JP5116900B1 - Transfer sheet to suppress ink flow - Google Patents

Abstract

A transfer sheet capable of suppressing ink flow in a pattern layer is provided.
A transfer sheet 1 of the present invention includes a base sheet 2, a design layer 4 formed on the base sheet 2, a first barrier layer 5 formed on the design layer, and the first sheet. A second barrier layer 6 formed on the first barrier layer 5, an anchor layer 7 formed on the second barrier layer 6, and an adhesive layer 8 formed on the anchor layer 7. The design layer 4 is made of polyurethane, and the first barrier layer 5 and the second barrier layer 6 are layers that protect the design layer 4 from heat generated during molding, and have a molecular weight of 100 to 500. An active energy ray-curable resin composition mainly composed of an acrylate to which a silane coupling agent represented by the following formula is added is a resin obtained by electron beam irradiation or light irradiation, and the anchor layer 7 is It comprised so that it might consist of polyurethane.
[Selection] Figure 1

Description

  The present invention relates to a transfer sheet, and more particularly to a transfer sheet that suppresses ink flow in a pattern layer.

  2. Description of the Related Art Conventionally, a method for protecting or decorating the surface of 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 a barrier layer is formed on a metal thin film. In addition, the said barrier layer has a role which protects a metal thin film from the heat pressure of resin inject | emitted from a metal mold | die at the time of shaping | molding, and prevents a metal thin film from flowing.

JP 2011-33296 A

  In the transfer sheet of Patent Document 1, it is described that a thermosetting resin is used for the barrier layer. However, it takes time to cure the resin as compared with an ultraviolet curable resin or an electron beam curable resin. Therefore, there is a problem that the production efficiency is poor as compared with the case where an ultraviolet curable resin or the like is used for the barrier layer. Further, when a thermosetting resin is used for the barrier layer, the resistance to the heat pressure of the resin is weaker than when an ultraviolet curable resin or an electron beam curable resin is used for the barrier layer. For this reason, when the above resin is used, the metal thin film cannot be completely protected from the heat pressure of the resin, and there is a problem that ink flow occurs in the metal thin film.

  However, when an ultraviolet curable resin or an electron beam curable resin is used for the barrier layer, peeling occurs between the metal thin film and the barrier layer when only the base sheet is peeled after being attached to the transfer target product. The cause is that an anchor layer that enhances adhesion is not formed between the metal thin film and the barrier layer. However, when an anchor layer is formed between the metal thin film and the barrier layer, the anchor layer is melted by the hot pressure of the molten resin at the time of molding, and this causes a problem that ink flow occurs in the metal thin film. This tendency is prominent when a pattern layer is used instead of the metal thin film.

  In addition, when an ultraviolet curable resin or an electron beam curable resin is used as the barrier layer, a plurality of barrier layers may be formed from the viewpoint of protecting the design layer. In such a case, after the barrier layer is formed once, the next barrier layer is formed. However, in such a case, the adhesion between the barrier layers is lowered. Therefore, there is a problem that peeling occurs between the barrier layers when only the base sheet is peeled off after being attached to the transfer target product.

  The present invention prevents delamination that occurs between barrier layers and between a barrier layer and a design layer in a transfer sheet in which a plurality of barrier layers made of an ultraviolet curable resin or an electron beam curable resin are formed on the design layer. In addition, an object is to provide a transfer sheet that can suppress ink flow in the design layer.

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

  Below, it demonstrates in detail based on embodiment concerning this invention.

式中のＲは、エポキシ基、ビニル基、メタクリル基、メルカプト基、スチリル基のいずれかを少なくとも１以上含むアルキル直鎖であり、Ｄは、ＯＭｅ、ＯＥｔ、ＯＥｔＯＭｅ、ＯＥｔＯＥｔのいずれか１つであり、Ｍｅはメチル基、Ｅｔはエチル基を示す。 The first aspect of the present invention is characterized in that a base sheet, a design layer formed on the base sheet, a first barrier layer formed on the design layer, and the first barrier layer A second barrier layer to be formed; an anchor layer formed on the second barrier layer; and an adhesive layer formed on the anchor layer, wherein the design layer is made of polyurethane, The first barrier layer and the second barrier layer are layers that protect the pattern layer from heat generated during molding, and an acrylate added with a silane coupling agent represented by the following formula having a molecular weight of 100 to 500 is added. It is a resin obtained by irradiating an active energy ray-curable resin composition as a main component with electron beam irradiation or light irradiation, and the anchor layer is made of polyurethane.

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.

  Here, when the silane coupling agent is added to the first barrier layer, the silane coupling agent reacts with the active energy ray-curable resin composition mainly composed of the acrylate of the first barrier layer. Similarly, in the second barrier layer, when a silane coupling agent is added to the second barrier layer, an active energy ray-curable resin composition mainly composed of the silane coupling agent and the acrylate of the second barrier layer is obtained. react. Here, the first barrier layer and the second barrier layer are in contact with each other. If it does so, the reaction materials obtained by the said reaction will interact, and the adhesiveness of a 1st barrier layer and a 2nd barrier layer will improve. As a result, delamination that occurs between the first barrier layer and the second barrier layer can be suppressed.

  Further, the first barrier layer and the design layer are in contact with each other. Therefore, in the first barrier layer to which the silane coupling agent is added, the reaction product obtained by reacting as described above is in contact with the design layer. If it does so, the polyurethane which comprises the reaction material and a design layer will interact, and the adhesiveness of a 1st barrier layer and a design layer will improve. As a result, delamination between the first barrier layer and the design layer can be suppressed.

  As a result of the improved adhesion between the first barrier layer and the design layer, it is not necessary to form an anchor layer between the first barrier layer and the design layer. As a result, ink flow in the design layer can be suppressed.

  Furthermore, according to this configuration, a silane coupling agent having a molecular weight of 100 to 500 is added to the first barrier layer and the second barrier layer containing acrylate as a main component, and irradiation with an electron beam or light is performed.

  By irradiating the first barrier layer and the second barrier layer with light irradiation, electron beam or light, the components of the first barrier layer and the second barrier layer react, and the hardness of the first barrier layer and the second barrier layer. Will improve. Then, when creating a decorative molded product using the transfer sheet, the design layer formed on the first barrier layer can be protected from the heat pressure of the resin. As a result, ink flow in the design layer can be suppressed.

