JP2013094998A - Partial mat transfer sheet and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a partial mat transfer sheet for applying highly designed decoration to a molding without using a large number of steps in order to mat the molding.SOLUTION: The partial mat transfer sheet includes a base sheet; a mold release layer formed on the base sheet and comprising a (meth) acrylate resin with a number average molecular weight of 1,000 or less to the number of double bonding; and a mat layer partially formed on the mold release layer and comprising the (meth) acrylate resin constituting the mold release layer and a filler contained at a ratio of 5-45 wt.% with respect to the (meth) acrylate resin.

Description

  The present invention relates to a partial mat transfer sheet that partially imparts a matte feeling to a molded product, and particularly relates to a partial mat transfer sheet that can impart a matte feeling having a high design property to a molded product.

  A method for protecting or decorating the surface of an article such as a plastic part or an exterior product by using a transfer sheet has been conventionally known. For example, in Patent Document 1, a transfer sheet in which a transfer layer is formed on the surface of a base sheet that is a support, and the transfer sheet is inserted into an injection mold and decorated by in-mold injection molding. It is described that an injection molded body is obtained.

  The transfer sheet has a configuration in which a transfer layer is provided on a base sheet as a support, and this transfer layer is transferred to the surface of a molded product. The transfer layer transferred to the surface of the molded product is a laminate in which a resin or a pattern is laminated in a layer shape, and forms a protective coating or a decorative coating on the surface of the molded product.

  Conventionally, a protection function for a molded product may be emphasized. When this protective function is important, a hard coat layer is provided on the outermost side of the transfer sheet. Further, depending on the application, a part of the hard coat layer is required to have a matte feeling. In this case, a material in which a mat layer is partially formed between the base sheet and the hard coat layer is used (for example, Patent Document 2). However, in the partial mat transfer sheet of Patent Document 2, since the mat layer is composed of a water-soluble resin and a mat agent, a hard coat layer or the like is transferred to the molded product in order to obtain a molded product having a matte feeling. Later, the mat layer must be washed away from the molded article. Therefore, there is a problem that it takes too many steps to obtain the molded product. Furthermore, since it is difficult to completely remove the mat layer when washing and removing in the above, the mat layer remains in a part of the molded product even after the washing and removing, thereby obtaining a molded product with high design properties. There was also a problem that it was difficult.

  Furthermore, as another configuration of the partial mat transfer sheet, there is one in which a mat layer, a release layer, and a hard coat layer are formed in this order on a base sheet (for example, Patent Document 3). However, the partial mat transfer sheet of Patent Document 3 is different in the resin used as the base of the release layer and the mask layer, so the adhesion between the release layer and the mask layer is poor, and the hard coat layer and the like are transferred to the molded product. Sometimes peeling occurs between the release layer and the mask layer. As a result, there is a problem that the mask layer remains in the molded product and a molded product with high designability cannot be obtained.

JP-A-10-58895 JP 2001-260596 A JP 2010-149383 A

  The present invention solves the above-mentioned conventional problems, and is a partial mat that can be decorated with a high design property without going through a number of steps in order to impart a mat feeling to the molded product. It is to provide a transfer sheet.

  In the partial mat transfer sheet of the present invention, the partial mat transfer sheet is formed on a base sheet and the base sheet, the number average molecular weight is 10,000 to 100,000, and the number average molecular weight is the number of double bonds. On the other hand, a release layer made of (meth) acrylate resin having a glass transition temperature of 40 ° C. to 150 ° C. is 1000 or less and partially formed on the release layer to constitute the release layer ( A mat layer comprising the same (meth) acrylate resin as the (meth) acrylate resin, and a filler contained in a proportion of 5 to 45 W% with respect to the (meth) acrylate resin; and on the release layer and the mat layer A partial mat transfer sheet comprising: a hard coat layer formed on the hard coat layer; and an adhesive layer formed on the hard coat layer.

  The partial mat transfer sheet of the present invention is partially formed on a base sheet and the base sheet, has a number average molecular weight of 10,000 to 100,000, and the number average molecular weight is 1000 or less with respect to the number of double bonds. The release layer is formed of a (meth) acrylate resin having a glass transition temperature of 40 ° C. to 150 ° C. and the region of the base sheet where the release layer is not formed, and constitutes the release layer A mat layer comprising the same (meth) acrylate resin as the (meth) acrylate resin and a filler contained in a proportion of 5 to 45 W% with respect to the (meth) acrylate resin, the release layer and the mat layer A partial mat transfer sheet comprising a hard coat layer formed on the upper surface and an adhesive layer formed on the hard coat layer.

  The partial mat transfer sheet of the present invention is formed on the base sheet and the base sheet, has a number average molecular weight of 10,000 to 100,000, and the number average molecular weight is 1000 or less with respect to the number of double bonds, A (meth) acrylate resin having a glass transition temperature of 40 ° C. to 150 ° C., a mat layer containing a filler contained in a proportion of 5 to 45 W% with respect to the (meth) acrylate resin, and the mat layer A partially formed release layer made of the same (meth) acrylate resin as the (meth) acrylate resin constituting the mat layer, and a hard coat layer formed on the release layer and the mat layer And a partial mat transfer sheet comprising an adhesive layer formed on the hard coat layer.

  In one certain form, the thickness of the said release layer is thicker than the thickness of the said mat | matte layer.

  In one certain form, the said mold release layer and the said mat | matte layer are each provided with a silicon chain containing (meth) acrylate resin in the ratio of 1-10 W% with respect to the said (meth) acrylate resin.

（式中、ｎは１〜２０の整数、Ｒは水素又は炭素数１〜４のアルキル基、フェニル基のいずれかを示す。） In one embodiment, the silicon chain-containing (meth) acrylate resin is obtained by polymerizing a silicate oligomer represented by the following chemical formula and an acrylic monomer in a ratio of 5/95 to 85/15.

(In the formula, n represents an integer of 1 to 20, and R represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.)

  In one certain form, the thickness of the said mold release layer and the said mat | matte layer is 0.2-2 micrometers, respectively.

  The method for producing a partial mat transfer sheet according to the present invention has a number average molecular weight of 1000 or less, a number average molecular weight of 10,000 to 100,000, and a glass transition temperature of 40 to 150 ° C. A first step of forming a release layer using a photocurable ink comprising an acrylate resin and an organic solvent for gravure ink, wherein the non-volatile component is 50% by mass or more and the viscosity is 200 mP · S or less at room temperature; The release layer is partially composed of the (meth) acrylate resin, a filler contained in a proportion of 5 to 45 W% with respect to the (meth) acrylate resin, and an organic solvent for gravure ink, and a non-volatile component A second step of forming a matte layer using a filler-containing photocurable ink having a viscosity of 50% by mass or more and a viscosity of 200 mP · S or less at room temperature; the release layer; A third step of forming a protective layer on the protective layer, a fourth step of irradiating the release layer, the mat layer, and the hard coat layer with light, and a second step of forming an adhesive layer on the protective layer. A process for producing a partial mat transfer sheet comprising 5 steps is provided.

  The partial mat transfer sheet of the present invention is a partial mat transfer sheet that imparts a matte design to a molded product, wherein the partial mat transfer sheet is formed on the base sheet and the base sheet, and the number average molecular weight is doubled. A release layer made of (meth) acrylate resin having a number of bonds of 1000 or less with respect to the number of bonds, a (meth) acrylate resin partially formed on the release layer and constituting the release layer, And a mat layer composed of a filler contained in a proportion of 5 to 45 W% with respect to the (meth) acrylate resin. As a result, in order to give the molded product a matte feeling, the molded product can be decorated with a high design without passing through many steps.

