JP5159980B1 - Transfer sheet that can suppress the occurrence of cracks - Google Patents

Abstract

An object of the present invention is to provide a transfer sheet in which cracks do not easily occur in a metal vapor deposition layer in the step of injecting resin onto the transfer sheet in a mold.
The transfer sheet of the present invention comprises a transfer layer on a substrate sheet, a plurality of transfer layers are formed on the substrate sheet, and the shape thereof is in the direction in which the transfer layer of the substrate sheet is formed. A convex-shaped concavo-convex forming layer, a base sheet and a shock-absorbing layer formed on the concavo-convex-forming layer, and a metal vapor-deposited layer formed on the shock-absorbing layer. An acrylic polyol having a molecular weight of 72000-77000, a hydroxyl value of 8-15 mg KOH / g, and a glass transition temperature (Tg) of 60-100 ° C. was used.
[Selection] Figure 1

Description

  The present invention relates to a transfer sheet, and more particularly to a transfer sheet in which cracks are unlikely to occur in a metal vapor deposition layer during molding.

  2. Description of the Related Art Conventionally, a method for decorating the surface of an article such as a plastic part or an exterior product using a transfer sheet is known. The transfer sheet has a structure in which a transfer layer is provided on one side of a base sheet as a support, and this transfer layer is transferred from the base sheet to the surface of the article. The transfer layer transferred to the surface of the article is a laminate in which a resin, a pattern, or the like is laminated, and forms a protective coating or a decorative coating on the article surface.

  For example, Patent Document 1 discloses a transfer sheet in which an anchor layer and a transparent uneven layer are formed on a metal vapor deposition layer. The transparent concavo-convex layer has a fine concavo-convex surface, and the width of the fine concavo-convex surface is 0.2 to 200 μm and the depth is 0.1 to 10 μm even when the transfer sheet is stretched to a predetermined size. It is configured to fit within.

JP 2007-245725 A

  However, when a decorative molded product is created using the transfer sheet of Patent Document 1, in the manufacturing process (mainly, the process of injecting the resin into the transfer sheet in the mold), the metal vapor deposition layer is the hot pressure of the resin. There was a problem that the metal vapor deposition layer cracked.

  An object of the present invention is to provide a transfer sheet in which cracks do not easily occur in a metal vapor-deposited layer when a decorative molded product is created using the transfer sheet.

  In order to achieve the above object, the present invention is configured as follows.

  The first aspect of the present invention is characterized in that, in a transfer sheet comprising a transfer layer on a base sheet, a plurality of transfer layers are formed on the base sheet, and the shape of the transfer layer of the base sheet is formed. A concavo-convex forming layer having a convex shape with respect to the direction in which the base sheet is formed, a shock absorbing layer formed on the base sheet and the concavo-convex forming layer, and a metal vapor deposition layer formed on the shock absorbing layer. The impact absorbing layer has an average molecular weight of 72000-77000, a hydroxyl value of 8-15 mgKOH / g, and an acrylic polyol resin having a glass transition temperature (Tg) of 60-100 ° C.

  A feature of the second aspect of the present invention includes a protective layer formed between the base sheet and the concavo-convex forming layer and between the base sheet and the shock absorbing layer, and the protective layer has a polymerization average. It has a molecular weight of 70,000 to 75,000, a hydroxyl value of 3 to 10 mgKOH / g, and an epoxy melamine having a glass transition temperature (Tg) of 80 to 120 ° C.

The feature of the third aspect of the present invention resides in that the resin constituting the concavo-convex forming layer contains acrylate as a main component and a silane coupling agent represented by the following formula having a molecular weight of 100 to 500 is added. .

  R in the formula is an alkyl straight chain containing at least one of an epoxy group, a vinyl group, a methacryl group, a mercapto group, and a styryl group, and D is any one of OMe, OEt, OEtOMe, and OEtOEt. Yes, Me represents a methyl group, and Et represents an ethyl group.

  The feature of the fourth aspect of the present invention resides in that the resin constituting the concavo-convex forming layer is made of the same resin as the shock absorbing layer.

  The feature of the fifth aspect of the present invention resides in that the resin constituting the unevenness forming layer is made of the same resin as the protective layer.

  The feature of the sixth aspect of the present invention is that the convex portions constituting the concave-convex forming layer have a size of 200 μm to 1000 μm in the width direction and 1 μm to 30 μm in the height direction.

It is sectional drawing of the transfer sheet of this invention. It is sectional drawing of the decorative molded product created from the transfer sheet of this invention. It is a manufacturing sectional view when creating a decorative molded product from the transfer sheet of the present invention. It is a manufacturing sectional view when creating a decorative molded product from the transfer sheet of the present 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.