  Furthermore, according to this configuration, the anchor layer made of polyurethane is formed on the second barrier layer. As described above, when the silane coupling agent is added to the second barrier layer, the active energy ray-curable resin composition mainly composed of the silane coupling agent and the acrylate of the second barrier layer reacts. Here, the second barrier layer and the anchor layer are in contact with each other. If it does so, the adhesiveness of a 2nd barrier layer and an anchor layer will improve by interaction with the polyurethane which comprises the said reaction material and an anchor layer. As a result, delamination between the second barrier layer and the anchor layer can be suppressed.

  Furthermore, an adhesive layer having good adhesion to the anchor layer is formed on the anchor layer. Therefore, when the transfer sheet is used for the transfer object and the base sheet is peeled from the transfer object, delamination between the layers can be suppressed.

式中のＲは、エポキシ基、ビニル基、メタクリル基、メルカプト基、スチリル基のいずれかを少なくとも１以上含むアルキル直鎖であり、Ｄは、ＯＭｅ、ＯＥｔ、ＯＥｔＯＭｅ、ＯＥｔＯＥｔのいずれか１つであり、Ｍｅはメチル基、Ｅｔはエチル基を示す。 The second aspect of the present invention is characterized by a first hard coat layer formed between the base sheet and the design layer, and a second hard coat formed between the first hard coat layer and the design layer. And the first hard coat layer and the second hard coat layer are layers that protect the surface of the transferred product, and are made of an active energy ray-curable resin composition mainly composed of acrylate. In the second hard coat layer, at least 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.

  According to this configuration, at least a silane coupling agent having a molecular weight of 100 to 500 is added to the second hard coat layer made of the active energy ray-curable resin composition containing acrylate as a main component.

  When at least the silane coupling agent is added to the second hard coat layer, the silane coupling agent and the active energy ray-curable resin composition mainly composed of the acrylate of the second hard coat layer react. Here, the first hard coat layer and the second hard coat layer are in contact with each other. Then, this reaction product interacts with the active energy ray-curable resin composition mainly composed of the acrylate of the first hard coat layer. As a result, since the adhesion between the first barrier layer and the second barrier layer is improved, delamination that occurs between the first hard coat layer and the second hard coat layer can be suppressed.

  Further, the second hard coat layer and the design layer are in contact with each other. Therefore, in the second hard coat layer to which the silane coupling agent is added, the reaction product obtained by reacting as described above is in contact with the design layer. If it does so, the polyurethane which comprises the reaction material and a design layer will interact, and the adhesiveness of a 2nd hard-coat layer and a design layer will improve. As a result, delamination between the second hard coat layer and the design layer can be suppressed.

  Further, as a result of improving the adhesion between the second hard coat layer and the design layer, it is not necessary to form an anchor layer between the second hard coat layer and the design layer. As a result, ink flow in the design layer can be suppressed.

  The design layer is sandwiched between the first barrier layer and the second hard coat layer. If it does so, since it becomes difficult to transmit the impact by the resin pressure to a design layer at the time of shaping | molding, the deformation | transformation of the design layer at the time of shaping | molding can be suppressed. As a result, the ink flow of the pattern layer generated by the resin pressure during molding can be further suppressed.

  The third aspect of the transfer sheet of the present invention is characterized in that the amount of the silane coupling agent added is 0.5 to 5.0 w% of the resin component in the first barrier layer or the second barrier layer. .

  When the addition amount of the silane coupling agent is less than 0.5 w% of the resin component in the first barrier layer or the second barrier layer, the adhesion between the first barrier layer and the second barrier layer is hardly improved. On the other hand, if the addition amount of the silane coupling agent exceeds 5.0 w%, the first barrier layer and the second barrier layer are gelled. Therefore, the first barrier layer and the second barrier layer should be appropriately laminated. Can not be. In view of the above points, the addition amount of the silane coupling agent is preferably 0.5 to 5.0 w% of the resin component in the first barrier layer or the second barrier layer according to the addition.

  A feature of the fourth aspect of the transfer sheet of the present invention is that the amount of the silane coupling agent added is 0.5 to 5.0 w% of the resin component in the second hard coat layer.

  When the addition amount of the silane coupling agent is less than 0.5 w% of the resin component in the second hard coat layer, the adhesion between the first hard coat layer and the second hard coat layer is hardly improved. On the other hand, when the addition amount of the silane coupling agent exceeds 5.0 w%, the second hard coat layer is gelled. Therefore, the second hard coat layer can be appropriately laminated on the first hard coat layer. become unable. In view of the above points, the amount of the silane coupling agent added is preferably 0.5 to 5.0 w% of the resin component in the second hard coat layer.

  The fifth aspect of the transfer sheet of the present invention is characterized in that the total thickness of the first barrier layer and the second barrier layer is 1 μm to 10 μm.

  When the total thickness of the first barrier layer and the second barrier layer is less than 1 μm, heat resistance is lost and ink flow occurs in the pattern layer. On the other hand, if the thickness exceeds 10 μm, blocking occurs. In view of the above points, the total thickness of the first barrier layer and the second barrier layer is preferably 1 to 10 μm.

  A feature of the sixth aspect of the transfer sheet of the present invention is that the total thickness of the first hard coat layer and the second hard coat layer is 1 μm to 10 μm.

  When the thickness is less than 1 μm, the wear resistance of the entire hard coat layer is weakened. On the other hand, if the thickness exceeds 10 μm, a blocking problem occurs.

  A feature of the seventh aspect of the transfer sheet of the present invention is that the base sheet is a resin sheet, a metal foil, a cellulosic sheet, or a composite of the sheets.

  When the base sheet is a resin sheet, a metal foil, a cellulosic sheet, or a composite of the above sheets, the adhesion between the first hard coat layer and the second hard coat layer is improved by the addition of the silane coupling agent. Combined with this, the peelability of the base sheet from the first hard coat layer is improved.

It is sectional drawing of the transfer sheet of 1st Embodiment. It is a figure which shows the manufacturing process of the molded article using the transfer sheet of this invention. It is a figure which shows the manufacturing process of the molded article using the transfer sheet of this invention. It is sectional drawing of the transfer sheet of 2nd Embodiment.

