KR20140056399A - Transfer sheet and method for producing transfer sheet - Google Patents

Abstract

The present invention relates to a transfer sheet comprising a first protective layer formed on a base sheet and a second protective layer formed on the first protective layer. Wherein at least one of the first protective layer and the second protective layer has a silane coupling agent represented by SiR ₃ D having a molecular weight of 100 to 500. The first protective layer and the second protective layer are both hard coat layers mainly composed of acrylate, Is added to bond the barrier layer. R is an alkyl linear chain containing at least one of an epoxy group, a vinyl group, a methacryl group, a mercapto group and a styryl group, D is any one of OMe, OEt, OEtOMe and OEtOEt, Me is a methyl group, Et Represents an ethyl group.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transfer sheet,

The present invention relates to a transfer sheet which can be used, for example, when transferring a resin layer or a pattern layer laminated on one surface of a base sheet to the surface of an article.

A method of protecting or decorating the surface of an article such as a plastic part or an exterior article using a transfer sheet has been known. The transfer sheet has a structure in which a transfer layer is provided on one side of a base sheet, which is a support, and the transfer layer is transferred from the base sheet to the surface of the article. The transferred transfer layer is a laminate in which a resin or a pattern (protective layer) is laminated, and a protective layer such as a protective cloth or a decorative cloth is formed on the surface of the article.

For example, Patent Document 1 shows a transfer sheet in which an anchor layer and a hard coat layer are laminated on a base sheet side adjacent to a metal thin film. In addition to the hard coat layer, the anchor layer adjacent to the metal thin film also protects the metal thin film from scratches and improves corrosion resistance.

Japanese Patent Application Laid-Open No. 2010-82963

In the transfer sheet of Patent Document 1, two protective layers of an anchor layer and a hard coat layer are formed on a metal thin film. In such a configuration, peeling may occur between the hard coat layer and the anchor layer in the case where only the base sheet is peeled after being attached to the article to be delivered. This can also occur when an anchor layer and a hard coat layer are formed by a printing method to form a transfer layer as a thin film. The reason for this is considered that when the anchor layer is formed on the hard coat layer, the hard coat layer is dried and then the anchor layer is formed, so that the adhesion between the hard coat layer and the anchor layer is reduced.

An object of the present invention is to provide a transfer sheet and a method for manufacturing a transfer sheet which can prevent peeling between protective layers in a transfer sheet in which a plurality of protective layers are laminated.

The transfer sheet of the present invention is characterized in that it comprises a base sheet, a first protective layer formed on the base sheet, and a second protective layer formed on the first protective layer, Wherein the second protective layer is a hard coat layer for protecting the surface of the object to be transferred, and the hard coat layer constituting the first protective layer and the second protective layer are all made of acrylate as a main component, Wherein a silane coupling agent represented by the following formula having a molecular weight of 100 to 500 is added to at least one of the protective layer and the second protective layer to adhere the two layers.

Wherein R is an alkyl linear chain containing at least one of an epoxy group, a vinyl group, a methacryl group, a mercapto group and a styryl group, D is any one of OMe, OEt, OEtOMe and OEtOEt, 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 at least one of the first protective layer and the second protective layer and the both layers are adhered to each other as in the characterizing feature, in the protective layer to which the silane coupling agent is added, The ring agent and the resin material in the protective layer react. The reactant is in contact with the resin constituting the other adjacent protective layer, and the adhesion between the first protective layer and the second protective layer is improved by the interaction between the reactant and the resin. As a result, it is possible to prevent delamination between the first protective layer and the second protective layer in the transfer sheet.

Further, by improving the cohesive force of the protective layer to which the silane coupling agent is added, the hardness of the protective layer is improved. As a result, the hardness of the entire protective layer can be improved.

In the above characteristic feature, the first protective layer and the second protective layer are both hard coat layers for protecting the surface of the article to be transferred, and the hard coat layer constituting the first protective layer and the second protective layer All are made up of acrylate as the main component.