It is sectional drawing which shows typically the structure of the partial mat transfer sheet of this invention. It is sectional drawing which shows typically the structure of the partial mat transfer sheet of this invention. It is sectional drawing which shows typically the structure of the partial mat transfer sheet of this invention. It is sectional drawing which shows typically the manufacturing method of the partial mat transfer sheet of this invention.

  Hereinafter, embodiments according to the present invention will be described in more detail with reference to the drawings. It should be noted that the dimensions, materials, shapes, relative positions, etc. of the parts and portions described in the embodiments of the present invention are not intended to limit the scope of the present invention only to those unless otherwise specified. This is just an illustrative example.

Partial Mat Transfer Sheet FIG. 1 is a view showing a partial mat transfer sheet according to the first embodiment of the present invention. Referring to FIG. 1, a partial mat transfer sheet 100 of the present invention includes a base sheet 1, a release layer 2 formed on the base sheet 1, and a mat layer 3 partially formed thereon. The protective layer 4 formed on the release layer 2 and the mat layer 3, the pattern layer 5 formed on the protective layer 4, and the adhesive layer 6 are provided.

Base sheet A base sheet is a base film for holding a release layer, a mat layer and the like on a sheet, and is made of a synthetic resin or the like. Examples of the material of the base sheet include resin sheets such as polypropylene resin, polyethylene resin, polyamide resin, polyester resin, acrylic resin and polyvinyl chloride resin, metal foil such as aluminum foil and copper foil, glassine As the substrate sheet, a cellulose sheet such as paper, coated paper, cellophane, etc., or a composite of the above-mentioned sheets can be used.

Release layer The release layer is a layer that is released from the molded product together with the sheet when the substrate sheet is peeled off after the protective layer is transferred to the molded product. Further, the release layer is also a layer for imparting gloss to the protective layer, and its surface shape is smooth.

  The release layer is composed of (meth) acrylate resin. The (meth) acrylate resin preferably has a number average molecular weight of 10,000 to 100,000. More preferably, it is 20000-50000. If the number average molecular weight of the (meth) acrylate resin is less than 10,000, the peelability between the release layer and the protective layer is lowered, so the partial mat transfer sheet 100 is attached to the molded product, and the release layer is used as the base sheet. At the same time, part of the release layer remains in the protective layer when peeling from the molded product. As a result, a molded product with high designability cannot be created. On the other hand, if the number average molecular weight of the (meth) acrylate resin exceeds 10,000, the synthesis of the (meth) acrylate resin becomes difficult, and the cost increases.

  Moreover, when the number average molecular weight is Mw, the number n of double bonds contained in the (meth) acrylate resin is preferably in the range of 200 to 1000 in terms of Mw / n. More preferably, it is 400-600. When the value of Mw / n exceeds 1000, the photopolymerization reaction of the (meth) acrylate resin that forms the release layer even if the release layer is irradiated with ultraviolet rays after the release layer is formed on the substrate sheet Becomes dull, and the crosslinking density of the (meth) acrylate resin decreases. As a result, the peelability between the release layer and the protective layer is lowered, and when the release layer is peeled off from the molded product together with the base sheet, a part of the release layer remains in the protective layer and has high design properties. I can't create a molded part. On the contrary, when Mw / n is less than 200, synthesis of (meth) acrylate resin becomes difficult.

  The (meth) acrylate resin preferably has a glass transition temperature in the range of 40 ° C to 150 ° C. More preferably, it is 70 degreeC-110 degreeC. When the glass transition temperature of the (meth) acrylate resin is less than 40 ° C., the peelability between the release layer and the protective layer is lowered. As a result, when the release layer is peeled from the molded product together with the base sheet, a part of the release layer remains in the protective layer, and a molded product with high designability cannot be created. On the other hand, if the glass transition temperature exceeds 150 ° C., synthesis of (meth) acrylate resin becomes difficult.

  Further, the release layer may contain a silicon chain-containing (meth) acrylate. When silicon chain-containing (meth) acrylate is contained, the peelability between the release layer and the protective layer is improved, and when the partial mat transfer sheet is attached to a molded product, the release layer is applied by the force of attachment. It is possible to suppress cracks from occurring. If generation | occurrence | production of a crack can be suppressed, since the said crack can be suppressed to propagate to the protective layer adjacent to a mold release layer, a molded article with high design property without a crack can be created.

  In addition, it is preferable that silicon chain containing (meth) acrylate is contained in the mold release layer in the ratio of 1-10 W% by weight ratio with respect to the said (meth) acrylate resin. When the ratio of the silicon chain-containing (meth) acrylate is less than 1 W%, sufficient peelability between the release layer and the protective layer cannot be ensured. On the other hand, if it exceeds 10 W%, a so-called rust phenomenon occurs between the release layer and the protective layer, and the protective layer is not uniformly formed on the release layer.

As the silicon chain-containing methacrylate, it is preferable to use a polymer obtained by polymerizing an acrylic monomer in the presence of a silicate oligomer represented by the following chemical formula (1) (hereinafter referred to as a silicate oligomer). (In the formula, n represents an integer of 1 to 20, and R represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.)

  The silicate oligomer can be obtained by hydrolyzing tetraalkoxysilane or tetraphenoxysilane such as tetramethoxysilane, tetraethoxysilane, tetrapropoxyoxysilane, and tetrabutoxysilane. n can be adjusted by controlling the hydrolysis rate.

  The acrylic monomer typically includes an alkoxysilyl group-containing acrylic monomer, (meth) acrylic acid alkyl ester, and (meth) acrylic acid, and these are used alone or in combination. Preferably, it is a combination of an alkoxysilyl group-containing acrylic monomer and a (meth) acrylic acid alkyl ester, and a combination with an unsaturated monomer other than the above is also possible if necessary.

  Examples of the (meth) acrylic acid alkyl ester include butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, ( Hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc. These are used alone or in combination of two or more.

  The mixing polymerization ratio of the silicate oligomer and acrylic monomer is preferably 5/95 to 85/15. More preferably, it is 10 / 90-80 / 20. If it is less than 5/95, the hardness of the release layer is reduced, and if it exceeds 85/15, the adhesion between the release layer and the substrate sheet is reduced.

  The silicon chain-containing acrylic resin obtained by the above method preferably has a weight average molecular weight of 10,000 to 100,000. When the weight average molecular weight is less than 10,000, the release layer has insufficient hardness. When the weight average molecular weight exceeds 100,000, the viscosity of the release layer becomes high, and a problem arises in coating suitability of the release layer.

  The thickness of the release layer is preferably 0.1 μm to 5 μm. More preferably, it is 1 μm to 3 μm. When the thickness of the release layer is less than 0.1 μm, not only is it difficult to coat, but also the coating with sufficient hardness cannot be obtained due to the inhibition of oxygen curing during UV curing. When the partial mat transfer sheet exceeds 5 μm, when the partial mat transfer sheet is attached to the molded product, a crack is generated in the release layer due to the adhesive force, and the crack propagates to the protective layer. You will not be able to get.

  Examples of the method for forming the release layer include coating methods such as a roll coating method and a spray coating method, and printing methods such as a gravure printing method and a screen printing method.