[Transfer sheet]
FIG. 1 is a cross-sectional view of the transfer sheet of the present invention, and FIG. 2 is a cross-sectional view of a decorative molded product 100 created using the transfer sheet of the present invention. As shown in FIG. 1, a transfer layer 3 is provided on one side of the base sheet 2. The transfer layer 3 has a configuration in which a hard coat layer 4, a design layer 5, a protective layer 6, a concavo-convex forming layer 7, a shock absorbing layer 8, a metal vapor deposition layer 9, and an adhesive layer 10 are laminated in order from the base sheet 2 side. The hard coat layer 4, the design layer 5, and the protective layer 6 are laminated on the entire surface of the base sheet 2, and the concavo-convex forming layer 7 is formed on the protective layer 6 so as to be convex toward the adhesive layer 10 side. It is partially laminated on top. The shock absorbing layer 8 is laminated on the protective layer 6 and the concavo-convex forming layer 7 so as to cover the concavo-convex forming layer 7 and the protective layer 6, and the metal vapor deposition layer 9 and the adhesive layer 10 are shock-absorbing in this order. It is laminated on the layer 8.

  Of the layers constituting the transfer layer 3, each resin layer can be formed by a method similar to the conventional method unless otherwise specified. Examples of conventional layer forming methods include coating methods such as gravure coating, roll coating, and comma coating, printing methods such as gravure printing, and screen printing.

[Base sheet]
The base sheet 2 is made of a sheet material or a film material conventionally used for supporting the design layer 4 and the like on the sheet. Film material refers to a sheet material made of synthetic resin. As the synthetic resin, polypropylene resin, polyethylene resin, polyamide resin, polyester resin, acrylic resin, polyvinyl chloride resin and the like can be used. In addition, a metal sheet such as aluminum foil or copper foil, a cellulose sheet such as glassine paper, coated paper, cellophane, or a composite of each of the above-mentioned sheets having releasability as a base sheet of a normal transfer sheet It can be used as a base sheet. In addition, the thickness of the base sheet 1 is 10 μm to 150 μm.

[Transfer layer]
The transfer layer 3 is a layer provided on one side of the substrate sheet 2 and transferred from the substrate sheet 2 to the surface of the transfer target. The transfer layer 3 includes a hard coat layer 4, a design layer 5, a protective layer 6, an unevenness forming layer 7, a shock absorbing layer 8, a metal vapor deposition layer 9, and an adhesive layer 10.

<Hard coat layer>
As shown in FIG. 2, the hard coat layer 4 is disposed on the surface of a decorative molded product 100 created using the transfer sheet 1, and has a certain hardness to protect the transfer layer 3. . Examples of the material of the hard coat layer 4 include ionizing radiation curable resins such as cyanoacrylate and urethane acrylate, and thermosetting resins such as acrylic and urethane, but are not particularly limited. The hard coat layer 4 has a thickness of 0.5 μm to 30 μm.

<Design layer>
As shown in FIG. 2, the design layer 5 is a layer that is arranged on the surface of the molding resin 11 in the decorative molded product 100 and decorates the molding resin 11. As a material of the pattern layer 5, 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, and a pigment or dye of an appropriate color is used. A color ink contained as a colorant 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. In addition, it is preferable to use an acrylic resin among the binders constituting the pattern layer 5. When an acrylic resin is used as the binder constituting the design layer 5, the acrylic resin and the resin constituting the protective layer 6 interact to improve the adhesion between the design layer 5 and the protective layer 6. In addition, the thickness of the pattern layer 5 is 0.5 micrometer-15 micrometers.

  As a method for forming the pattern layer 5, an offset printing method and a gravure printing method are particularly suitable for performing multicolor printing and gradation expression.

<Protective layer>
The protective layer 6 is a layer that protects the shock absorbing layer 8 and the metal deposition layer 9 from external factors in the decorative molded product 100 created from the transfer sheet 1. Specifically, it is a layer that protects the shock absorbing layer 8 and the metal vapor-deposited layer 9 from impact, wear, or chemicals. The protective layer 6 is composed of epoxy melamine having a polymerization average molecular weight of 70000-75000, a hydroxyl value of 3-10 mg KOH / g, and a glass transition temperature (Tg) of 80-120 ° C. When the resin constituting the protective layer 6 is configured as described above, the pencil hardness of the protective layer 6 is HB to 2H.