With this configuration, it is possible to improve the hardness of the hard coat layer as well as improve the adhesion between the hard coat layers.

Here, in the transfer sheet of the present invention, it is preferable that the hard coat layer constituting the first protective layer and the second protective layer consist of a varnish mainly comprising glycidyl methacrylate and methyl methacrylate .

In the transfer sheet of the present invention, the amount of the silane coupling agent added is preferably 0.5 to 5.0 wt% of the resin component in the protective layer to which the silane coupling agent is added.

In addition, " w% " represents weight percentage (percentage by weight).

If the addition amount of the silane coupling agent is less than 0.5 wt% of the resin component in the added protective layer, adhesion between the first protective layer and the second protective layer is not improved much.

On the other hand, if the added amount of the silane coupling agent exceeds 5.0 wt%, the protective layer to be added becomes gelled, so that there is a possibility that the first protective layer and the second protective layer can not be properly stacked.

In view of the above, the amount of the silane coupling agent to be added is preferably 0.5 to 5.0 wt% of the resin component in the protective layer to be added.

In the transfer sheet of the present invention, the thickness of the protective layer to which the silane coupling agent is added is preferably 0.5 to 5 mu m.

When the thickness of the protective layer to which the silane coupling agent is added is less than 0.5 mu m, the abrasion resistance and chemical resistance of the protective layer are lowered.

On the other hand, if the thickness of the protective layer to which the silane coupling agent is added exceeds 5 mu m, there is a possibility that defects such as an increase in cost and deterioration of thinning of the transfer sheet and an unnecessary protective layer remain in the articles to be transferred.

In view of the above points, the thickness of the protective layer to which the silane coupling agent is added is preferably 0.5 to 5 占 퐉.

In the transfer sheet of the present invention, it is preferable that the base sheet is a resin sheet, a metal foil sheet, a cellulose sheet, or a complex of any two or more thereof.

According to this structure, the adhesion of the first protective layer and the second protective layer is improved by the addition of the silane coupling agent, and the releasability of the base sheet from the first protective layer is improved.

It is also possible to apply each of the above-described configurations as a preferable configuration in combination with other preferable configurations.

The method for manufacturing a transfer sheet of the present invention is characterized in that the method comprises the steps of forming a first protective layer containing acrylate as a main component on a base sheet and forming a second protective layer containing acrylate as a main component on the first protective layer Wherein at least one of the first protective layer and the second protective layer is provided with a protective layer which is in an uncured state at the time of lamination of both of the silane coupling agents having a molecular weight of 100 to 500 represented by the following formula To form a hard coat layer for protecting the surface of the object to be transferred by both the first protective layer and the second protective layer.

Wherein R is an alkyl linear chain containing at least one of an epoxy group, a vinyl group, a methacryl group, a mercapto group and a styryl group, D is any one of OMe, OEt, OEtOMe and OEtOEt, Me Represents a methyl group, and Et represents an ethyl group.

If a silane coupling agent having a molecular weight of 100 to 500 is added to the protective layer in an uncured state in both of the first protective layer and the second protective layer as in this characteristic configuration, In the protective layer to which the coupling agent is added, the silane coupling agent and the resin material in the protective layer react with each other so that the reactant is in contact with the resin constituting the other adjacent protective layer. The adhesion between the reactant and the first protective layer and the second protective layer is improved by the interaction with the resin constituting the other protective layer adjacent thereto. As a result, a transfer sheet which can prevent delamination between the first protective layer and the second protective layer can be manufactured. In addition, the adhesion between the first protective layer and the second protective layer can be improved, and the hardness of the hard coat layer as a whole can be improved.

1 is a schematic cross-sectional view of a transfer sheet of the first embodiment.
2 is a schematic cross-sectional view of the transfer sheet of the third embodiment.
Fig. 3 is a view showing a process for producing a molded article using the transfer sheet of the present invention. Fig.
4 is a view showing a step of manufacturing a molded article using the transfer sheet of the present invention.