The mat layer is a layer that peels off both the base sheet and the release layer from the molded product when the base sheet is peeled off after the protective layer is transferred to the molded product. Furthermore, the mat layer is a layer for imparting a mat feeling to the protective layer, and the surface shape thereof is an uneven shape. The mat layer is partially formed on the release layer. By combining the release layer having a smooth surface shape and the mat layer, a matte feeling can be partially imparted to the protective layer.

  The mat layer is composed of the same (meth) acrylate resin and filler as those of the release layer. Since the resin constituting the mat layer is made of the same resin as the release layer, the adhesion between the mat layer and the release layer is improved. Furthermore, when the resin constituting the mat layer is made of a (meth) acrylate resin, the peelability between the mat layer and the protective layer is improved. That is, when the mat layer is composed of the same (meth) acrylate resin as the release layer, the adhesion between the mat layer and the release layer is improved, and the peelability between the mat layer and the protective layer is improved. As a result, when a partial mat transfer sheet is attached to a molded product and a base sheet or the like is peeled off from the molded product, a part of the mat layer is not peeled off from the protective layer and is prevented from peeling off from the release layer. be able to. Therefore, it is possible to produce a molded article having a high design property in which no mat layer is present in the protective layer.

  Further, when all of the mat layer is peeled off from the protective layer, a molded product having a mat feeling can be created without going through the mat layer removing step. Therefore, a molded product having a matte feeling can be produced with a small number of steps.

The mat layer preferably contains a silicon chain-containing (meth) acrylate. As the silicon chain-containing methacrylate, a silicate oligomer represented by the following chemical formula (2) and an acrylic monomer are used. Those polymerized at a ratio of 95 to 85/15 are preferred. (In the formula, n represents an integer of 1 to 20, and R represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.)

  The reason why the mat layer preferably contains a silicon chain-containing methacrylate, and as the silicon chain-containing methacrylate, the silicate oligomer represented by the chemical formula (2) and the acrylic monomer are 5/95 to 85/15. The reason why the polymerized at a ratio of 1 is preferable, the type of the silicate oligomer, and the type of the acrylic monomer are the same as those in the case of the release layer, and will be omitted.

  An inorganic material is used for the filler. As the inorganic material, silicon, fluorine, silica, alumina, titanium dioxide, magnesium oxide, zinc oxide, magnesium carbonate, calcium carbonate, or the like can be used.

  The average particle diameter of the filler is JIS Z 8901 and is preferably 0.5 μm to 10 μm. More preferably, it is 1 micrometer-5 micrometers. When the thickness is less than 0.5 μm, a sufficient mat feeling cannot be imparted. On the other hand, if it exceeds 10 μm, the filler settles in the mat layer, and streaks, unevenness, etc. occur in the mat layer. As a result, a partial mat transfer sheet lacking in design is obtained.

  The filler is preferably contained in the mat layer at a weight ratio of 5 to 45 W% with respect to the (meth) acrylate resin. When the proportion of the filler is less than 5 W% by weight, a sufficient mat feeling cannot be imparted to the protective layer. On the contrary, if it exceeds 50 W%, the filler settles in the mat layer, and streaks, unevenness, etc. occur in the mat layer. As a result, a partial mat transfer sheet lacking in design is obtained.

  The thickness of the mat layer is preferably 0.1 μm to 5 μm. More preferably, it is 1 μm to 3 μm. If the thickness of the mat layer 3 is less than 0.1 μm, it is not only difficult to coat, but also a mat layer having sufficient hardness cannot be obtained due to inhibition of oxygen curing during UV curing. If the thickness exceeds 5 μm, when the partial mat transfer sheet is stuck to the molded product, cracks and cracks are generated in the mat layer due to the sticking force, and it becomes impossible to obtain a molded product with high design properties.

  Examples of the method for forming the mat layer include a coating method such as a roll coating method and a spray coating method, a printing method such as a gravure printing method and a screen printing method.

Protective layer The protective layer is a layer in which the concavo-convex shape of the mat layer is copied, and is a layer that gives a mat feeling to the molded product when decorating the molded product using the partial mat transfer sheet. Moreover, a protective layer is a layer arrange | positioned on the surface of articles | goods, and is also a layer which protects the pattern layer, adhesive layer, etc. which are arrange | positioned under a protective layer from a physical or chemical injury.

  The thickness of the protective layer is preferably in the range of 1 μm to 20 μm. When the thickness of the protective layer is less than 1 μm, it is too thin to sufficiently exhibit the above functions. On the other hand, when the thickness of the protective layer exceeds 20 μm, cracks occur in the protective layer during molding, which is not preferable.

  As the material of the protective layer, homopolymers of acrylic or methacrylic monomers such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate, etc., or acrylic resins of copolymers containing these monomers In addition, melamine resin, acrylic resin, urethane resin, epoxy resin, and the like can be used.

  Specifically, two-component curable resins such as melamine, acrylic melamine, epoxy melamine, alkyd, urethane, acrylic, etc. and a mixture of these, or a combination with a curing agent such as isocyanate, polyester acrylate Polyester methacrylate, epoxy acrylate, epoxy methacrylate, urethane acrylate, urethane methacrylate, polyether acrylate, polyether methacrylate, polyol acrylate, melamine acrylate, melamine methacrylate and other monomers and prepolymers that have ethylenically unsaturated bonds Ultraviolet rays, electron beam curable resins, and the like can be used. When an ultraviolet curable resin is used, a photoinitiator is further added.

  As a photoinitiator, it can select suitably. Examples include radical photopolymerization initiators such as benzoin ether, ketal, acetophenone, and thioxanthone, diazonium salts, diaryliodonium salts, triarylsulfonium salts, and complex cationic photopolymerization initiators. One or more of these can be used.

  Examples of the method for forming the protective layer include a method in which the active energy ray-curable resin composition is formed on a base sheet by a printing method such as gravure printing, screen printing, or offset printing.

Pattern layer The pattern layer is a layer for decorating the molded product with a pattern, etc., when decorating the molded product using a partial mat transfer sheet, and if necessary, on the protective layer It is formed. As the material of the pattern layer, a resin such as polyvinyl resin, polyamide resin, polyacrylic resin, polyurethane resin, polyvinyl acetal resin, polyester urethane resin, cellulose ester resin, alkyd resin 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. Further, the pattern layer may be transmissive or light-shielding. Examples of the method for forming the picture layer include normal printing methods such as an offset printing method, a gravure printing method, and a screen printing method.

The adhesive layer adhesive layer is a layer for adhering the molded product and the partial mat transfer sheet, and is formed on the picture layer. As a material used for the adhesive layer, a heat-sensitive or pressure-sensitive resin suitable for the type of molded product to be decorated is used. If the resin portion is a PMMA resin, the adhesive layer may be a PMMA resin. If the resin part is a PC or polystyrene (PS) resin, the adhesive layer may be made of PMMA, PS, or PA resin that has an affinity for these resins. The adhesive layer is formed on the partial mat transfer sheet 100 by a gravure coating method, a roll coating method, a comma coating method, a gravure printing method, a screen printing method, an offset printing method, or the like.

Second Embodiment Next, a partial mat transfer sheet according to a second embodiment of the present invention will be described. Since the basic configuration of the partial mat transfer sheet of this embodiment is the same as that of the first embodiment, only the differences will be described here.