  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. Hereinafter, embodiments of the present invention will be described with reference to the drawings.

[First Embodiment]
[Transfer sheet]
FIG. 1 is a cross-sectional view showing the structure of a transfer sheet 1 according to this embodiment of the present invention. The transfer sheet 1 is provided with a transfer layer 3 on one side of a base sheet 2. The transfer layer 3 includes a pattern layer 4, a first barrier layer 5, a second barrier layer 6, an anchor layer 7, and an adhesive layer 8 that are sequentially stacked from the base sheet 2 side.

  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]
A base sheet is comprised from the sheet material or film material conventionally used for the use which supports a design layer etc. on a sheet | seat. 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.

[Transfer layer]
Referring to FIG. 1 again, the transfer layer 3 is a layer provided on one side of the base sheet 2 and transferred from the base sheet 2 to the surface of the transfer target. The transfer layer 3 includes a pattern layer 4, a first barrier layer 5, a second barrier layer 6, an anchor layer 7, and an adhesive layer 8 that are sequentially stacked from the base sheet 2 side.

<Design layer>
The design layer is a layer that is arranged on the surface of the molded product and decorates the molded product. As the material of the pattern layer, a resin such as polyvinyl, polyamide, polyacryl, polyurethane, polyvinyl acetal, polyester urethane, cellulose ester, alkyd resin is used as a binder, and a colored ink containing an appropriate color pigment or dye as a colorant is used. Use it. 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. Among the binders constituting the design layer, it is preferable to use polyurethane. This is because when polyurethane is used as the binder constituting the design layer, the polyurethane and a resin constituting the first barrier layer described later interact to improve the adhesion between the design layer and the first barrier layer.

  As a pattern layer forming method, a normal printing method such as an offset printing method, a gravure printing method, or a screen printing method may be used. In particular, the offset printing method and the gravure printing method are suitable for performing multicolor printing and gradation expression. In the case of a single color, a coating method such as a gravure coating method, a roll coating method, or a comma coating method may be employed.

<First barrier layer, second barrier layer>
The first barrier layer and the second barrier layer are heat-resistant layers for protecting the pattern layer from ink flow when a transfer sheet is placed in a mold and a resin is injected from the mold. Have.

  Examples of the material of the first barrier layer and the second barrier layer include ionizing radiation curable resins such as acrylate. As the acrylate, polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, melamine (meth) acrylate, triazine acrylate, epoxy-modified (meth) A composition in which a polymerization initiator or a sensitizer is added to an appropriate mixture of an unsaturated ethylene oligomer such as an acrylate, urethane-modified (meth) acrylate, or (meth) acryl-modified polyester or an unsaturated ethylene monomer is used. You can also.

  Moreover, as a material of a 1st barrier layer and a 2nd barrier layer, what has a (meth) acryloyl group which is a compound which has a reactive double bond 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.

  In addition, although it mentioned above about resin which comprises a 1st barrier layer and a 2nd barrier layer, it is preferable to use the same resin material for a 1st barrier layer and a 2nd barrier layer. When the resin material of the first barrier layer and the resin material of the second barrier layer are the same, the adhesion between them is improved.

  The polymer constituting the resin of the first barrier layer and the second barrier layer has a specific blending amount in consideration of the physical and chemical performance requirements 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 thermal crosslinking degree of the first barrier layer and the second barrier layer of the transfer sheet 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 first barrier layer and the second barrier layer of the transfer sheet, and solvent resistance is insufficient. There are disadvantages such as making it difficult to obtain clear pictures. 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 first barrier layer and the second barrier layer are laminated on the pattern layer, the first barrier layer and the second barrier before irradiation with active energy rays are used. This is because the adhesiveness of the layer is kept low and the resistance to the solvent contained in the ink is satisfied to some extent when forming the pattern layer or the adhesive layer. 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 first barrier layer and the second barrier layer can contain the following components as needed in addition to the polymer and the polyfunctional isocyanate. 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 first barrier layer and the second barrier layer may be colored or uncolored.

  The active energy ray-curable resin composition used for the first barrier layer and the second barrier layer may contain a lubricant as necessary. This is because the surfaces of the first barrier layer and the second barrier layer are roughened, so that the first barrier layer and the second barrier layer are easily wound as a sheet, and blocking is hardly generated. In addition, resistance to rubbing and scratching can be increased. As the lubricant, for example, waxes such as polyethylene wax, paraffin wax, synthetic wax and montan wax, and synthetic resins such as silicone and fluorine can be used. The lubricant is contained in an amount of 0.5 to 15% by weight, preferably 1 to 6% by weight. When the amount of the lubricant is less than 0.5% by weight, the effects of blocking prevention and friction scratch resistance are reduced, and when it exceeds 15% by weight, the transparency of the first barrier layer and the second barrier layer is extremely deteriorated.

  The active energy ray-curable resin composition used for the first barrier layer and the second barrier layer 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 first barrier layer and the second barrier layer is crosslinked by both heat and active energy rays.

ここで、式中のＲは、エポキシ基、ビニル基、メタクリル基、メルカプト基、スチリル基のいずれかを少なくとも１以上含むアルキル直鎖であり、Ｄは、ＯＭｅ、ＯＥｔ、ＯＥｔＯＭｅ、ＯＥｔＯＥｔのいずれか１つである。Ｍｅはメチル基、Ｅｔはエチル基を示す。 A silane coupling agent represented by the following chemical formula is added to the first barrier layer and the second barrier layer.

Here, 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. One. Me represents a methyl group, and Et represents an ethyl group.

  Here, when the silane coupling agent is added to the first barrier layer, the silane coupling agent reacts with the active energy ray-curable resin composition mainly composed of the acrylate of the first barrier layer. Similarly, in the second barrier layer, when a silane coupling agent is added to the second barrier layer, an active energy ray-curable resin composition mainly composed of the silane coupling agent and the acrylate of the second barrier layer is obtained. react. Here, the first barrier layer and the second barrier layer are in contact with each other. If it does so, the reaction materials obtained by the said reaction will interact, and the adhesiveness of a 1st barrier layer and a 2nd barrier layer will improve. As a result, delamination that occurs between the first barrier layer and the second barrier layer can be suppressed.