The transfer sheet 1 of the present invention comprises a base sheet 2, a first protective layer (a first hard coat layer 4, a hard coat layer 7) formed on the base sheet 2, And a second protective layer (second hard coat layer 5, design layer 8) formed on the first protective layer and the second protective layer, wherein at least one of the first protective layer and the second protective layer has a specific structural formula of a molecular weight of 100 to 500 Is characterized in that a silane coupling agent is added and both layers are bonded. DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described with reference to the drawings.

[First Embodiment]

[Transfer sheet]

1 is a cross-sectional view showing the structure of a transfer sheet 1 of the present embodiment of the present invention. The transfer sheet 1 is provided with a base sheet 2 and a transfer layer 3 abutting one surface of the base sheet 2. The transfer layer 3 has a first hard coat layer 4, a second hard coat layer 5, and an adhesive layer 6. In the present embodiment, the first hard coat layer 4 corresponds to the "first protective layer" in the present invention, and the second hard coat layer 5 corresponds to the "second protective layer" in the present invention.

The layers 4, 5, and 6 constituting the transfer layer 3 can be formed by the same method as the conventional method unless otherwise specified. Examples of the conventional layer forming method include a coating method such as a gravure coating method, a roll coating method and a comma coating method, a gravure printing method, and a screen printing method.

[Gas sheet]

The base sheet 2 is made of a sheet material conventionally used for supporting a pattern layer or a hard coat layer on a sheet. The sheet material is preferably a film material. The film material refers to a sheet material made of a synthetic resin. As the synthetic resin, a polypropylene resin, a polyethylene resin, a polyamide resin, a polyester resin, an acrylic resin, a polyvinyl chloride resin, or the like can be used. In addition to such a resin sheet, a base sheet of a conventional transfer sheet such as a metal foil sheet such as an aluminum foil or a copper foil, or a cellulose-based sheet such as a gloss paper, a coat paper or a cellophane can be used as a base sheet. Or a composite sheet of two or more of a resin sheet, a metal foil sheet and a cellulose sheet may be used as a base sheet.

[Transfer layer]

The transfer layer 3 is provided on one surface of the base sheet 2 and is a layer transferred from the base sheet 2 to the surface of the article to be transferred (the body to be transferred). The transfer layer 3 has a first hard coat layer 4, a second hard coat layer 5, and an adhesive layer 6 stacked in order from the base sheet 2 side.

The first hard coat layer 4 and the second hard coat layer 5 are disposed on the surface of the article to be transferred when the base sheet 2 is peeled off from the article to be transferred after the transfer. For this reason, the first hard coat layer 4 and the second hard coat layer 5 have a hardness higher than a certain level in order to protect the articles to be transferred. Examples of the materials of the hard coat layers 4 and 5 include ionizing radiation curable resins such as cyanoacrylate type and urethane acrylate, and thermosetting resins such as acrylic type urethane. The first hard coat layer 4 and the second hard coat layer 5 are preferably made of the same resin material. If the resin material of the first hard coat layer 4 and the resin material of the second hard coat layer 5 are the same, the adhesion of both is improved. Further, the resin materials may be different from each other.

In the present embodiment, a silane coupling agent represented by the following formula is added to the second hard coat layer 5.

Here, R in the formula is an alkyl linear 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. Hereinafter, the silane coupling agent having such a specific structural formula is referred to as " specific silane coupling agent ".