  Then, as shown in FIG. 2, in the decorative molded product 100 created using the transfer sheet 1, the protective layer 6 is arranged on the surface side of the decorative molded product 100 with respect to the shock absorbing layer 8 and the metal vapor deposition layer 9. Is done. As a result, in the decorative molded product 100, the shock absorbing layer 8 and the metal vapor-deposited layer 9 are protected by the protective layer 6 having a pencil hardness of HB to 2H, so that the decorative molded product 100 has wear resistance and impact resistance. Excellent in design and can maintain high design properties for a long time.

  Further, as described above, in the decorative molded product 100 created from the transfer sheet 1 of the present invention, the protective layer 6 is disposed on the surface side of the decorative molded product 100 with respect to the shock absorbing layer 8. If it does so, an ultraviolet-ray will be absorbed by the epoxy melamine which comprises the protective layer 6, and the quantity of the ultraviolet-ray which will hit the impact-absorbing layer 8 arrange | positioned under the protective layer 6 will reduce. Therefore, since it can suppress that resin which comprises the shock absorption layer 8 discolors yellow by an ultraviolet-ray, the decorative molded product 100 can hold | maintain high designability for a long time.

  Moreover, the thickness of the protective layer 6 is 0.1 micrometer-2.0 micrometers. When the thickness of the protective layer 6 is in the above range, the protective layer 6 itself does not generate cracks in the injection process, and the impact absorbing layer 8 can be prevented from being discolored to yellow.

<Unevenness forming layer>
As shown in FIG. 2, the concavo-convex forming layer 7 is a three-dimensional representation of the metal vapor-deposited layer 9 laminated below the concavo-convex forming layer 7 in the decorative molded product 100 created using the transfer sheet 1. This is a layer that improves the design of the decorative molded product 100. As shown in FIG. 1, the concavo-convex forming layer 7 is composed of a plurality of convex portions, and the size per convex portion is 200 μm to 1000 μm in the width direction and 1 μm to 30 μm in the height direction.

  In addition, when the size of the convex portion is 200 μm to 1000 μm in the width direction and 1 μm to 30 μm in the height direction, it is easy to visually recognize the unevenness forming layer 7, and in combination with the metal vapor deposition layer 9 The design of the unevenness forming layer 7 can be expressed three-dimensionally.

  Examples of the material of the unevenness forming layer 7 include polyvinyl resins, polyamide resins, polyester resins, vinyl acetate vinyl acetate resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins, cellulose ester resins, alkyd resins, and the like, acrylic resins, and the like. . Among the above, an acrylic resin is preferable. This is because the acrylic resin has excellent thermal shock resistance and can suppress the crushing of the convex portion in the step of injecting the resin into the mold.

<Shock absorbing layer>
The shock absorbing layer 8 is a layer that protects the metal vapor deposition layer 9 from the heat pressure of the resin in the step of integrating the transfer sheet 1 and the resin when the decorative molded product 100 is created from the transfer sheet 1. The polymerization average molecular weight is 72000-77000, the hydroxyl value is 8-15 mgKOH / g, and the glass transition temperature (Tg) is comprised from the acrylic polyol which is 60-100 degreeC. When the shock absorbing layer 8 is configured as described above, the stretch rate of the shock absorbing layer 8 is 100 to 200%.

  When the stretch ratio of the impact absorbing layer 8 is 100 to 200%, when the resin is injected from the adhesive layer 10 side in the step of injecting the resin to the transfer sheet 1, the impact absorbing layer 8 causes the metal vapor deposition layer 9 to A part of the heat pressure can be absorbed. As a result, it is possible to suppress cracks in the metal vapor deposition layer 9 in the above process.

  Moreover, if comprised as mentioned above, the pencil hardness of the impact-absorbing layer 8 will be BH. Then, in the step of injecting the resin onto the transfer sheet 1, the shape of the shock absorbing layer 8 is maintained even if pressure acts on the shock absorbing layer 8 from the resin. As a result, since the shape of the concavo-convex forming layer 7 formed adjacent to the shock absorbing layer 8 is also maintained, it is possible to suppress the deformation or disappearance of the shape of the concavo-convex forming layer 7 in the above process.

  Further, when the shock absorbing layer 8 is configured as described above, the shock absorbing layer 8 has a large polarity. Then, the adhesion between the shock absorbing layer 8 and the metal vapor deposition layer 9 is improved by the interaction with the metal vapor deposition layer 9. As a result, the metal vapor deposition layer 9 can be prevented from being oxidized by oxygen or moisture in the air.

  Further, as described above, when the shock absorbing layer 8 is configured, the shock absorbing layer 8 and the protective layer 6 are formed by the interaction between the polyol component of the resin that forms the shock absorbing layer 8 and the epoxy component that forms the protective layer 6. Adhesion with is improved. As a result, delamination that occurs between the shock absorbing layer 8 and the protective layer 6 can be suppressed.