  FIG. 2 is a view showing a partial mat transfer sheet 100 according to the second embodiment of the present invention. Referring to FIG. 2, a partial mat transfer sheet 100 of the present invention includes a base sheet 1, a release layer 2 formed on the base sheet 1, and a mat layer formed adjacent to the release layer 2. 3, a hard coat layer 4 formed on the release layer 2 and the mat layer 3, a pattern layer 5 formed thereon, and an adhesive layer 6.

  In the partial mat transfer sheet 100 according to the second embodiment, the mat layer 3 and the hard coat layer 4 are formed adjacent to each other on the base sheet 1. Therefore, the thickness of the hard coat layer 4 can be increased by the thickness of the mat layer 3 as compared with the partial mat transfer sheet of the first embodiment. As a result, a sufficient thickness of the hard coat layer 4 can be secured, so that the hard coat layer 4 having an excellent protective function can be disposed.

Third Embodiment Next, a partial mat transfer sheet 100 according to a third embodiment of the present invention will be described. Since the basic configuration of the partial mat transfer sheet 100 of this embodiment is the same as that of the first embodiment, only the differences will be described here.

  FIG. 3 is a view showing a partial mat transfer sheet 100 according to the third embodiment of the present invention. Referring to FIG. 3, a partial mat transfer sheet 100 of the present invention includes a base sheet 1, a mat layer 3 formed on the base sheet 1, and a release partly formed on the mat layer 3. A layer 2, a protective layer 4 formed on the release layer 2, a pattern layer 5 formed thereon, and an adhesive layer 6 are provided.

  In the partial mat transfer sheet according to the third embodiment, the release layer 2 is preferably thicker than the mat layer 3. The reason is as follows. As described above, the mat layer 3 is a layer that gives the protective layer 4 a matte feeling, whereas the release layer is a layer that gives the protective layer 4 a glossy feeling. Therefore, the surface shape of the mat layer 3 is uneven, and the surface shape of the release layer 2 is smooth. When the release layer 2 having a smooth surface shape is formed on the mat layer 3 having an uneven surface shape, if the release layer 2 is not thicker than the mat layer 3, the uneven shape of the mat layer 3 is the release layer. 2 is reflected, and the smoothness of the release layer is lost. As a result, a mat feeling is imparted over the entire surface of the protective layer 4, and the mat feeling cannot be partially imparted to the protective layer 4.

  In the partial mat transfer sheet 100 according to the third embodiment, the release layer 2 is partially formed on the mat layer 3 and the protective layer 4 is formed thereon. By simply changing the film thickness, the matte feeling (gross feeling) can be adjusted freely. Furthermore, in the case of gravure coating, the release layer 2 can be formed by a relatively simple method such as adjusting the number of lines of the plate and the viscosity of the ink.

  Next, a method for manufacturing the partial mat transfer sheet 100 will be described.

Method for Manufacturing Partial Mat Transfer Sheet FIG. 4 shows a method for manufacturing the partial mat transfer sheet 100 according to the present invention. Referring to FIG. 4, in the method for manufacturing a partial mat transfer sheet according to the present invention, a first step of forming release layer 2 on base sheet 1 and formation of mat layer 3 on release layer 2 are performed. A second step of forming a hard coat layer 7 on the release layer 2 and the mat layer 3, and a fourth step of irradiating the release layer 2, the mat layer 3 and the hard coat layer 7 with light. And a fifth step of forming the adhesive layer 6 on the hard coat layer 7.

  With reference to FIG. 4A, in the first step of the method for manufacturing the partial mat transfer sheet 100 according to the present invention, the release layer 2 is formed on the base sheet 1.

  The release layer 2 uses a photocurable ink obtained by dissolving a part of the (meth) acrylate resin with an organic solvent for gravure ink.

  The (meth) acrylate resin preferably has a number average molecular weight of 10,000 to 100,000. More preferably, it is 20000-50000. When the number average molecular weight is less than 10,000, the release layer becomes tack-free after the solvent is volatilized, and it is difficult to perform gravure printing. (Tack-free state means that the release layer remains sticky, so that the resin constituting the release layer adheres to the pass roll on the printing machine, resulting in poor appearance. (The same applies to the following.) If the viscosity exceeds 100,000, the viscosity of the ink increases significantly, causing appearance problems, and diluting with a solvent to a printable viscosity. Therefore, the solid content of the resin constituting the release layer is reduced. As a result, the release layer cannot maintain a sufficient film thickness.

  Moreover, when the number average molecular weight is Mw, the number n of double bonds contained in the (meth) acrylate resin is preferably in the range of 200 to 1000 in terms of Mw / n. More preferably, it is 300-500. If the above value exceeds 1000, the photopolymerization reaction of the (meth) acrylate resin is difficult to proceed even if the release layer 2 is irradiated with ultraviolet rays after the release layer 2 is formed on the base sheet 1. Become. As a result, it becomes difficult to create the partial mat transfer sheet 100 on the same production line. On the other hand, if Mw / n is less than 200, synthesis is difficult.

  The (meth) acrylate resin preferably has a glass transition temperature in the range of 40 ° C to 150 ° C. More preferably, it is 70 degreeC-110 degreeC. When the glass transition temperature is less than 40 ° C., the viscosity of the ink becomes too high, and the release layer does not become tack-free after the solvent is volatilized. The matte layer is formed on the release layer by gravure printing. It becomes difficult to form. Moreover, it is difficult to synthesize a glass transition temperature exceeding 150 ° C.

  The organic solvent for gravure ink is preferably a volatile organic solvent conventionally used for gravure ink. This is because they are excellent in volatility, and the release layer can be easily dried even during a short time of printing interval when a plurality of layers are continuously printed on the same production line. Examples of the organic solvent for gravure ink include aromatic solvents such as toluene and xylene having a boiling point of 80 to 120 ° C., alcohol solvents such as normal propyl alcohol and isopropyl alcohol, ketone solvents such as methyl ethyl ketone, and ethyl acetate. An ester solvent can be used. Preferred are toluene, methyl ethyl ketone and the like.

  The non-volatile component of the organic solvent for gravure ink is 15 to 50, preferably 20 to 40 of the entire photocurable ink. When the non-volatile component of the organic solvent for gravure ink is less than 15 W%, the drying speed of the release layer is slowed, and the thickness of the protective layer to be formed becomes insufficient. On the other hand, if the non-volatile component of the organic solvent for gravure ink exceeds 50 W%, the viscosity of the photocurable ink becomes high and it is difficult to perform gravure printing, which is not preferable.

  The viscosity of the photocurable ink is 200 mPa · s or less, preferably 100 mPa · s or less, more preferably 20 to 70 mPa · s at room temperature. If comprised in this way, it can heat and dry also for a short time called the printing interval in the case of printing a several layer continuously in the same manufacturing line.

  As a result, after forming the release layer on the base sheet using the photocurable ink, it is possible to immediately shift to the next step of forming the mat layer on the release layer. As a result, the release layer and the mat layer can be formed on the same production line.

  In addition, since it becomes difficult to perform gravure printing that the viscosity of photocurable ink is outside the said range at room temperature, it is not preferable.

  The photocurable ink preferably contains silicon chain-containing (meth) acrylate at a weight ratio of 1 to 10 W% with respect to the (meth) acrylate resin. In addition, sufficient releasability is not acquired as the ratio of a silicon chain containing (meth) acrylate is less than 1 W%. On the other hand, if it exceeds 10 W%, the peelability of the release layer becomes excessive, which not only causes blocking problems in the production process of the transfer sheet, but also inhibits the leveling of the mat layer and hard coat layer to be formed next. A transfer sheet having excellent design properties cannot be obtained.