The polymer used for the hard coat layers 4 and 5 has a specific blending amount considering the physical required performance and the chemical required performance of the protective layer before and after the active energy ray irradiation. That is, the (meth) acrylic equivalent is preferably 100 to 300 g / eq from the viewpoint of the curability at the time of irradiation with active energy rays. More preferably 150 to 300 g / eq. When the (meth) acrylic equivalent is more than 300 g / eq, the abrasion resistance after irradiation with the active energy ray is insufficient, and it is difficult to obtain a resin having a (meth) acryl equivalent less than 100 g / eq. From the viewpoint of reactivity with the polyfunctional isocyanate to be used in combination, the hydroxyl value of the polymer is preferably 20 to 500. More preferably, it is 100 to 300. When the hydroxyl value is less than 20, the reaction with the polyfunctional isocyanate is insufficient, and the thermal coatability of the hard coat layers 4 and 5 of the transfer sheet 1 is low. Therefore, there is a possibility that the transfer sheet 1 may not be printed, rolled up, or wound by stickiness or insufficient solvent resistance. In addition, it is difficult to obtain a hydroxyl value of more than 500. The weight average molecular weight of the polymer is preferably 5000 to 50000. More preferably 8000 to 40000. If the weight average molecular weight of the polymer is less than 5,000, the hard coat layers 4, 5 of the transfer sheet 1 may remain sticky or the solvent resistance may be insufficient. For this reason, it is difficult to print or superimpose the transfer sheet 1, and there is a possibility that a clear pattern can not be obtained. On the other hand, when the number average molecular weight is more than 50,000, the viscosity of the resin becomes too high, and the coating workability of the ink may be deteriorated.

The method for producing the polymer is not particularly limited, and conventionally known methods can be employed. (1) a method of introducing a (meth) acryloyl group into a part of the side chain of a polymer containing a hydroxyl group, [2] a method of condensing an?,? - unsaturated monomer containing a hydroxyl group in a copolymer containing a carboxyl group [3] a method in which an alpha, beta -unsaturated monomer containing an epoxy group is added to a carboxyl group-containing copolymer, [4] a method in which an alpha, beta -unsaturated carboxylic acid is reacted with an epoxy group-containing polymer, and the like .

As an example of the method [4], a method for producing the polymer used in the present invention will be described in more detail. For example, the polymer used in the present invention can be easily obtained by a method in which a polymer having a glycidyl group is reacted with an?,? - unsaturated carboxylic acid such as acrylic acid. Preferable examples of the polymer having a glycidyl group include a homopolymer of glycidyl (meth) acrylate, a copolymer of glycidyl (meth) acrylate and an?,? - unsaturated monomer not containing a carboxyl group And the like. Examples of the?,? - unsaturated monomer not containing a carboxyl group include various (meth) acrylic esters, styrene, vinyl acetate, and acrylonitrile. Use of an?,? - unsaturated monomer containing a carboxyl group is not preferable because crosslinking occurs at the time of copolymerization reaction with glycidyl (meth) acrylate to increase viscosity or gelation.

In the case of adopting any one of the above-mentioned methods [1] to [4], the kind of the used monomer or polymer, the amount of these used, and the like may be adjusted so that the (meth) acrylic equivalent, the hydroxyl value and the weight- Condition setting can be done properly. The operation for this is given to the parties.

The polyfunctional isocyanate used in combination with the polymer in the present invention is not particularly limited and any known polyfunctional isocyanate may be used. For example, there may be mentioned isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, 1,6-hexane diisocyanate, A prepolymer obtained by reacting a polyhydric alcohol with the diisocyanate, and the like can be used. When the polyfunctional isocyanate is used in combination with the polymer, the adhesiveness of the hard coat layers 4 and 5 before the activation energy ray irradiation is lowered at the time of laminating the adhesive layer 6 on the hard coat layers 4 and 5, The resistance to the solvent contained in the ink for forming the ink 6 can be somewhat satisfied. That is, the above performance can be imparted by reacting a hydroxyl group contained in the polymer with an isocyanate group of a polyfunctional isocyanate to form a thermally crosslinked product of hardness.

The content of the polymer and the polyfunctional isocyanate is preferably determined such 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. More preferably from 1 / 0.05 to 1 / 0.8.