  When the acrylic polyol has a polymerization average molecular weight of less than 72,000, an ink flow is generated in the impact absorbing layer 8 due to the thermal pressure of the resin in the injection process. On the other hand, if it exceeds 77000, cracks occur in the shock absorbing layer 8 in the injection process. Moreover, the adhesiveness with the metal vapor deposition layer 9 and the protective layer 6 falls that the hydroxyl value of an acrylic polyol is less than 8 mgKOH / g. If it exceeds 15 mgKOH / g, cracks occur in the shock absorbing layer 8 in the injection process. Furthermore, if the glass transition temperature (Tg) of the acrylic polyol resin is less than 60 ° C., blocking occurs in the transfer sheet 1 in the production process, and if it exceeds 100 ° C., cracks occur in the impact absorbing layer 8.

  In addition, it is preferable that the thickness of the shock absorbing layer 8 is 0.1 μm to 5.0 μm. If the thickness of the shock absorbing layer 8 is less than 0.1 μm, the heat pressure in the injection process cannot be sufficiently suppressed, and ink flow occurs in the shock absorbing layer 8. On the other hand, when the thickness of the shock absorbing layer 8 exceeds 5.0 μm, cracks and blocking occur in the shock absorbing layer 8.

<Metal vapor deposition layer>
The metal deposition layer 9 is a layer that gives the transfer layer 3 a metallic luster appearance. The metal vapor-deposited layer 9 may be formed on the entire sheet surface of the transfer layer 3 or a part thereof. When the metal vapor deposition layer 9 is formed on a part of the sheet surface, a known patterning method can be used.

  The metal deposition layer 9 is formed by depositing metal on the surface of the shock absorbing layer 8. The metal can be deposited by evaporating the metal and attaching a metal vapor to the surface of the shock absorbing layer. What is necessary is just to select the kind of metal suitably according to the metallic luster color to express.

  In addition, the metal used for the metal vapor deposition layer 9 has preferable aluminum, tin, chromium, or indium. This is because these metal vapor-deposited layers are excellent in flexibility and have good followability with respect to the three-dimensional shape, so that the metal vapor-deposited layer 9 is unlikely to crack.

  The thickness of the metal vapor deposition layer 9 is 30-200 nm, Preferably it is 40-190 nm, More preferably, it is 50-180 nm. If the thickness of the metal vapor deposition layer 9 is less than 30 nm, the gloss of the metal color is insufficient, and if it exceeds 200 nm, vapor deposition defects are likely to occur in the metal vapor deposition layer 9.

<Adhesive layer>
The adhesive layer 10 is a layer for adhering the molding resin and the transfer sheet 1, and is formed on the surface of the transfer sheet 1 opposite to the base sheet 2. For the adhesive layer 10, a heat-sensitive or pressure-sensitive resin suitable for the type of molding resin is used. If the molding resin is a PMMA resin, for example, the adhesive layer may be a PMMA resin. If the molding resin is PC or polystyrene (PS) resin, for example, the adhesive layer may be made of PMMA, PS, or PA resin that has an affinity for these resins. The adhesive layer 10 has a thickness of 0.1 μm to 20 μm.

[Other Embodiments]
<Unevenness forming layer>
Furthermore, as the material of the unevenness forming layer 7, the same resin as that of the shock absorbing layer 8 can be used.

  When the unevenness forming layer 7 is made of the same resin as the shock absorbing layer 8, the adhesion between the unevenness forming layer 7 and the shock absorbing layer 8 is improved. Further, as described above, the resin constituting the shock absorbing layer 8 and the resin forming the protective layer 6 have high adhesion. Therefore, when the unevenness forming layer 7 and the shock absorbing layer 8 are made of the same resin, the adhesion between the unevenness forming layer 7 and the protective layer 6 is also increased. As a result, it is possible to prevent delamination between the three members of the shock absorbing layer 8, the unevenness forming layer 7, and the protective layer 6.

  Further, the material of the unevenness forming layer 7 may be made of the same resin as that of the protective layer 6.

  When the resin forming the unevenness forming layer 7 is made of the same resin as the protective layer 6, the adhesion between the unevenness forming layer 7 and the protective layer 6 is improved. Further, as described above, the resin forming the protective layer 6 and the resin forming the shock absorbing layer 8 have high adhesion. Therefore, when the concavo-convex forming layer 7 is made of the same resin as the protective layer 6, the adhesion between the concavo-convex forming layer 7 and the shock absorbing layer 8 is also increased. As a result, it is possible to prevent delamination between the three members of the shock absorbing layer 8, the unevenness forming layer 7, and the protective layer 6.