  With reference to FIG.4 (b), in the 2nd process of the manufacturing method of the partial mat transfer sheet 100 which concerns on this invention, the mat layer 3 is partially formed on the mold release layer 2 using the gravure printing method. .

  As the matte layer, a material obtained by adding a filler to the photocurable ink is used. The material of the photocurable ink and the effects when using the ink are the same as in the case of the first step, and are omitted here.

  As the filler, silicon, fluorine, styrene, silica, alumina, titanium dioxide, magnesium oxide, zinc oxide, magnesium carbonate, calcium carbonate, or the like can be used.

  The average particle diameter of the filler is JIS Z 8901 and is preferably 0.5 μm to 10 μm. More preferably, it is 1.0 micrometer-5.0 micrometers. When the thickness is less than 0.5 μm, a sufficient mat feeling cannot be imparted. On the other hand, if it exceeds 10 μm, the filler settles in the mat layer, and streaks, unevenness, etc. occur in the mat layer. As a result, it becomes a partial mat transfer sheet lacking in design.

  It is preferable that the filler which comprises a mat layer is contained in the ratio of 5-50 W% by weight ratio with respect to (meth) acrylate resin.

  Referring to FIG. 4C, in the third step, a hard coat layer 7 is formed on the release layer 2 and the mat layer 3 using a gravure printing method. As the hard coat layer 7, a photo-curing resin composed of a monomer or prepolymer having an ethylenically unsaturated bond is used.

  In the fourth step, the release layer 2, the mat layer 3, and the hard coat layer 7 are irradiated with light.

  Examples of the type of light to be irradiated include electron beams, X-rays, ultraviolet rays, visible rays, and the like, preferably ultraviolet rays having a wavelength of 200 to 400 nm, more preferably 220 to 300 nm. Examples of the ultraviolet light source include a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, and an electrodeless lamp, and a high-pressure mercury lamp is preferably used.

  Referring to FIG. 4D, in the fifth step, the adhesive layer 6 is formed on the protective layer 4 using a gravure printing method. As the material of the adhesive layer 6, the above-described materials can be used.

  Thus, the partial mat transfer sheet 100 can be obtained through the steps from the first step to the fifth step.

  As described above, since the resin constituting the release layer in the first step is made of the photocurable ink, the release layer is dried and cross-linked more quickly than when other inks are used. Is very early. Therefore, the problem of ink tackiness and fluidity which becomes a problem when other inks are used for the release layer does not occur in the present invention. Therefore, after forming the release layer, the mat layer is immediately removed from the release layer. Can be formed on top.

  In the second step, since the resin constituting the mat layer is composed of the photocurable ink as described above, the mat layer is dried and crosslinked at a very high rate as in the case of the release layer. After forming the mat layer 3, a hard coat layer can be immediately formed thereon.

  Furthermore, since the resin constituting the hard coat layer is composed of the photocurable resin for the third step, and the hard coat layer is irradiated with light for the fourth step, the hard coat layer is Cured immediately after the fourth step. Therefore, an adhesive layer can be formed on the hard coat layer immediately after the fourth step.

  As a result, after the release layer, mat layer, or hard coat layer is formed, it is not necessary to remove the sheet on which the layer is formed from the production line in order to dry these layers. Therefore, from the release layer to the formation of the adhesive layer can be performed on the same production line, the cost for creating the partial mat transfer sheet can be reduced. Furthermore, since all the layers can be formed on the same production line, it is possible to suppress the occurrence of misalignment between the layers formed on the base sheet.

  If necessary, a step of forming the pattern layer 5 on the protective layer 4 may be introduced between the fourth step and the fifth step.

  If necessary, the mat layer may be formed adjacent to the release layer.

  In addition, you may reverse the order which forms a mold release layer and a mat | matte layer as needed. In such a case, a release layer may be partially formed on the mat layer.

Method for Decorating Molded Product A molded product can be decorated by hot roll transfer or in-mold molding using the partial mat transfer sheet of the present invention. For example, in heat roll transfer, first, the position of the partial mat transfer sheet is determined so that the pattern is arranged at a desired position of the molded product in consideration of the position of the pattern existing on the partial mat transfer sheet. Next, the inner surface (adhesive layer side) of the partial mat transfer sheet is superposed on the surface of the molded product, and heat and Apply pressure. By doing so, the partial mat transfer sheet adheres to the surface of the molded product, and the surface of the molded product is decorated.

  In in-mold injection molding, first, a partial mat transfer sheet is fed into a molding die. At that time, the orientation of the partial mat transfer sheet is adjusted so that the outer side faces the mold cavity surface, and the position of the partial mat transfer sheet is determined in consideration of the position of the pattern existing on the partial mat transfer sheet. It determines so that a pattern may be arrange | positioned in position.

  Next, the mold is closed, so that the molten resin comes into contact with the inner surface (that is, the adhesive layer side) of the partial mat transfer sheet, that is, the partial mat transfer sheet is sandwiched between the molten resin and the mold cavity surface. The molten resin is filled into the mold cavity. As a result, the molten resin is molded, and at the same time, the partial mat transfer sheet is bonded to the surface of the injection molded body. When the resin is cooled, the mold is opened, and the injection molded body is taken out, the transfer layer is adhered to the surface of the injection molded body, and the surface of the injection molded body is decorated. Finally, the base sheet is peeled off.

  The material of the molded product is not particularly limited as long as it has been conventionally decorated with a partial mat transfer sheet, or can devise the components of the adhesive layer to adhere the transfer layer to the surface. Various synthetic resins, members made of metal, glass, wood, paper, and these coated and decorative items are used as molded articles.

  The present invention will be specifically described by the following examples, but the present invention is not limited thereto. In the examples, the amount represented by “part” or “%” is based on weight unless otherwise specified.

[Example 1]
1. Production of photocurable ink and filler-containing photocurable ink (Synthesis Example 1)
In a stirrer of a reactor equipped with a stirrer, a cooling pipe, a dropping funnel and a nitrogen introduction pipe, 150 parts of glycidyl methacrylate (hereinafter referred to as GMA), 100 parts of methyl methacrylate (hereinafter referred to as MMA), lauryl mercaptan 3 parts, 1000 parts of butyl acetate, and 7.5 parts of 2,2′-azobisisobutyronitrile (hereinafter referred to as AIBN) are added, and the system is kept at about 90 ° C. over about 1 hour under a nitrogen stream. The internal temperature was raised, followed by stirring for 1 hour. Next, using a dropping funnel, a preliminarily prepared mixed solution consisting of 450 parts of GMA, 300 parts of MMA, 3.7 parts of lauryl mercaptan and 22.5 parts of AIBN was placed in a stirring apparatus for about 2 hours in a nitrogen stream. The solution was dropped at 90 ° C. for 3 hours after the completion of the dropping. After 3 hours, 10 parts of AIBN was added to the system, and the mixture was further stirred at 90 ° C. for 1 hour. Thereafter, the temperature inside the system was raised to 120 ° C., and further stirred for 2 hours to obtain a (meth) acrylate resin.