The hard coat layers 4 and 5 may be formed of an active energy ray-curable resin composition. Here, the active energy ray-curable resin composition is a resin composition having properties of curing upon irradiation with an active energy ray (electron beam, ultraviolet ray, or the like). The active energy ray curable resin composition may contain, in addition to the polymer and the polyfunctional isocyanate, a reactive dilution monomer, a solvent, a colorant, and the like, if necessary. When an electron beam is used at the time of irradiation with active energy rays, a sufficient effect can be exhibited without using a photopolymerization initiator. However, when ultraviolet rays are used, it is necessary to add a known photopolymerization initiator. The hard coat layers 4 and 5 may be colored or non-colored.

The active energy ray-curable resin composition used for the hard coat layers (4, 5) may further contain an activator if necessary. Since the surface of the hard coat layers 4 and 5 is roughened by the addition of the lubricant, the sheet becomes easy to roll as a sheet, and blocking is less likely to occur. It can also improve resistance to wear and scratches. Waxes such as polyethylene wax, paraffin wax, synthetic wax and montan wax, and synthetic resins such as silicon and fluorine can be used as the activator. The content of the lubricant is preferably 0.5 to 15% by weight. More preferably 1 to 6% by weight. When the amount of the lubricant is less than 0.5 w%, the effect of preventing blocking and scratch resistance is reduced. When the amount of the lubricant is more than 15 w%, the transparency of the hard coat layers 4 and 5 may be extremely lowered.

The active energy ray curable resin composition used for the hard coat layers (4, 5) includes an ethylenic unsaturated group, a hydroxyl group and an isocyanate group. When the active energy ray-curable resin composition is heated, the hydroxyl group and the isocyanate group react with each other to crosslink the resin. When the active energy ray-curable resin composition is irradiated with an active energy ray, the ethylenic unsaturated group is polymerized to crosslink the resin. That is, the active energy ray-curable resin composition used for the hard coat layers 4 and 5 is crosslinked by both heat and active energy rays.

The adhesive layer 6 is provided on the side closest to the article to be transferred in the transfer layer 3, if necessary. The adhesive layer 6 adheres the transfer layer 3 and the articles to be transferred at the time of transferring. As the adhesive layer 6, a heat-sensitive resin or a pressure-sensitive resin suitable for the material to be transferred may be used. For example, when the material to be transferred is an acrylic resin, an adhesive layer 6 made of an acrylic resin may be used. When the material to be transferred is a polyphenylene oxide · polystyrene type resin, a polycarbonate type resin, a styrene type copolymer type resin or a polystyrene type blend resin, an acrylic resin, a polystyrene type resin and a polyamide type An adhesive layer 6 made of a resin or the like may be used. When the material to be transferred is a polypropylene resin, an adhesive layer 6 made of a chlorinated polyolefin resin, a chlorinated ethylene-vinyl acetate copolymer resin, a cyclized rubber, a coumarone indene resin or the like can be used.

The transfer sheet 1 may further include a release layer between the base sheet 2 and the transfer layer 3. The releasing layer may be separated from the transfer layer 3 together with the base sheet 2 at the time of transfer and may be separated from the base sheet 2 together with the transfer layer 3 to form the outermost surface of the transfer layer 3 Or the like. As the material of the release layer, a melamine resin, a silicone resin, a fluorine resin, a cellulose derivative, a urea resin, a polyolefin resin, and a paraffin resin can be used. A combination of these may be used.

[Production method of transfer sheet]

The transfer sheet 1 of the present invention is produced by adding a specific silane coupling agent to the second hard coat layer 4 of the transfer layer 3. Regarding the other points, the transfer sheet 1 of the present invention is manufactured in the same manner as the conventional transfer sheet.

For example, the base sheet 2 is prepared, and the layers constituting the transfer layer 3 are formed in order on one surface thereof. The layer constituting the transfer layer 3 is the first hard coat layer 4, the second hard coat layer 5 and the adhesive layer 6 as described above. A release layer may be formed between the base sheet 2 and the transfer layer 3 as necessary.

