

  The configuration of the transfer layer 16a or 16b is not limited to the above-described embodiment. For example, when the material of the decorative layer 15 is excellent in adhesiveness to a molded product, the adhesive layer 14 is used. Can be omitted.

  Examples of the molded product 6 include resin molded products, rubber products, metal products, woodwork products, glass products, ceramic products, and composite products made of various materials. The molded product 6 may be transparent, translucent, or opaque. The molded product 6 may be colored or uncolored. Examples of the resin include general-purpose resins such as polystyrene resin, polyolefin resin, ABS resin, AS resin, and AN resin. General engineering resins such as polyphenylene oxide / polystyrene resins, polycarbonate resins, polyacetal resins, acrylic resins, polycarbonate-modified polyphenylene ether resins, polyethylene terephthalate resins, polybutylene terephthalate resins, ultrahigh molecular weight polyethylene resins, and polysulfone resins, 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. Furthermore, you may use the composite resin which added reinforcing materials, such as glass fiber and an inorganic filler.

When the molded product 6 is an injection molded resin molded product, there is a simultaneous molding transfer method as a method for performing the transfer method more rationally. Next, a method for decorating the surface of an injection-molded resin molded product, which is a molded product, using the simultaneous transfer method using the transfer sheet according to the present invention will be described.
FIG. 5 is an explanatory diagram for explaining the steps of the simultaneous molding and transfer method.

  First, the mat hard coat transfer sheet 1a is fed into a molding die composed of a die A41 and a die B42. At that time, the single sheet partial mat hard coat transfer sheet 1 may be fed one by one for each injection molding, or a transfer in which a number of mat hard coat transfer sheets 1a are formed on a belt-like base sheet. A sheet may be prepared, and the mat hard coat transfer sheet 1a portion may be intermittently fed for each injection molding. The latter is preferable in view of productivity. After the molding die is closed, the injection molding resin melted from the gate 43 is filled into the molding die, and at the same time as forming the molded product, the partial mat hard coat transfer sheet 1a is adhered to the surface. At this time, the mat mold 12 is pressed against the inner surface of the mold B42. As a result, the base sheet 11 is deformed, and the uncured or semi-cured hard coat layer 13a is formed into a mat shape.

  After cooling and solidification, the molding die is opened and the molded product is taken out. Next, when the base sheet 11 is peeled off, peeling occurs at the boundary surface between the base sheet 11 and the ionized radiation curable hard coat layer 13b in the mat-molded state, and the transfer is completed. The removal of the molded product and the peeling of the base sheet may be performed simultaneously. Subsequently, a mat hard coat molded product can be obtained by irradiating with ionizing radiation to crosslink and cure the hard coat layer 13b in the mat molded state.

  A sheet obtained by subjecting a polyethylene terephthalate film having a thickness of 38 μm to a release treatment as a base sheet, and forming the following layers, a transfer sheet for a partial mat hard coat for a window panel of a cellular phone was produced.

  That is, an ultraviolet curable ink composed of a urethane acrylate resin containing 1% isocyanate was reverse-coated, and a semi-cured ionizing radiation curable hard coat layer was formed through a dry hood at 150 ° C. Then, the ink which consists of an acrylic resin and vinyl resin containing a coloring agent was gravure-printed, and the decoration layer was formed through the 80 degreeC dry hood. Finally, gravure printing was performed with an ink composed of a vinyl chloride / vinyl acetate copolymer resin, and an adhesive layer was formed through a dry hood at 80 ° C. Subsequently, on the surface opposite to the above layers of the base sheet, partial screen printing was performed using an ink obtained by adding 20% silicon resin particles having an average particle diameter of 12 μm to a thermoplastic polyester resin, and a finger was passed through a 80 ° C. dry hood. Touch drying was performed to form a mat mold having a maximum film thickness of 38 μm.

  The partial mat hard coat transfer sheet was fixed to an injection mold, clamped and injected with acrylic resin. After cooling, the mold is opened, the base sheet of the partial mat hard coat transfer sheet is peeled off, and then a high pressure mercury lamp (1 kW / cm) is applied to the surface of the semi-cured ionizing radiation curable hard coat layer formed on the surface of the molded product. It was irradiated with ultraviolet rays for 7 seconds at an irradiation distance of 3 cm to crosslink and cure the ionizing radiation curable hard coat layer in a semi-cured state.

  The partial mat hard coat molded article thus obtained had a mat portion reliably formed on the surface, and had excellent surface scratch resistance, friction resistance, and solvent resistance.

  A sheet obtained by subjecting a polyethylene terephthalate film having a thickness of 25 μm to a release treatment as a base sheet, and forming the following layers, a transfer sheet for a partial mat hard coat for an acoustic device panel was produced.