The number average molecular weight of the (meth) acrylate resin obtained above, the number average molecular weight with respect to the number of double bonds, and the glass transition temperature were measured. The results are shown below.
(1) Number average molecular weight: Mw = 36000
(2) Number average molecular weight relative to the number of double bonds: Mw / n = 314
(3) Glass transition temperature: 73 ° C

Next, the above-mentioned (meth) acrylate resin, silicon chain-containing (meth) acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: UT-4314), and methyl ethyl ketone in a stainless steel container equipped with a stirrer at the following ratio: The mixture was added and stirred at room temperature for 30 minutes. After 30 minutes, it was confirmed by visual inspection that the components were uniformly dispersed, and a photocurable ink was obtained. The non-volatile component at this time was 33.3% of the whole.
(1) (Meth) acrylate resin: 90 parts by weight of solid content (apparently 180 parts)
(2) Silicon chain-containing (meth) acrylate: apparently 10 parts by weight (3) methyl ethyl ketone: 110 parts by weight

Finally, silica (average particle diameter: 3 to 4 μm, manufactured by Fuji Silysia Co., Ltd., trade name: Silo Hovic 702) was added to the photocurable ink, and the mixture was stirred at room temperature for 30 minutes. After 30 minutes, it was confirmed by visual inspection that silica was uniformly dispersed, and a filler-containing photocurable ink was obtained. The mixing ratio of the photocurable ink and silica is as shown below.
(1) Photocurable ink: 90 parts by weight (in terms of solid content)
(2) Silica: 10 parts by weight

2. Production of Partial Mat Transfer Sheet A biaxially stretched polyethylene terephthalate film having a thickness of 50 μm was used as the substrate sheet. This substrate sheet was set on a gravure printing machine (Orient Sogaku Co., Ltd .: 10-color distribution gravure rotary printing machine, Fuji Machine Industry Co., Ltd. 11-color distribution gravure rotary printing machine), and the resulting photocurable ink was used. A release layer was formed. And the release layer was dried using the dryer installed in the gravure printing machine. Next, a mat layer was partially formed on the release layer using the filler-containing photocurable ink, and the mat layer was dried in the same manner as the release layer. Next, the coating film was cured by irradiating 300 mJ / cm ² of ultraviolet rays. Finally, a protective layer, a handle layer, and an adhesive layer were formed on the obtained film to obtain a partial mat transfer sheet.

3. Evaluation of Partial Mat Transfer Sheet The release layer and the mat layer of the partial mat transfer sheet obtained above were evaluated from the following viewpoints.

1) Peelability After placing the partial mat transfer sheet obtained by the above method in a mold and performing in-mold injection molding of polycarbonate / ABS alloy resin, the base sheet, release layer and mat layer are removed. , I got a personal computer casing that is a part of the personal computer. In the case of the obtained personal computer casing, the area where the protective layer was present was 20 cm long × 30 cm wide. Thereafter, the surface of the protective layer was visually observed to confirm the presence or absence of a peeling trace. In addition, the release layer and mat layer formed on the base sheet were observed, and it was observed and evaluated whether or not peeling traces were generated on the release layer and mat layer. The results are shown in Table 1. The evaluation criteria are as follows.

Evaluation criteria ( circle): Generation | occurrence | production of peeling trace was not observed.
X: The occurrence of peeling marks was observed at one or more locations.

2) Crack resistance The surface of the protective layer in the personal computer casing of the personal computer casing obtained by the above-described method was visually observed to determine whether cracks were generated in the protective layer. Further, the release layer and the mat layer formed on the removed base sheet were observed, and it was also observed whether or not cracks occurred in the release layer and the mat layer. Finally, the correlation between cracks generated in the protective layer and cracks generated in the release layer and the mat layer was observed and evaluated. The results are shown in Table 1. The evaluation criteria are as follows.

Evaluation criteria ( circle): Generation | occurrence | production of the crack was not recognized by the mold release layer or the mat | matte layer, but the crack and crack originating in the said crack were not confirmed also in the protective layer.
(Triangle | delta): The crack has generate | occur | produced in one place of a mold release layer and a mat | matte layer, and the crack and crack originating in the said crack were able to be confirmed 1 place also in the protective layer.
X: A plurality of cracks occurred in the release layer and the mat layer, and a plurality of cracks and cracks derived from the cracks were confirmed in the protective layer.

3) Printability A partial mat transfer sheet comprising a substrate sheet, a release layer, a mat layer, and a protective layer and having a surface area of 100 cm ² was produced using the above method. The obtained partial mat transfer sheet is irradiated with white light using a fluorescent lamp from the base sheet side and visually observed from a distance of 30 cm, and at the interface between the protective layer and the release layer, and the protective layer and the mat layer. It was observed and evaluated whether or not defects such as unevenness and doctor streaks occurred. The results are shown in Table 1. The evaluation criteria are as follows.

Evaluation criteria ○: No defective phenomenon could be confirmed in the sheet of 1 m ² .
△: 1 place in the 1m ² sheet, failure phenomenon was confirmed.
X: A defective phenomenon was confirmed at two or more places in a sheet of 1 m ² .

[Examples 2-3]
The amount of silica added was changed as shown in Table 1 to create a filler-containing photocurable ink, and the same procedure as in Example 1 except that the matte layer was formed using the filler-containing photocurable ink. A partial mat transfer sheet and a decorative molded product were prepared, and the partial mat transfer sheet was evaluated. The results are shown in Table 1. The evaluation method is the same as in Example 1.

[Example 4]
1. Production of photocurable ink and filler-containing photocurable ink (Synthesis Example 2)
In a stirring apparatus of a reaction apparatus equipped with a stirrer, a cooling pipe, a dropping funnel and a nitrogen introduction pipe, 150 parts of glycidyl methacrylate (hereinafter referred to as GMA), 100 parts of methyl methacrylate (hereinafter referred to as MMA), 1000 parts of butyl acetate Then, 2.5 parts of 2,2′-azobisisobutyronitrile (hereinafter referred to as AIBN) was added, and the system temperature was raised to about 90 ° C. over about 1 hour under a nitrogen stream. The mixture was then stirred for 1 hour. Next, using a dropping funnel, a mixture of 450 parts of GMA, 300 parts of MMA, and 27.5 parts of AIBN prepared in advance was dropped into the stirring apparatus over about 2 hours under a nitrogen stream, and the dropping was completed. Thereafter, the mixture was stirred at 90 ° C. for 3 hours. After 3 hours, 10 parts of AIBN was added to the system, and the mixture was further stirred at 90 ° C. for 1 hour. Thereafter, the temperature inside the system was raised to 120 ° C., and further stirred for 2 hours to obtain a (meth) acrylate resin.