A first hard coat layer 4 is formed on one surface of the base sheet 2 and an unhardened second hard coat layer 5 is formed on the first hard coat layer 4, . In this manner, the transfer sheet 1 of the present invention in which the transfer layer 3 is formed on one side of the base sheet 2 is obtained.

[Transfer method to article]

By using the transfer sheet 1 of the present invention, the surface of the article can be coated by thermal roll transfer or in-mold molding. 3, the surface of the transfer sheet 3 (more specifically, the adhesive layer 6; see Fig. 1) of the transfer sheet 1 is bonded to the surface of the article 10 to be transferred, And heat and pressure are applied to the transfer sheet 1 from the base sheet 2 side using a transfer unit such as a roll transfer unit 11 or an up-down transfer unit. As a result, the transfer sheet 1 adheres to the surface of the article 10 to be transferred. When the base sheet 2 is peeled off after cooling, the transfer layer 3 is transferred to the surface of the article 10 to be transferred, and the surface of the article is coated with the transfer layer 3.

4, first, the transfer sheet 1 (1) is placed in the mold for molding having the stationary die 12 and the movable die 13 so that the base sheet 2 is in contact with the inner surface of the stationary die 12 ). Next, the fixed die 12 and the movable die 13 are closed so that the molten resin 14 is adhered to the transfer layer 3 side (more specifically, the adhesive layer 6 (see Fig. 1)) of the transfer sheet 1 The molten resin 14 is filled in the mold such that the transfer sheet 1 is sandwiched between the molten resin 14 and the inner surface of the stationary die 12. [ As a result, the resin molded article is molded from the molten resin 14, and at the same time, the transfer sheet 1 is bonded to the surface of the resin molded article. After cooling, the mold is opened to take out the resin molded article to which the transfer sheet 1 is adhered. Finally, when the base sheet 2 is peeled off, the transfer layer 3 is transferred to the surface of the resin molded article, and the surface of the resin molded article is coated with the transfer layer 3.

The material of the article to be transferred 10 is not particularly limited as long as it has been conventionally transferred by the transfer sheet 1 or that the transfer layer 3 can be adhered to the surface of the transferred layer 3 by devising the components of the adhesive layer 6 Do not. Members made of various synthetic resins, metals, glass, wood, and paper, and their painted objects and ornaments can be used as the articles 10 to be delivered.

In the present invention, a specific silane coupling agent may be added to at least one of the first hard coat layer (4) and the second hard coat layer (5) in an uncured state at the time of lamination of both. In the present embodiment, a specific silane coupling agent is added only to the second hard coat layer 5, but may be added only to the first hard coat layer 4. It may also be added to both the first hard coat layer 4 and the second hard coat layer 5. Specific silane coupling agents having a molecular weight of 100 to 500 may be used. When a specific silane coupling agent having a molecular weight of 100 to 500 is added to at least one of the first hard coat layer (4) and the second hard coat layer (5), in the hard coat layer to which the specific silane coupling agent is added, The coupling agent reacts with the resin material in the hard coat layer. The reactant is in contact with the resin constituting the adjacent hard coat layer and the adhesion between the first hard coat layer 4 and the second hard coat layer 5 is improved by the interaction between the reactant and the resin. As a result, delamination between the first hard coat layer 4 and the second hard coat layer 5 in the transfer sheet 1 can be prevented.

Further, by improving the cohesive force of the hard coat layer to which the specific silane coupling agent is added, the hardness of the hard coat layer is improved. As a result, the hardness of the entire hard coat layers 4, 5 is improved.

Further, by improving the adhesion between the first hard coat layer 4 and the second hard coat layer 5, the hard coat layer to which the specific silane coupling agent is added is adjacent to the other hard coat layer, Layer can be suppressed even if a layer is formed. When three or more hard coat layers are formed in this way, the hardness of the entire hard coat layer becomes extremely high.