Furthermore, as a material for the unevenness forming layer 7, a material obtained by adding a silane coupling agent represented by the following formula having a molecular weight of 100 to 500 to an ionizing radiation curable resin mainly composed of acrylate may be used.

  R in the formula is an alkyl straight chain containing at least one of an epoxy group, a vinyl group, a methacryl group, a mercapto group, and a styryl group, and D is any one of OMe, OEt, OEtOMe, and OEtOEt. Yes, Me represents a methyl group, and Et represents an ethyl group.

  When a silane coupling agent having a molecular weight of 100 to 500 is added to an ionizing radiation curable resin containing acrylate as a main component, the silane coupling agent and the acrylate of the concavo-convex forming layer 7 in the concavo-convex forming layer to which the silane coupling agent has been added. It reacts with a resin whose main component is. The reaction product comes into contact with the adjacent shock absorbing layer 8, and the adhesion between the unevenness forming layer 7 and the shock absorbing layer 8 is improved by the interaction between the reaction product and the acrylic polyol constituting the shock absorbing layer 8. As a result, delamination between the unevenness forming layer 7 and the shock absorbing layer 8 in the transfer sheet can be prevented.

  Furthermore, when a silane coupling agent is added to a resin containing acrylate as a main component, the hardness of the unevenness forming layer 7 becomes higher than the hardness of the shock absorbing layer 8. Specifically, the pencil hardness is HB to 2H. As a result, the impact resistance of the decorative molded product 100 created from the transfer sheet 1 of the present invention is improved.

  In addition, when the hardness of the unevenness forming layer 7 is higher than the hardness of the shock absorbing layer 8 and the pencil hardness is HB to 2H, the shock absorbing layer 8 is damaged in the process of injecting the resin onto the transfer sheet 1 and its shape The shape of the concavo-convex forming layer 7 is maintained even when the angle changes. As a result, it is possible to prevent the shape of the unevenness forming layer 7 from being deformed or lost.

  Further, in the unevenness forming layer 7 to which the silane coupling agent is added, the reaction product obtained by the reaction as described above is also in contact with the adjacent protective layer 6. If it does so, the adhesiveness of the protective layer 6 and the uneven | corrugated formation layer 7 will improve by interaction of this reaction material and the epoxy melamine which comprises the protective layer 6. FIG. As a result, delamination that occurs between the protective layer 6 and the unevenness forming layer 7 can be prevented.

  Such ionizing radiation curable resins mainly composed of acrylate include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, melamine Polymerized into an appropriate mixture of unsaturated ethylene oligomers and unsaturated ethylene monomers such as (meth) acrylate, triazine acrylate, epoxy-modified (meth) acrylate, urethane-modified (meth) acrylate, and (meth) acryl-modified polyester What added the composition etc. which added the initiator and the sensitizer are mentioned.

  Moreover, what has a (meth) acryloyl group which is a compound which has a reactive double bond as ionizing radiation curable resin can also be used. For example, monofunctional types such as methyl (meth) acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and 1,6-hexanediol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) It may be a polyfunctional type such as acrylate or dipentaerythritol hexa (meth) acrylate.

  Moreover, oligomers, such as polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, oligo acrylate, alkyd acrylate, polyol acrylate, etc. may be sufficient. Furthermore, for example, a styrene monomer, α-methylstyrene, divinylbenzene, vinyl acetate, pentene, hexene, an unsaturated compound or the like having a vinyl group or an allyl group may be used. These compounds are further introduced with polar groups such as hydroxyl groups, amino groups, carboxyl groups, carbonyl groups, and epoxy groups in order to improve adhesion to the printing surface (described later) and compatibility with the base protection material. There are things to do.

  The polymer constituting the ionizing radiation curable resin is set to a specific blending amount in consideration of physical and chemical required performance of the barrier layer before and after irradiation with active energy rays. That is, the (meth) acryl equivalent is 100 to 300 g / eq, preferably 150 to 300 g / eq, from the viewpoint of curability when irradiated with active energy rays. When the (meth) acrylic equivalent is greater than 300 g / eq, the wear resistance after irradiation with active energy rays is insufficient, and it is difficult to obtain a product with a weight less than 100 g / eq. Moreover, the hydroxyl value of a polymer is 20-500, Preferably it is set to 100-300 from the reactive point with the polyfunctional isocyanate used together. When the hydroxyl value is less than 20, the reaction with the polyfunctional isocyanate is insufficient, and the degree of thermal crosslinking of the concavo-convex forming layer 7 is lowered. Therefore, there is a disadvantage that it becomes difficult to print and roll up the transfer sheet due to remaining adhesiveness or insufficient solvent resistance. Also, it is difficult to obtain those having a hydroxyl value exceeding 500. The weight average molecular weight of the polymer is 5000 to 50000, preferably 8000 to 40000. If the weight average molecular weight of the polymer is less than 5,000, adhesiveness remains in the unevenness forming layer 7 of the transfer sheet or solvent resistance is insufficient, so that it is difficult to print and roll the transfer sheet 1 again. There is a disadvantage that a clear picture cannot be obtained. On the other hand, if it exceeds 50000, the resin viscosity becomes too high and the ink application workability is lowered.