  Further, the first barrier layer and the design layer are in contact with each other. Therefore, in the first barrier layer to which the silane coupling agent is added, the reaction product obtained by reacting as described above is in contact with the design layer. If it does so, the polyurethane which comprises the reaction material and a design layer will interact, and the adhesiveness of a 1st barrier layer and a design layer will improve. As a result, delamination between the first barrier layer and the design layer can be suppressed.

  Further, as a result of improving the adhesion between the first barrier layer and the design layer, it is not necessary to form an anchor layer between the first barrier layer and the design layer. As a result, ink flow in the design layer can be suppressed.

  The addition amount of the silane coupling agent is preferably 0.5 to 5.0 w% of the resin component in the first barrier layer or the second barrier layer. When the addition amount of the silane coupling agent is less than 0.5 w% of the resin component in the first barrier layer and the second barrier layer, the adhesion between the first barrier layer and the second barrier layer is hardly improved. On the other hand, if the addition amount of the silane coupling agent exceeds 5.0 w%, the first and second barrier layers are gelled, so that the first barrier layer and the second barrier layer can be appropriately laminated. Disappear.

  If the third barrier layer to which the silane coupling agent is added is formed on the second barrier layer after the adhesion between the layers is improved, the adhesion between the second barrier layer and the third barrier layer is increased. Property is improved, and delamination between them can be suppressed. As a result, a plurality of barrier layers can be formed, and the hardness of the entire barrier layer becomes very high.

  In addition, it is preferable that the sum total of the thickness of a 1st barrier layer and a 2nd barrier layer is 1 micrometer-10 micrometers. When the thickness is less than 1 μm, the heat resistance is lost and ink flow occurs in the pattern layer. On the other hand, if the total thickness exceeds 10 μm, blocking occurs. In view of the above points, the total thickness is preferably 1 μm to 10 μm.

  Moreover, the hardness of a 1st barrier layer and a 2nd barrier layer improves by irradiating light irradiation or an electron beam to a 1st barrier layer and a 2nd barrier layer. Then, when creating a decorative molded product using the transfer sheet, the pattern layer formed on the first barrier layer can be protected from the thermal pressure of the resin injected from the mold. As a result, ink flow in the design layer can be suppressed.

<Anchor layer>
The anchor layer is formed between the second barrier layer and the adhesive layer in order to improve the adhesion between the second barrier layer and the adhesive layer. That is, the anchor layer prevents delamination that occurs between the second barrier layer and the adhesive layer. As the material of the anchor layer, polyurethane, melamine resin, cellulose ester resin, chlorine-containing rubber resin, chlorine-containing vinyl resin, acrylic resin, epoxy resin, vinyl copolymer resin, etc. can be used. It is preferable to use it.

  Here, when the silane coupling agent is added to the second barrier layer, the active energy ray-curable resin composition containing the silane coupling agent and the acrylate of the second barrier layer as main components reacts. Here, the second barrier layer and the anchor layer are in contact with each other. If it does so, the adhesiveness of a 2nd barrier layer and an anchor layer will improve by interaction with the polyurethane which comprises the said reaction material and an anchor layer. As a result, delamination between the second barrier layer and the anchor layer can be suppressed.

  Moreover, it is because the adhesiveness with the below-mentioned contact bonding layer is high compared with the case where other resin is used. Therefore, when polyurethane is used for the anchor layer, it is possible to suppress delamination that occurs between the second barrier layer and the anchor layer and between the anchor layer and the adhesive layer when the base sheet is peeled from the transfer target.

<Adhesive layer>
If necessary, the adhesive layer is provided on the surface of the transfer layer closest to the transfer target. The adhesive layer adheres the transfer layer 3 and the transfer object during transfer. As the adhesive layer, a heat-sensitive or pressure-sensitive resin suitable for the transfer target is appropriately used. For example, when the material of the transfer object is an acrylic resin, an acrylic resin may be used.

  In addition, when the material of the transferred material is polyphenylene oxide / polystyrene resin, polycarbonate resin, styrene copolymer resin, or polystyrene blend resin, acrylic resin, polystyrene resin, polyamide having an affinity for these resins A series resin or the like may be used. Furthermore, when the material of the decoration object is polypropylene resin, chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, and coumarone indene resin can be used.

  Further, a release layer may be further formed between the base sheet and the transfer layer. The release layer may be separated from the transfer layer together with the base sheet during transfer, or may be separated from the base sheet to form the outermost surface of the transfer layer. As the material of the release layer, melamine resin, silicone resin, fluorine resin, cellulose derivative, urea resin, polyolefin resin, paraffin resin, and composites thereof can be used.

[Transfer sheet manufacturing method]
Below, the manufacturing method of the transfer sheet of this invention is demonstrated. The transfer sheet of the present invention is produced in the same manner as a conventional transfer sheet except that a silane coupling agent is added to the first barrier layer and the second barrier layer of the transfer layer.

  For example, a base sheet is prepared, and layers constituting the transfer layer are sequentially formed on one side thereof. As described above, the layers constituting the transfer layer are a pattern layer, a first barrier layer, a second barrier layer, an anchor layer, and an adhesive layer. If necessary, a release layer is formed on the surface of the base sheet that is in contact with the transfer layer.

[Transfer method to article]
Next, a method for producing a decorative molded product using the transfer sheet of the present invention will be described. FIG. 2 is a cross-sectional view when a decorative molded product is manufactured using the transfer sheet and transfer machine of the present invention. FIG. 3 is a cross-sectional view when a decorative molded product is manufactured using the transfer sheet of the present invention for in-mold molding. As shown in FIG. 2, when a transfer machine is used, the transfer layer 3 side (opposite side of the base sheet 2) of the transfer sheet is superimposed on the surface of the transfer target 20, and a roll transfer machine, an up-down transfer machine, etc. Using the transfer machine 21, heat and pressure are applied from the substrate sheet 2 side of the transfer sheet 1. 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

  As shown in FIG. 3, in the in-mold molding, 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).

[Second Embodiment]
FIG. 4 is a cross-sectional view of a transfer sheet according to the second embodiment. As shown in FIG. 4, in this embodiment, the transfer layer 3 includes, in order from the base sheet 2 side, the first hard coat layer 9, the second hard coat layer 10, the design layer 4, the first barrier layer 5, 2 having a barrier layer 6, an anchor layer 7, and an adhesive layer 8.