The number average molecular weight of the (meth) acrylate resin obtained above, the number average molecular weight with respect to the number of double bonds, and the glass transition temperature were measured. The results are shown below.
(1) Number average molecular weight: Mw = 90000
(2) Number average molecular weight relative to the number of double bonds: Mw / n = 314
(3) Glass transition temperature: 73 ° C

Next, the above-mentioned (meth) acrylate resin, silicon chain-containing (meth) acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: UT-4314), and methyl ethyl ketone in a stainless steel container equipped with a stirrer at the following ratio: The mixture was added and stirred at room temperature for 30 minutes. After 30 minutes, it was confirmed by visual inspection that the components were uniformly dispersed, and a photocurable ink was obtained. The non-volatile component at this time was 33.3% of the whole.
(1) (Meth) acrylate resin: 90 parts by weight of solid content (apparently 180 parts)
(2) Silicon chain-containing (meth) acrylate: apparently 10 parts by weight (3) methyl ethyl ketone: 110 parts by weight

Finally, silica (average particle diameter: 3 to 4 μm, manufactured by Fuji Silysia Co., Ltd., trade name: Silo Hovic 702) was added to the photocurable ink, and the mixture was stirred at room temperature for 30 minutes. After 30 minutes, it was confirmed by visual inspection that silica was uniformly dispersed, and a filler-containing photocurable ink was obtained. The mixing ratio of the photocurable ink and silica is as shown below.
(1) Photocurable ink: 70 parts by weight (in terms of solid content)
(2) Silica: 30 parts by weight

  Next, using the photocurable ink and filler-containing photocurable ink obtained above, a partial mat transfer sheet and a decorative molded product were prepared, and the partial mat transfer sheet was evaluated. The results are shown in Table 1. The method for producing the partial mat transfer sheet, the method for producing the decorative molded article, and the method for evaluating the partial mat transfer sheet are the same as in Example 1.

[Example 5]
1. Production of photocurable ink and filler-containing photocurable ink (Synthesis Example 3)
In a stirrer of a reactor equipped with a stirrer, a cooling pipe, a dropping funnel and a nitrogen introduction pipe, 150 parts of glycidyl methacrylate (hereinafter referred to as GMA), 100 parts of methyl methacrylate (hereinafter referred to as MMA), lauryl mercaptan 3 parts, 1000 parts of butyl acetate and 10.5 parts of 2,2′-azobisisobutyronitrile (hereinafter referred to as AIBN) are added to the system until it reaches about 90 ° C. over about 1 hour under a nitrogen stream. The internal temperature was raised, followed by stirring for 1 hour. Next, using a dropping funnel, a previously prepared mixed solution consisting of 450 parts of GMA, 300 parts of MMA, 10.0 parts of lauryl mercaptan and 31.5 parts of AIBN was placed in a stirring apparatus in a nitrogen stream over about 2 hours. The solution was dropped at 90 ° C. for 3 hours after the completion of the dropping. After 3 hours, 10 parts of AIBN was added to the system, and the mixture was further stirred at 90 ° C. for 1 hour. Thereafter, the temperature inside the system was raised to 120 ° C., and further stirred for 2 hours to obtain a (meth) acrylate resin.

The number average molecular weight of the (meth) acrylate resin obtained above, the number average molecular weight with respect to the number of double bonds, and the glass transition temperature were measured. The results are shown below.
(1) Number average molecular weight: Mw = 18000
(2) Number average molecular weight relative to the number of double bonds: Mw / n = 314
(3) Glass transition temperature: 73 ° C

Next, the above-mentioned (meth) acrylate resin, silicon chain-containing (meth) acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: UT-4314), and methyl ethyl ketone in a stainless steel container equipped with a stirrer at the following ratio: The mixture was added and stirred at room temperature for 30 minutes. After 30 minutes, it was confirmed by visual inspection that the components were uniformly dispersed, and a photocurable ink was obtained. The non-volatile component at this time was 33.3% of the whole.
(1) (Meth) acrylate resin: 90 parts by weight of solid content (apparently 180 parts)
(2) Silicon chain-containing (meth) acrylate: apparently 10 parts by weight (3) Methyl ethyl ketone: 110 parts by weight

Finally, silica (average particle diameter: 3 to 4 μm, manufactured by Fuji Silysia Co., Ltd., trade name: Silo Hovic 702) was added to the photocurable ink, and the mixture was stirred at room temperature for 30 minutes. After 30 minutes, it was confirmed by visual inspection that silica was uniformly dispersed, and a filler-containing photocurable ink was obtained. The mixing ratio of the photocurable ink and silica is as shown below.
(1) Photocurable ink: 70 parts by weight (in terms of solid content)
(2) Silica: 30 parts by weight

  Next, using the photocurable ink and filler-containing photocurable ink obtained above, a partial mat transfer sheet and a decorative molded product were prepared, and the partial mat transfer sheet was evaluated. The results are shown in Table 1. The method for producing the partial mat transfer sheet, the method for producing the decorative molded article, and the method for evaluating the partial mat transfer sheet are the same as in Example 1.

[Example 6]
1. Production of photocurable ink and filler-containing photocurable ink (Synthesis Example 4)
In a stirring device of a reactor equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube, 200 parts of glycidyl methacrylate (hereinafter referred to as GMA), 50 parts of methyl methacrylate (hereinafter referred to as MMA), lauryl mercaptan 3 parts, 1000 parts of butyl acetate, and 7.5 parts of 2,2′-azobisisobutyronitrile (hereinafter referred to as AIBN) are added, and the system is kept at about 90 ° C. over about 1 hour under a nitrogen stream. The internal temperature was raised, followed by stirring for 1 hour. Next, using a dropping funnel, a previously prepared mixed solution consisting of 600 parts of GMA, 150 parts of MMA, 3.7 parts of lauryl mercaptan, and 22.5 parts of AIBN was stirred in a stirring apparatus for about 2 hours under a nitrogen stream. The solution was dropped at 90 ° C. for 3 hours after the completion of the dropping. After 3 hours, 10 parts of AIBN was added to the system, and the mixture was further stirred at 90 ° C. for 1 hour. Thereafter, the temperature inside the system was raised to 120 ° C., and further stirred for 2 hours to obtain a (meth) acrylate resin.

The number average molecular weight of the (meth) acrylate resin obtained above, the number average molecular weight with respect to the number of double bonds, and the glass transition temperature were measured. The results are shown below.
(1) Number average molecular weight: Mw = 43000
(2) Number average molecular weight relative to the number of double bonds: Mw / n = 514
(3) Glass transition temperature: 88 ° C

The above (meth) acrylate resin, silicon chain-containing (meth) acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: UT-4314), and methyl ethyl ketone were charged into a stainless steel container equipped with a stirrer at the following ratio, Stir at room temperature for 30 minutes. After 30 minutes, it was confirmed by visual inspection that the components were uniformly dispersed, and a photocurable ink was obtained. The non-volatile component at this time was 33.3% of the whole.
(1) (Meth) acrylate resin: 90 parts by weight of solid content (apparently 180 parts)
(2) Silicon chain-containing (meth) acrylate: apparently 10 parts by weight (3) methyl ethyl ketone: 110 parts by weight

Silica (average particle size: 3 to 4 μm, manufactured by Fuji Silysia Co., Ltd., trade name: Silo Hovic 702) was added to the photocurable ink, and the mixture was stirred at room temperature for 30 minutes. After 30 minutes, it was confirmed by visual inspection that silica was uniformly dispersed, and a filler-containing photocurable ink was obtained. The mixing ratio of the photocurable ink and silica is as shown below.
(1) Photocurable ink: 70 parts by weight (in terms of solid content)
(2) Silica: 30 parts by weight

  Next, using the photocurable ink and filler-containing photocurable ink obtained above, a partial mat transfer sheet and a decorative molded product were prepared, and the partial mat transfer sheet was evaluated. The results are shown in Table 1. The method for producing the partial mat transfer sheet, the method for producing the decorative molded article, and the method for evaluating the partial mat transfer sheet are the same as in Example 1.