  There is no limitation in particular as a manufacturing method of a polymer, A conventionally well-known method is employable. For example, [1] a method of introducing a (meth) acryloyl group into a part of a side chain of a polymer containing a hydroxyl group, [2] α, β-unsaturation containing a hydroxyl group in a copolymer containing a carboxyl group A method in which a monomer is subjected to a condensation reaction, [3] a method in which an α, β-unsaturated monomer containing an epoxy group is added to a copolymer containing a carboxyl group, and [4] an epoxy group-containing polymer. There is a method of reacting an α, β-unsaturated carboxylic acid.

  Taking the method [4] as an example, the method for producing the polymer used in the present invention will be described more specifically. For example, the polymer used in the present invention can be easily obtained by a method in which an α, β-unsaturated carboxylic acid such as acrylic acid is reacted with a polymer having a glycidyl group. Preferred polymers having a glycidyl group include, for example, a homopolymer of glycidyl (meth) acrylate and a copolymer of glycidyl (meth) acrylate and an α, β-unsaturated monomer not containing a carboxyl group. Can be mentioned. Examples of the α, β-unsaturated monomer not containing a carboxyl group include various (meth) acrylic acid esters, styrene, vinyl acetate, acrylonitrile and the like. Use of an α, β-unsaturated monomer containing a carboxyl group is not preferred because crosslinking occurs during the copolymerization reaction with glycidyl (meth) acrylate, resulting in increased viscosity or gelation.

  In any case, when adopting each of the methods [1] to [4], the conditions such as the types of monomers and polymers used, the amount of these used, etc. are set so as to satisfy the numerical limit range related to the polymer. Must be performed as appropriate. Such operations are well known to those skilled in the art.

  In the present invention, the polyfunctional isocyanate used in combination with the polymer is not particularly limited, and various known ones can be used. For example, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, 1,6-hexane diisocyanate, the above trimer, a prepolymer obtained by reacting a polyhydric alcohol with the above diisocyanate, etc. Can be used. In the present invention, the reason why the polyfunctional isocyanate is used in combination with the polymer is that when the concavo-convex forming layer 7 is laminated on the protective layer 6, the adhesiveness of the concavo-convex forming layer 7 before irradiation with active energy rays is kept low, and the impact is reduced. This is because when the absorption layer 8 is formed, the resistance to the solvent contained in the ink is satisfied to some extent. That is, a hydroxyl group contained in a polymer is reacted with an isocyanate group of a polyfunctional isocyanate to form a mild thermal cross-linked product, thereby imparting the above performance.

  The proportion of the polymer and polyfunctional isocyanate used is determined so that the ratio of the number of hydroxyl groups to the number of isocyanate groups in the polymer is 1 / 0.01 to 1/1, preferably 1 / 0.05 to 1 / 0.8. Is done.

  Moreover, the active energy ray curable resin composition used for the uneven | corrugated formation layer 7 can contain the following components other than a polymer and polyfunctional isocyanate as needed. That is, reactive diluent monomers, solvents, colorants, and the like. In addition, when an electron beam is used for irradiation with active energy rays, a sufficient effect can be exhibited without using a photopolymerization initiator. However, when ultraviolet rays are used, various known photopolymerization initiators are added. There is a need to. The unevenness forming layer 7 may be colored or uncolored.

    The active energy ray-curable resin composition used for the unevenness forming layer 7 contains an ethylenically unsaturated group, a hydroxyl group, and an isocyanate group. When this active energy ray-curable resin composition is heated, the hydroxyl group and the isocyanate group react to crosslink the resin. Moreover, when this active energy ray-curable resin composition is exposed to active energy rays, ethylenically unsaturated groups are polymerized and the resin is crosslinked. That is, the active energy ray-curable resin composition used for the unevenness forming layer 7 is crosslinked by both heat and active energy rays.