<First hard coat layer / second hard coat layer>
The first hard coat layer and the second hard coat layer are disposed on the surface of the transfer target when the substrate sheet is peeled off from the transfer target after the transfer, and have a certain hardness or more to protect the transfer target. have. The polymer used for the first hard coat layer and the second hard coat layer, the polyfunctional isocyanate, and the production method thereof are the same as those shown for the first barrier layer and the second barrier layer, respectively. In addition, it is preferable to use the same resin material for the first hard coat layer and the second hard coat layer. When the resin materials of the first hard coat layer and the second hard coat layer are the same, the adhesion between them is improved.

ここで、式中のＲは、エポキシ基、ビニル基、メタクリル基、メルカプト基、スチリル基のいずれかを少なくとも１以上含むアルキル直鎖であり、Ｄは、ＯＭｅ、ＯＥｔ、ＯＥｔＯＭｅ、ＯＥｔＯＥｔのいずれか１つである。Ｍｅはメチル基、Ｅｔはエチル基を示す。 A silane coupling agent represented by the following chemical formula is added to the second hard coat layer.

Here, 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. One. Me represents a methyl group, and Et represents an ethyl group.

  When at least the silane coupling agent is added to the second hard coat layer, the silane coupling agent and the active energy ray-curable resin composition mainly composed of the acrylate of the second hard coat layer react. Here, the first hard coat layer and the second hard coat layer are in contact with each other. Then, this reaction product interacts with the active energy ray-curable resin composition mainly composed of the acrylate of the first hard coat layer. As a result, since the adhesion between the first barrier layer and the second barrier layer is improved, delamination that occurs between the first hard coat layer and the second hard coat layer can be suppressed.

  Further, the second hard coat layer and the design layer are in contact with each other. Therefore, in the second hard coat layer to which the silane coupling agent is added, the reaction product obtained by reacting as described above is in contact with the design layer. If it does so, the polyurethane which comprises the reaction material and a design layer will interact, and the adhesiveness of a 2nd hard-coat layer and a design layer will improve. As a result, delamination between the second hard coat layer and the design layer can be suppressed.

  Further, as a result of improving the adhesion between the second hard coat layer and the design layer, it is not necessary to form an anchor layer between the second hard coat layer and the design layer. As a result, ink flow in the design layer can be suppressed.

  The addition amount of the silane coupling agent is preferably 0.5 to 5.0 w% of the resin component in the second hard coat layer. When the addition amount of the silane coupling agent is less than 0.5 w% of the resin component in the second hard coat layer, the adhesion between the second hard coat layer and the first hard coat layer is hardly improved. On the other hand, when the addition amount of the silane coupling agent exceeds 5.0 w%, the second hard coat layer is gelled. Therefore, the second hard coat layer can be appropriately laminated on the first hard coat layer. become unable.

  When a silane coupling agent having a molecular weight of 100 to 500 is added to the second hard coat layer, in the second hard coat layer, an active energy ray curable resin mainly composed of the silane coupling agent and the acrylate of the second hard coat layer The composition reacts. The reactant is in contact with the design layer. And the adhesiveness of a 2nd hard-coat layer and a design layer improves by interaction with this reaction material and the polyurethane resin which comprises a design layer. As a result, delamination between the second hard coat layer and the design layer can be prevented.

  Further, as a result of improving the adhesion between the second hard coat layer and the design layer, it is not necessary to form an anchor layer between the second hard coat layer and the design layer. As a result, it is possible to suppress the ink flowing in the pattern layer generated by the resin pressure during molding.

  Furthermore, the design layer is sandwiched between the first barrier layer and the second hard coat layer. As a result, since the impact due to the resin pressure is less likely to be transmitted to the design layer during molding, deformation of the design layer during molding can be suppressed. As a result, the ink flow in the design layer can be suppressed by the resin pressure generated during molding.

  After the adhesion between the first hard coat layer and the second hard coat layer is improved, a third hard coat is formed on the first hard coat layer by adding a silane coupling agent to the first hard coat layer. Even if the layer is formed, delamination between the first hard coat layer and the third hard coat layer can be suppressed. Thus, when a plurality of hard coat layers are formed, the hardness of the entire hard coat layer becomes very high.

  Further, when the base sheet is a resin sheet, a metal foil, a cellulosic sheet, or a composite of each of the above sheets, the adhesion between the first hard coat layer and the second hard coat layer is increased by the addition of the silane coupling agent. Combined with the improvement, the peelability of the base sheet from the first hard coat layer is improved.

  In addition, when the first hard coat layer, the second hard coat layer, the design layer, the first barrier layer, and the second barrier layer are exposed to an environment where the laminated transfer sheet is humid or alcohol is used, water is applied to the design layer. If alcohol or alcohol enters, the design layer may swell and the shape of the design constituting the design layer may be impaired.

  However, when the design layer is sandwiched between the first barrier layer to which the silane coupling agent is added and the second hard coat layer as in this configuration, the adhesion between the first barrier layer and the design layer, and the second Adhesion between the hard coat layer and the design layer is improved. Thereby, the design layer is reliably protected by the first barrier layer and the second hard coat layer.

  The total thickness of the first hard coat layer and the second hard coat layer is preferably 1 μm to 10 μm. When the thickness is less than 1 μm, the wear resistance and chemical resistance of the entire hard coat layer are weakened. On the contrary, if the thickness exceeds 10 μm, a blocking problem occurs.