  In other words, it was partially screen-printed using an ink in which 30% acrylic resin particles having an average particle diameter of 5 μm were added to urethane acrylate resin, and irradiated with ultraviolet rays for 10 seconds at an irradiation distance of 3 cm using a high pressure mercury lamp (1 kW / cm). Then, a mat mold 12 having a maximum film thickness of 50 μm was formed. Subsequently, an ultraviolet curable ink composed of a cyanoacrylate resin containing 3% isocyanate is gravure-printed on the surface opposite to the mat mold 12 of the base sheet, and the ionizing radiation curable type is semi-cured through a 90 ° C. drying hood. A hard coat layer was formed. Then, the ink which consists of an acrylic resin and vinyl resin containing a coloring agent was gravure-printed, and the decoration layer was formed through the 80 degreeC dry hood. Finally, gravure printing was performed with an ink composed of a vinyl chloride / vinyl acetate copolymer resin, and an adhesive layer was formed through a dry hood at 80 ° C.

  The transfer sheet for the partial mat hard coat described above is installed in a roll transfer machine having a heat-resistant rubber-like elastic body made of silicon rubber, and the transfer sheet is passed through the heat-resistant rubber-like elastic body set at a temperature of about 80 to 260 ° C. Heat and pressure were applied from the substrate sheet side. Then, after cooling, the substrate sheet is peeled off, and the semi-cured ionizing radiation curable hard coat layer is irradiated with ultraviolet rays for 7 seconds at an irradiation distance of 3 cm using a high-pressure mercury lamp (1 kW / cm). The hard coat layer was crosslinked and cured.

  The partial mat hard coat molded article thus obtained had a mat portion reliably formed on the surface, and had excellent surface scratch resistance, friction resistance, and solvent resistance.

  The mat hard coat molded product obtained by the present invention is used for panel members used for communication equipment, acoustic equipment, home appliances, housing equipment, office equipment, automobile parts, and the like.

FIG. 3 is a cross-sectional explanatory view showing a configuration of an example of a transfer sheet for mat hard coat according to the present invention. FIG. 3 is a cross-sectional explanatory view showing a method for decorating a molded article by a transfer method using the mat hard coat transfer sheet according to the present invention. It is a model presumed sectional view of mat type 12 fabricated using ink which consists of resin particulates and a binder. It is sectional explanatory drawing which shows the structure of the transfer sheet for mat | matte hard coat containing the decorating layer concerning this invention. It is explanatory drawing explaining the process of the shaping | molding simultaneous transfer method using the transfer sheet for mat | matte hard coat concerning this invention.

DESCRIPTION OF SYMBOLS 1a Transfer sheet for mat | matte hard coat 1b Transfer sheet for mat | matte hard coat including a decoration layer 6 Molded article 11 Base sheet 12 Mat type | mold 13a Hard-coating layer of uncured or semi-cured state 13b Hard-coating layer of mat-molded state 13c Hard coat layer 14 Adhesive layer 15 Decorating layer 16a, 16b Transfer layer 21 Matte forming ink 22 Resin fine particles 23 Binder 31 Pressure heat roller 36 Ionizing radiation 41 Mold A
42 Mold B
43 Gate

Claims (4)

  A mat type in which a transfer layer including at least an uncured or semi-cured ionizing radiation curable hard coat layer is formed on one surface of a substrate sheet, and resin particles having an average particle diameter of 5 to 25 μm are formed on the other surface of the substrate sheet A transfer sheet for mat hard coat on which is formed. The equation (1) is satisfied, where an average thickness of the base sheet is t (μm) and a weight average particle diameter of the resin fine particles obtained by a Coulter counter method is d (μm). The transfer sheet for mat hard coat according to 1.
0.06 ≦ t / d ² ≦ 1.9 (1)
(However, 12 ≦ t ≦ 50) A method for producing a mat hard coat molded article comprising the following steps.
(B) Step of preparing the mat hard coat transfer sheet according to any one of claims 1 to 2 (b) The transfer layer side of the mat hard coat transfer sheet is a molded product side, and the mart hard coat transfer sheet is formed of a molded product. The transfer sheet for mat hard coat is formed on the mat hard coat by positioning on the surface, applying heat and pressure from the mat mold side, transferring the transfer layer to a molded product, and molding the mat shape into an uncured or semi-cured hard coat layer. And c) a step of obtaining a molded product with a hard coat by peeling off the base sheet from the integrated product and obtaining a molded product with a hard coat in a mat-molded state. Curing the hard coat layer in the mat-molded state to obtain a mat hard-coat molded product The mat hard coat transfer sheet according to claim 1, wherein the mat mold is disposed in the injection mold with the mat mold facing an inner wall surface of the injection mold,
Said press-fitting the injection molding molten resin into the injection mold, as well as transferring the transfer layer to the molded article, the base sheet uncured or semi by deformation interposed by the Utsushitoru the mat-like shape of the Form a mat shape on the cured ionizing radiation curable hard coat layer,
After the injection-molded resin is cooled and solidified, the mold is opened and the molded product is taken out and the base sheet is peeled off, and then the molded product is irradiated with ionizing radiation to form the mat shape. A method for producing a mat hard coat molded article comprising curing the ionizing radiation curable hard coat layer.

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