[Transfer method to article]
Below, the method to produce the decorative molded product 100 using the transfer sheet 1 of this invention is demonstrated. 3 and 4 are production cross-sectional views when the decorative molded product 100 is created using the transfer sheet 1 of the present invention. In addition, as a method of creating the decorative molded product 100 using the transfer sheet 1 of the present invention, hot roll transfer, in-mold molding, and the like can be given. For example, in thermal roll transfer, as shown in FIG. 3, the transfer layer 3 side (opposite side of the base sheet 2) of the transfer sheet 1 is overlaid on the surface of the transfer target 20, and a roll transfer machine 21, up-down Heat and pressure are applied from the substrate sheet 2 side of the transfer sheet 1 using a transfer machine such as a transfer machine. By doing so, the transfer sheet 1 adheres to the surface of the transfer target 20. Next, when the base sheet 2 is peeled after cooling, the transfer layer 3 is transferred to the surface of the transfer target 20, and the surface of the article is coated (decorated).

  The material of the transfer target 20 is not particularly limited as long as it has been conventionally transferred by a transfer sheet, or can be used to adhere the transfer layer to the surface by devising the components of the adhesive layer. Various synthetic resins, metal, glass, wood, paper members, these paints and decorations are used as transferred objects

  In the in-mold molding, as shown in FIG. 4, first, the transfer sheet 1 is fed into the molding die in such a direction that the base sheet 2 is in contact with the inner surface of the die (fixed die 22). Next, the mold (fixed mold 22, movable mold 23) is closed, and the molten resin 24 is in contact with the surface of the transfer sheet 1 on the transfer layer 3 side (opposite side of the base sheet 2), that is, the transfer sheet 1 is melted. The molten resin 24 is filled in the mold so as to be sandwiched between the resin 24 and the inner surface of the mold (movable mold 23). As a result, the molten resin 24 is molded, and at the same time, the transfer sheet 1 is bonded to the surface of the resin molded product. The resin molded product is cooled, the mold is opened, and the resin molded product is taken out. When the base sheet 2 is finally peeled off, the transfer layer 3 is transferred onto the surface of the resin molded product, and the surface of the resin molded product is coated (decorated).

  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. Examples and comparative examples were evaluated based on the following evaluation criteria.

[Example of Embodiment 1]
[Example 1]
A polyester resin film having a thickness of 38 μm was used as the base sheet, and an epoxy melamine release agent was applied on the base sheet to a thickness of 1 μm by a gravure printing method to form a release layer. Thereafter, polyurethane was applied on the release layer by a gravure printing method to form a pattern layer. Next, an epoxy melamine having a polymerization average molecular weight of 72000-74000, a hydroxyl value of 5 KOH / g, and a glass transition temperature of 80 to 90 ° C. was applied on the design layer by a gravure printing method to form a protective layer. In addition, the thickness of the protective layer was 1.2 μm. Next, an acrylic polyol having a polymerization average molecular weight of 72000 to 74000, a hydroxyl value of 10 KOH / g, and a glass transition temperature of 70 to 90 ° C. was applied on the protective layer by a gravure printing method to form an unevenness forming layer. . The thickness of the concavo-convex forming layer was 1.0 μm. Furthermore, on the unevenness forming layer, the same resin as that used for forming the unevenness forming layer was applied by a gravure printing method to form an impact absorbing layer. The thickness of the shock absorbing layer was 1.3 μm. Finally, the sheet was fed into a metal vapor deposition machine (manufactured by ULVAC), and a tin film was vapor-deposited on the shock absorbing layer to form a metal vapor deposition layer. In addition, the thickness of the metal vapor deposition layer was 0.08 micrometer. Finally, an adhesive layer was formed on the metal vapor-deposited layer by applying vinyl acetate with a gravure printing method to obtain a transfer sheet.

  In addition, a decorative molded product was obtained by applying the molding simultaneous transfer method to the obtained transfer sheet. Therefore, (1) blocking resistance was evaluated for the transfer sheet, and (2) adhesion, (3) cracks, and (4) ink flow were evaluated for the decorative molded product. Evaluation methods are shown below, and the evaluation results are shown in Table 1.

〔Evaluation method〕
(1) Blocking resistance It measured about the blocking resistance of the transfer layer in a transfer sheet. The measuring method of blocking resistance was performed based on the blocking resistance described in 6.2.2 of JIS K5701-1. In addition, the blocking resistance evaluation of the said layer evaluated in either of the following.
○: When the transfer sheets are peeled off one by one from a plurality of superimposed transfer sheets, each transfer sheet is peeled off between the base sheet and the hard coat layer, and peeling between the transfer layers cannot be confirmed. It was.
×: When the transfer sheets are peeled off one by one from a plurality of the superimposed transfer sheets, each transfer sheet or a part of the transfer sheet is not peeled between the base sheet and the adhesive layer, and is peeled between the transfer layers. It was confirmed.