  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 with a thickness of 38 μm was used as a base sheet, and a release layer was formed on the base sheet by applying a melamine resin release agent to a thickness of 1 μm by a gravure printing method. Polyurethane was applied to the film by a gravure printing method to form a pattern layer. Furthermore, 200 parts of the following varnish A (solid content 100 parts), 1,6-hexane diisocyanate trimer (trade name Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.), photopolymerization initiator (trade name Irgacure 184, A first barrier layer containing 5 parts of Ciba Geigy Co., Ltd. and 1 part of vinyltrimethoxysilane (silane coupling agent, product name KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.) was formed by a gravure printing method. The thickness of the first barrier layer was 4 μm. Furthermore, the first barrier layer was half-crosslinked and cured by heating at 150 ° C. for 20 seconds. On the first barrier layer, 200 parts of the following varnish A (solid content 100 parts), 1,6-hexane diisocyanate trimer ( Product name Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd. 5 parts, photopolymerization initiator (trade name Irgacure 184, manufactured by Ciba Geigy) and vinyltrimethoxysilane (silane coupling agent, product name KBM-1003, Shin-Etsu) The 2nd barrier layer which mix | blended 1 part of Chemical Industry Co., Ltd. was formed with the gravure printing method. The thickness of the second barrier layer was 4 μm. The second barrier layer was half-crosslinked and cured by heating at 150 ° C. for 20 seconds, and formed on the second barrier layer using polyurethane as the anchor layer and acrylic resin as the adhesive layer to obtain a transfer sheet. Each layer was formed using a gravure printing method.

  Varnish A was obtained as follows. First, 175 parts of glycidyl methacrylate (hereinafter referred to as GMA), 75 parts of methyl methacrylate (hereinafter referred to as MMA), 1.3 parts of lauryl mercaptan are added to a reactor equipped with a stirrer, a cooling pipe, a dropping funnel and a nitrogen introduction pipe. After charging 1,000 parts of butyl acetate and 7.5 parts of 2,2′-azobisisobutyronitrile (hereinafter referred to as AIBN), the system temperature is about 90 ° C. over about 1 hour under a nitrogen stream. The temperature was raised to 1, and the temperature was kept for 1 hour. Next, the mixture was dropped into the system in about 2 hours under a nitrogen stream from a dropping funnel previously charged with a mixture consisting of 525 parts of GMA, 225 parts of MMA, 3.7 parts of lauryl mercaptan and 22.5 parts of AIBN. After keeping the same temperature for 3 hours, 10 parts of AIBN was charged and kept warm for 1 hour. Then, it heated up at 120 degreeC and heat-retained for 2 hours. After cooling to 60 ° C, the nitrogen inlet tube was replaced with an air inlet tube, 355 parts of acrylic acid (hereinafter referred to as AA), 2.0 parts of methoquinone and 5.4 parts of triphenylphosphine were charged and mixed, and then under air bubbling The temperature was raised to 110 ° C. After incubating at the same temperature for 8 hours, 1.4 parts of methoquinone was added and cooled, and ethyl acetate was added so that the non-volatile content was 50% to obtain varnish A. The polymer contained in varnish A had an acrylic equivalent of 270 g / eq, a hydroxyl value of 204, and a weight average molecular weight of 18000 (based on styrene conversion by GPC).

  The transfer sheet was transferred to the surface of the molded product using a simultaneous molding transfer method, and then the base sheet was peeled off, and the first barrier layer and the second barrier layer were completely crosslinked and cured by irradiation with ultraviolet rays. In the following evaluation methods (1) to (3), the molding conditions are a resin temperature of 240 ° C., a mold temperature of 55 ° C., a resin pressure of about 300 kg / cm 2, and an acrylic resin is used as the molding resin, and the length is 95 mm. A tray-shaped molded product (decorative molded product) having a width of 65 mm, a rise of 4.5 mm, and a corner portion of R2.5 mm was prepared and evaluated in various ways. In addition, regarding the ink flow evaluation method of (4) below, the molding conditions are a resin temperature of 240 ° C., a mold temperature of 50 ° C., a resin pressure of about 300 kg / cm 2, and a polycarbonate resin is used as the molding resin. A plate-shaped molded product (decorative molded product) having a width of 50 mm and a width of 0.7 mm was prepared and evaluated. In either case, the irradiation conditions were 120 w / cm, 6 lamps, a lamp height of 10 cm, and a belt speed of 15 m / min. The evaluation results are shown in Table 1.

[Examples 2 to 10 and Comparative Examples 1 to 10]
The first barrier layer resin, the second barrier layer resin, the type and amount of the silane coupling agent, and the total thickness of the first barrier layer and the second barrier layer were changed as shown in Table 1 A transfer sheet was prepared in the same manner as in Example 1, a transferred molded product (decorated molded product) was obtained, and various evaluations were performed. The evaluation results are shown in Table 1.

〔Evaluation method〕

(1) Adhesiveness (cross cut)
It measured about the adhesiveness in a decorative molded product. The measuring method of adhesiveness was performed based on the cross-cut method described in JIS K5600-5-6. In addition, the said adhesion evaluation between the layers evaluated in 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 was able to be confirmed to the coating film in the intersection of cut. Peeling was less than 5% of the cross-cut portion.
X: Small peeling was confirmed in the coating film at the intersection of cuts. Peeling was 5% or more of the cross-cut portion.

(2) Blocking resistance It measured about the blocking resistance of 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 were peeled off one by one from the plurality of transfer sheets that were superimposed, each transfer sheet was peeled between the base sheet and the adhesive layer, and peeling at other locations could not be confirmed.
×: When the transfer sheets are peeled off one by one from a plurality of superimposed transfer sheets, each transfer sheet or a part of the transfer sheet is not peeled between the base sheet and the adhesive layer, Peeling was confirmed.

(3) Alcohol resistance The decorative molded article was immersed in a methanol solution for 10 minutes and then naturally dried for 60 minutes. Next, the decorative molded product that had been naturally dried was tested in accordance with the cross-cut method described in JIS K5600-5-6. In addition, in accordance with the above results, the evaluation was performed in any of the following.
○: The edge of the cut was completely smooth, and no peeling was confirmed in any lattice eye.
(Triangle | delta): The small peeling was able to be confirmed to the coating film in the intersection of cut. Peeling was less than 30% of the cross-cut portion.
X: Small peeling was confirmed in the coating film at the intersection of cuts. Peeling was 30% or more of the cross-cut portion.

(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. And the ink flow which generate | occur | produced in the pattern layer was measured. The ink flow in the pattern layer was evaluated by either of the following.
○: One hole having a diameter of 3.5 mm or less was confirmed on the surface of the decorative molded product.
Δ: One hole having a diameter of 3.5 mm to 4.5 mm or less was confirmed on the surface of the decorative molded product.
X: One hole exceeding 4.5 mm in diameter was confirmed on the surface of the decorative molded product.