[Example 7]
1. Production of photocurable ink and filler-containing photocurable ink (Synthesis Example 5)
In a stirring device of a reactor equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube, 250 parts of glycidyl methacrylate (hereinafter referred to as GMA), 1.3 parts of lauryl mercaptan, 1000 parts of butyl acetate, 2, 2 After adding 7.5 parts of ′ -azobisisobutyronitrile (hereinafter referred to as AIBN), the temperature inside the system was raised to about 90 ° C. over about 1 hour under a nitrogen stream, followed by stirring for 1 hour did. Next, using a dropping funnel, a previously prepared liquid mixture consisting of 750 parts of GMA, 3.7 parts of lauryl mercaptan and 22.5 parts of AIBN was dropped into the stirring apparatus over about 2 hours under a nitrogen stream. After the dropping, the mixture was stirred at 90 ° C. for 3 hours. After 3 hours, 10 parts of AIBN was added to the system, and the mixture was further stirred at 90 ° C. for 1 hour. Thereafter, the temperature inside the system was raised to 120 ° C., and further stirred for 2 hours to obtain a (meth) acrylate resin.

The number average molecular weight of the (meth) acrylate resin obtained above, the number average molecular weight with respect to the number of double bonds, and the glass transition temperature were measured. The results are shown below.
(1) Number average molecular weight: Mw = 34000
(2) Number average molecular weight relative to the number of double bonds: Mw / n = 214
(3) Glass transition temperature: 46 ° C

The above (meth) acrylate resin, silicon chain-containing (meth) acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: UT-4314), and methyl ethyl ketone were charged into a stainless steel container equipped with a stirrer at the following ratio, Stir at room temperature for 30 minutes. After 30 minutes, it was confirmed by visual inspection that the components were uniformly dispersed, and a photocurable ink was obtained. The non-volatile component at this time was 33.3% of the whole.
(1) (Meth) acrylate resin: 90 parts by weight of solid content (apparently 180 parts)
(2) Silicon chain-containing (meth) acrylate: apparently 10 parts by weight (3) methyl ethyl ketone: 110 parts by weight

Silica (average particle size: 3 to 4 μm, manufactured by Fuji Silysia Co., Ltd., trade name: Silo Hovic 702) was added to the photocurable ink, and the mixture was stirred at room temperature for 30 minutes. After 30 minutes, it was confirmed by visual inspection that silica was uniformly dispersed, and a filler-containing photocurable ink was obtained. The mixing ratio of the photocurable ink and silica is as shown below.
(1) Photocurable ink: 70 parts by weight (in terms of solid content)
(2) Silica: 30 parts by weight

  Next, a partial mat transfer sheet and a decorative molded product were prepared using the photocurable ink and filler-containing photocurable ink obtained above, and the partial mat transfer sheet was evaluated. The results are shown in Table 1. The method for producing the partial mat transfer sheet, the method for producing the decorative molded article, and the method for evaluating the partial mat transfer sheet are the same as in Example 1.

[Comparative Examples 1-3]
The addition amount of the silicon chain (meth) acrylate resin and silica is changed as shown in Table 1 to prepare photocurable ink and filler-containing photocurable ink, and using these inks, a release layer and a mat layer A partial mat transfer sheet and a decorative molded product were prepared in the same manner as in Example 1 except that was formed, and the partial mat transfer sheet was evaluated. The results are shown in Table 1. The evaluation method is the same as in Example 1.

1 ... Base sheet,
2 ... release layer,
3 ... Matte layer,
4 ... protective layer,
5 ... Pattern layer,
6 ... adhesive layer,
7 ... Hard coat layer,
100: Partial mat transfer sheet,

Claims (8)

In the partial mat transfer sheet for imparting a matte design to the molded product, the partial mat transfer sheet is a base sheet,
It is formed on the base sheet and has a number average molecular weight of 10,000 to 100,000, the number average molecular weight is 1000 or less with respect to the number of double bonds, and a glass transition temperature is 40 ° C. to 150 ° C. ) A release layer made of an acrylate resin;
(Meth) acrylate resin that is partially formed on the release layer and that constitutes the release layer, and a ratio of 5 to 45 W% with respect to the (meth) acrylate resin A mat layer composed of a filler contained in
A hard coat layer formed on the release layer and the mat layer;
A partial mat transfer sheet comprising: an adhesive layer formed on the hard coat layer. In the partial mat transfer sheet for imparting a matte design to the molded product, the partial mat transfer sheet is a base sheet,
Partially formed on the base sheet, the number average molecular weight is 10,000 to 100,000, the number average molecular weight is 1000 or less with respect to the number of double bonds, and the glass transition temperature is 40 ° C to 150 ° C. A release layer made of a certain (meth) acrylate resin;
5 for the (meth) acrylate resin that is the same as the (meth) acrylate resin that is formed in a region where the release layer of the base sheet is not formed and that constitutes the release layer. A mat layer composed of a filler contained in a ratio of ˜45 W%,
A hard coat layer formed on the release layer and the mat layer;
A partial mat transfer sheet comprising: an adhesive layer formed on the hard coat layer. In the partial mat transfer sheet that gives a mat-like design to the molded product,
The partial mat transfer sheet is a base sheet,
It is formed on the base sheet and has a number average molecular weight of 10,000 to 100,000, the number average molecular weight is 1000 or less with respect to the number of double bonds, and a glass transition temperature is 40 ° C. to 150 ° C. ) An acrylate resin, and a mat layer containing a filler included in a proportion of 5 to 45 W% with respect to the (meth) acrylate resin;
A release layer that is partially formed on the mat layer and is made of the same (meth) acrylate resin as the (meth) acrylate resin that constitutes the mat layer;
A hard coat layer formed on the release layer and the mat layer;
A partial mat transfer sheet comprising: an adhesive layer formed on the hard coat layer.   The partial mat transfer sheet according to claim 3, wherein the release layer is thicker than the mat layer.   5. The partial mat transfer sheet according to claim 1, wherein the release layer and the mat layer each comprise a silicon chain-containing (meth) acrylate resin at a ratio of 1 to 10 W% with respect to the (meth) acrylate resin. The partial mat transfer sheet according to claim 1, wherein the silicon chain-containing (meth) acrylate resin is obtained by polymerizing a silicate oligomer represented by the following chemical formula and an acrylic monomer at a ratio of 5/95 to 85/15. .

(In the formula, n represents an integer of 1 to 20, and R represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.)   The partial mat transfer sheet according to claim 1, wherein the release layer and the mat layer each have a thickness of 0.2 to 2 μm. It consists of a (meth) acrylate resin having a number average molecular weight of 1000 or less, a number average molecular weight of 10,000 to 100,000, and a glass transition temperature of 40 to 150 ° C. on the base sheet and an organic solvent for gravure ink. A first step of forming a release layer using a photocurable ink having a nonvolatile component of 50% by mass or more and a viscosity of 200 mP · S or less at room temperature;
It consists of the (meth) acrylate resin on the release layer, a filler contained in a proportion of 5 to 45 W% with respect to the (meth) acrylate resin, and an organic solvent for gravure ink, and contains 50 mass of nonvolatile components. A second step of partially forming a matte layer using a filler-containing photocurable ink having a viscosity of not less than% and a viscosity of not more than 200 mP · s at room temperature;
A third step of forming a hard coat layer on the release layer and the mat layer;
A fourth step of irradiating the release layer, the mat layer, and the protective layer with light;
And a fifth step of forming an adhesive layer on the protective layer,
A method for producing a partial mat transfer sheet, wherein the steps from the first step to the fifth step are carried out on the same production line.

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