(2) Adhesiveness It measured about the adhesiveness in the design layer, uneven | corrugated formation layer, metal vapor deposition layer, and uneven | corrugated formation layer in a decorative molded product. The measuring method of adhesiveness was performed based on the cross-cut method described in JIS K5600-5-6. The adhesion between the transfer layers was evaluated by either of the following.
○: The edges of the cuts are completely smooth, and there is no peeling in any lattice eye.
(Triangle | delta): The small peeling could be confirmed to the coating film in the intersection of cut, and the peeling had generate | occur | produced between the transfer layers. Peeling was less than 5% of the cross-cut portion.
X: Small peeling was confirmed in the coating film at the intersection of the cuts, and the peeling occurred between the transfer layers. Peeling was 5% or more of the cross-cut portion.

(3) Crack The surface of the decorative molded product was observed using a microscope (trade name: Digital Microscope, model number: VHX-900) manufactured by Keyence Corporation. And the crack which generate | occur | produced in the shock absorption layer and the metal vapor deposition layer was measured.
○: No cracks could be confirmed in the decorative molded product (per 9 cm ² ).
△: During decorative molded article ⁽² per 9cm), the impact-absorbing layer and the metal deposition layer, respectively confirmed 1-2 cracks 1 to 4 [mu] m ^2.
X: In the decorative molded product (per 9 cm ² ), 3 or more cracks of 1 to 4 μm ² were confirmed for each of the impact absorbing layer and the metal deposition layer.

(4) Ink Flow The surface of the decorative molded product was observed using a microscope (trade name: Digital Microscope, model number: VHX-900) manufactured by Keyence Corporation. Then, the ink flow generated in the shock absorbing layer was measured. The ink flow of the impact absorbing layer was evaluated by either of the following.
○: Ink flow could not be confirmed in the shock absorbing layer.
Δ: One hole having a diameter of 1 mm ^{2 to} 9 mm ² or less was confirmed in the shock absorbing layer.
X: One hole exceeding a diameter of 9 mm ² was confirmed in the shock absorbing layer.

[Examples 2 to 6 and Comparative Examples 1 to 6]
A transfer sheet was produced in the same manner as in Example 1 except that the type of resin constituting the shock absorbing layer was changed as shown in Table 1. And the transfer sheet decoration molded product was created and various evaluation was carried out. The evaluation results are shown in Tables 1 and 2.

1: Transfer sheet 2: Substrate sheet 3: Transfer layer 4: Hard coat layer 5: Design layer 6: Protective layer 7: Concavity and convexity formation layer 8: Shock absorption layer 9: Metal vapor deposition layer 10: Adhesive layer 11: Molding resin 20: Transfer object 21: Roll transfer machine 22: Fixed mold 23: Movable mold 24: Molten resin
100: Decorative molded product

Claims (6)

In a transfer sheet comprising a transfer layer on a substrate sheet,
The transfer layer is
A concavo-convex forming layer comprising a plurality of convex portions formed on the base sheet, the shape of which is convex with respect to the direction in which the transfer layer of the base sheet is formed;
An impact absorbing layer formed on the base sheet and the concavo-convex forming layer;
A metal vapor deposition layer formed on the shock absorbing layer,
The shock absorbing layer is
Polymerization average molecular weight: 72000-77000,
Hydroxyl value: 8-15 mg KOH / g,
Glass transition temperature (Tg): 60 to 100 ° C.
The transfer sheet containing the acrylic polyol which is. A protective layer formed between the base sheet and the concavo-convex forming layer and between the base sheet and the shock absorbing layer;
The protective layer is
Polymerization average molecular weight: 70000-75000,
Hydroxyl value: 3-10 mg KOH / g,
Glass transition temperature (Tg): 80 to 120 ° C.
The transfer sheet according to claim 1, comprising an epoxymelamine which is 3. The transfer sheet according to claim 1, wherein the resin constituting the unevenness forming layer contains acrylate as a main component and a silane coupling agent represented by the following formula having a molecular weight of 100 to 500 is added.

(In the formula, R is an alkyl straight chain containing at least one of an epoxy group, a vinyl group, a methacryl group, a mercapto group, and a styryl group, and D is any one of OMe, OEt, OEtOMe, and OEtOEt. Me represents a methyl group, and Et represents an ethyl group.)   The transfer sheet according to claim 1, wherein the resin constituting the unevenness forming layer is made of the same resin as the shock absorbing layer.   The transfer sheet according to claim 1, wherein the resin constituting the unevenness forming layer is made of the same resin as the protective layer.   The transfer sheet according to any one of claims 1 to 5, wherein a size of the convex portion constituting the unevenness forming layer is 200 µm to 1000 µm in the width direction and 1 µm to 30 µm in the height direction.

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