〔Evaluation results〕

  The following is clear from the evaluation results in Table 1. In Examples 1 to 9 in which the silane coupling agent was added to the first barrier layer and the second barrier layer in a polymer ratio of 0.5 to 5.0 w%, the adhesion, alcohol resistance, and ink flow were generally good. Excellent blocking resistance. On the other hand, Comparative Example 1 in which the silane coupling agent is not added to the first barrier layer does not provide satisfactory results in adhesion and alcohol resistance.

  In Comparative Example 2 in which the molecular weight of the silane coupling agent exceeds 500, satisfactory results cannot be obtained in adhesion, blocking resistance, and alcohol resistance. In Comparative Example 3 in which the molecular weight of the silane coupling agent is less than 100, the first The barrier layer coating process itself could not be performed.

  In Comparative Examples 4 and 5 in which the same silane coupling agent as in Examples 1 to 4 was added to the first barrier layer, Comparative Example 4 in which the amount of the silane coupling agent was too small was satisfactory in adhesion and alcohol resistance. In Comparative Example 5 in which the amount of the silane coupling agent was excessive, the first barrier layer coating process itself could not be performed.

  Moreover, in the comparative examples 6-8 which added the silane coupling agent which uses aminosilane, ureidosilane, and isocyanatesilane as a functional group, the coating process of the 1st barrier layer was not able to be performed.

  Further, in Comparative Example 9 in which the total thickness of the first barrier layer and the second barrier layer is 0.5 μm or less, satisfactory results with respect to the ink flow cannot be obtained, and the first barrier layer and the second barrier layer In Comparative Example 11 in which the total thickness was 10 μm or more, satisfactory results were not obtained with respect to blocking resistance.

  In Comparative Example 10 using hydrochloric acid-vinyl acetate instead of polyurethane as the resin used for the pattern layer, satisfactory results were not obtained with respect to adhesion, alcohol resistance, and ink flow.

[Example of Embodiment 2]
[Example 1]
A polyester resin film having a thickness of 38 μm was used as a base sheet, and a release layer was formed on the base sheet by applying a melamine resin release agent to a thickness of 1 μm by a gravure printing method. Then, 200 parts of the following varnish A (solid content 100 parts), 1,6-hexane diisocyanate trimer (trade name Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.), photopolymerization initiator (product) The first hard coat layer containing 5 parts of Irgacure 184, manufactured by Ciba-Geigy Co., Ltd. and 1 part of vinyltrimethoxysilane (silane coupling agent, product name KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.) was obtained by gravure printing. Formed. The thickness of the first hard coat layer was 0.7 μm. Furthermore, the first hard coat layer was half-crosslinked and cured by heating at 150 ° C. for 20 seconds. On the first hard coat layer, 200 parts of the following varnish A (solid content 100 parts), 1,6-hexane diisocyanate 3 amount Body (trade name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.), photopolymerization initiator (trade name: Irgacure 184, manufactured by Ciba Geigy) and vinyltrimethoxysilane (silane coupling agent, product name: KBM-1003) A second hard coat layer containing 1 part of Shin-Etsu Chemical Co., Ltd. was formed by a gravure printing method. The thickness of the second hard coat layer was 4 μm. The second hard coat layer was half-crosslinked and cured by heating at 150 ° C. for 20 seconds to form a second hard coat layer. On the second hard coat layer, a polyurethane resin was applied by a gravure printing method to form a pattern layer. On the pattern layer, 200 parts of the above varnish A (solid part 100 parts), 1,6-hexane diisocyanate trimer (trade name Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.), photopolymerization initiator (trade name Irgacure) The 1st barrier layer which mix | blended 5 parts of 184, the Ciba Geigy company) and 1 part of vinyl trimethoxysilane (a silane coupling agent, brand name KBM-1003, Shin-Etsu Chemical Co., Ltd.) was formed by the gravure printing method. The thickness of the first barrier layer was 4 μm. Furthermore, the first barrier layer was half-crosslinked and cured by heating at 150 ° C. for 20 seconds. On the first barrier layer, 200 parts of the following varnish A (solid content 100 parts), 1,6-hexane diisocyanate trimer ( Product name Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd. 5 parts and photopolymerization initiator (trade name Irgacure 184, manufactured by Ciba Geigy) and vinyltrimethoxysilane (silane coupling agent, product name KBM-1003, Shin-Etsu) The 2nd barrier layer which mix | blended 1 part) was formed with the gravure printing method. The thickness of the second barrier layer was 0.7 μm. The second barrier layer was half-crosslinked and cured by heating at 150 ° C. for 20 seconds, and polyurethane was used as the anchor layer and acrylic resin was used as the adhesive layer on the second barrier layer to obtain a transfer sheet. Each layer was formed using a gravure printing method.

  The transfer sheet was transferred to the surface of the molded product using a simultaneous molding transfer method, and then the base sheet was peeled off, and the first barrier layer and the second barrier layer were completely crosslinked and cured by irradiation with ultraviolet rays. In addition, about molding conditions, resin used, and irradiation conditions (hereinafter referred to as molding conditions and the like) of molded products (decorated molded products) created for evaluating the following (1) to (5), Embodiment 1 This is the same as the case of the molding conditions and the like of the molded product prepared for evaluating (1) to (3). The molding conditions and the like of the molded product created to evaluate (6) are the same as the molding conditions and the like of the molded product created to evaluate (4) of the first embodiment. The evaluation results are shown in Table 2.

[Examples 2 to 10 and Comparative Examples 1 to 10]
A transfer sheet was prepared in the same manner as in Example 1 except that the hard coat layer resin, the type and addition amount of the silane coupling agent, and the pattern layer resin were changed as shown in Table 2. (Decorated molded product) was obtained and subjected to various evaluations. The evaluation results are shown in Table 2.

〔Evaluation methods〕
(1) Pencil hardness As a hardness evaluation of the entire barrier layer (a combination of the first barrier layer and the second barrier layer) and the entire hard coat layer (a combination of the first hard coat layer and the second hard coat layer), The pencil hardness of the decorative molded product was measured by a method based on JIS K 5400.

(2) Adhesiveness (cross cut)
The adhesion between the first hard coat layer, the second hard coat layer, the design layer, the first barrier layer, and the second barrier layer (hereinafter referred to as transfer layer) in the decorative molded product was measured. 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) 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 were peeled off one by one from a plurality of superimposed transfer sheets, each transfer sheet was peeled off between the base sheet and the adhesive layer, and peeling between the transfer layers could not be confirmed. .
×: 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.

(4) Alcohol resistance The decorated molded article was immersed in a methanol solution for 10 minutes and then naturally dried for 60 minutes. Next, the decorative molded product that had been naturally dried was tested in accordance with the cross-cut method described in JIS K5600-5-6. In addition, in accordance with the above results, the evaluation was performed in any of the following.
○: The edges of the cut are completely smooth, and there is no peeling in the eyes of any lattice.
(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 30% 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 30% or more of the cross-cut portion.

(5) Wear resistance In accordance with JIS K7204, using a Taber friction tester (wear wheel: CS-10, load: 1 Kg / arm, rotation speed: 500 rotations) manufactured by Yasuda Seiki Seisakusho Co., Ltd. The surface of the molded product was rubbed. Then, the number of rotations of the wear wheel until the transfer layer was worn and penetrated was measured. The abrasion resistance of the transfer layer was evaluated by either of the following.
○: It took 1000 or more revolutions to penetrate.
Δ: It took 500 to 1000 revolutions to penetrate.
X: The number of rotations of less than 500 was required to penetrate.

(6) 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. And the ink flow which generate | occur | produced in the pattern layer was measured. The ink flow in the pattern layer was evaluated by either of the following.
○: One hole having a diameter of 3.5 mm or less was confirmed on the surface of the decorative molded product.
Δ: One hole having a diameter of 3.5 mm to 4.5 mm or less was confirmed on the surface of the decorative molded product.
X: One hole exceeding 4.5 mm in diameter was confirmed on the surface of the decorative molded product.

〔Evaluation results〕

  The following is clear from the evaluation results in Table 2. In Examples 1 to 9 in which a silane coupling agent was added to the second hard coat layer, the first barrier layer, and the second barrier layer in a polymer ratio of 0.5 to 5.0 w%, the pencil hardness was 2H or more, Abrasion resistance, adhesion, and ink flow are generally good, and blocking resistance and alcohol resistance are excellent.

  On the other hand, in Comparative Example 1 in which no silane coupling agent was added to the second hard coat layer, the first barrier layer, and the second barrier layer, satisfactory results were not obtained in alcohol resistance and adhesion. .

  In Comparative Example 2 in which the molecular weight of the silane coupling agent exceeds 500, satisfactory results cannot be obtained in adhesion, blocking resistance, and alcohol resistance. In Comparative Example 3 in which the molecular weight of the silane coupling agent is less than 100, the first The coating process itself of the hard coat layer and the first barrier layer could not be performed.

  In Comparative Examples 4, 5, and 9 in which the same silane coupling agent as in Examples 1 to 3 was added to the second hard coat layer, the first barrier layer, and the second barrier layer, the amount of the silane coupling agent was too small. In Comparative Example 4, satisfactory results in adhesion and alcohol resistance were not obtained, and in Comparative Example 5 in which the amount of the silane coupling agent was excessive, the coating process of the hard coat layer itself could not be performed. In Comparative Example 9, even when the amount of the silane coupling agent was substantially the same as in Example 2, when the pattern layer was a hydrochloric acid-vinyl acetate resin alone, satisfactory results were obtained in adhesion, alcohol resistance, and ink flow. I couldn't. In Comparative Example 10, even when the amount of the silane coupling agent was substantially the same as in Example 2, when the anchor layer was a hydrochloric acid-vinyl acetate resin alone, satisfactory results were not obtained in adhesion.

  Moreover, in the comparative examples 6-8 which added the silane coupling agent which uses aminosilane, ureidosilane, and isocyanatesilane as a functional group, the coating process of the hard-coat layer was not able to be performed.

  Further, in Comparative Example 11 in which the total thickness of the first hard coat layer and the second hard coat layer is 10 μm or more, a satisfactory result with respect to blocking resistance is not obtained, and conversely, the total thickness is 0.5 μm. In Comparative Example 12, which is less than the above, satisfactory results with respect to wear resistance were not obtained.

1: transfer sheet 2: base sheet 3: transfer layer 4: design layer 5: first barrier layer 6: second barrier layer 7: anchor layer 8: adhesive layer 9: first hard coat layer 10: second hard coat layer 20: Transfer object 21: Transfer machine 22: Fixed mold 23: Movable mold 24: Molten resin

Claims (7)

A base sheet;
A pattern layer formed on the base sheet;
A first barrier layer formed on the design layer;
A second barrier layer formed on the first barrier layer;
An anchor layer formed on the second barrier layer;
An adhesive layer formed on the anchor layer,
The pattern layer is made of polyurethane,
The first barrier layer and the second barrier layer are layers that protect the pattern layer from heat generated during molding, and an acrylate added with a silane coupling agent represented by the following formula having a molecular weight of 100 to 500 Is a resin obtained by irradiating an active energy ray-curable resin composition having a main component with electron beam irradiation or light irradiation,
A transfer sheet in which the anchor layer is made of polyurethane.

(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.) A first hard coat layer formed between the base sheet and the pattern layer;
A second hard coat layer formed between the first hard coat layer and the design layer,
The first hard coat layer and the second hard coat layer are layers for protecting the surface of the article to be transferred, and are composed of an active energy ray-curable resin composition containing acrylate as a main component, and the second hard coat layer The transfer sheet according to claim 1, wherein at least a silane coupling agent represented by the following formula having a molecular weight of 100 to 500 is added to the layer.

(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 or 2, wherein the addition amount of the silane coupling agent is 0.5 to 5.0 w% of the resin component in the first barrier layer or the second barrier layer.   The transfer sheet according to claim 1, wherein the addition amount of the silane coupling agent is 0.5 to 5.0 w% of the resin component in the hard coat layer to be added.   The transfer sheet according to claim 1, wherein the total thickness of the first barrier layer and the second barrier layer is 1 to 10 μm.   The transfer sheet according to claim 1, wherein the total thickness of the first hard coat layer and the second hard coat layer is 1 μm to 10 μm.   The transfer sheet according to any one of claims 1 to 6, wherein the base sheet is a resin sheet, a metal foil, a cellulose-based sheet, or a composite of the sheets.

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