Particularly, as in the present embodiment, if both the first hard coat layer 4 and the second hard coat layer 5 are hard coat layers for protecting the surface of the transferred article 10, the adhesion between the hard coat layers can be improved And the hard coat layer as a whole has a high hardness.

The addition amount of the specific silane coupling agent is preferably 0.5 to 5.0 wt% of the resin component in the hard coat layer to be added. If the addition amount of the specific silane coupling agent is less than 0.5 wt% of the resin component in the added hard coat layer, adhesion between the first hard coat layer 4 and the second hard coat layer 5 is not improved much. On the other hand, if the added amount of the specific silane coupling agent exceeds 5.0 wt%, the added hard coat layer becomes gelled, so that the first hard coat layer 4 and the second hard coat layer 5 can not be laminated properly There is a possibility.

The thickness of the hard coat layer to which the specific silane coupling agent is added is preferably 0.5 to 5 mu m. If the thickness of the hard coat layer to which the specific silane coupling agent is added is less than 0.5 mu m, the abrasion resistance and chemical resistance of the hard coat layers 4 and 5 are lowered. On the other hand, if the thickness of the hard coat layer to which the specific silane coupling agent is added exceeds 5 mu m, the cost becomes high and the thinning of the transfer sheet 1 becomes worse, and the hard coat layers 4, 5) is likely to occur.

If the base sheet 2 is a resin sheet, a metal foil sheet, a cellulosic sheet, or a combination of two or more of these (resin sheet, metal foil sheet, and cellulose sheet) The adhesion between the layer 4 and the second hard coat layer 5 is improved and the releasability of the base sheet 2 from the first hard coat layer 4 is improved.

[Second embodiment]

The transfer sheet 1 according to the present embodiment has the first hard coat layer 4 and the second hard coat layer 4 in which the transfer layer 3 is sequentially stacked from the base sheet 2 side, 5, and an adhesive layer 6. In the present embodiment, the first hard coat layer 4 corresponds to the "first protective layer" in the present invention, and the second hard coat layer 5 corresponds to the "second protective layer" in the present invention .

However, in this embodiment, a specific silane coupling agent is added only to the second hard coat layer 5, and no specific silane coupling agent is added to the first hard coat layer 4, unlike the first embodiment. The first hard coat layer 4 related to the present embodiment is formed of the following polymer. Examples of the polymer used for the first hard coat layer 4 include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyether Unsaturated ethylenic monomers such as unsaturated ethylenic oligomers or unsaturated ethylenic monomers such as acrylate, melamine (meth) acrylate, triazine acrylate, epoxy modified (meth) acrylate, urethane modified (meth) acrylate and And a composition prepared by appropriately mixing them. A polymerization initiator and a sensitizer may be added.

The polymer used for the first hard coat layer 4 may be a polymer having a (meth) acryloyl group which is a compound having a reactive double bond. For example, a monofunctional type such as methyl (meth) acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, 2- ethoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) . Examples of the diol (meth) acrylate include 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

The polymer used for the first hard coat layer 4 may be an oligomer such as a polyester acrylate, a polyurethane acrylate, an epoxy acrylate, a polyether acrylate, an oligocrylate, an alkyd acrylate, a polyol acrylate or the like do. Further, a styrene monomer having a vinyl group or an allyl group,? -Methylstyrene, divinylbenzene, vinyl acetate, pentene, hexene or an unsaturated compound may be used. These compounds may further contain a polar group such as a hydroxyl group, an amino group, a carboxyl group, a carbonyl group, and an epoxy group. By doing so, it is possible to improve the adhesion to the printed surface and the compatibility with the underpainting material.

In addition, the same polymer as in the first embodiment is used for the second hard coat layer 5 to which the specific silane coupling agent is added.

[Third embodiment]

The transfer layer 3 may be provided with the pattern layer 8. [ The transfer sheet 1 related to the present embodiment has a hard coat layer 7, a design layer 8 and an adhesive layer 6 in which the transfer layer 3 is laminated in order from the base sheet 2 side. Alternatively, the adhesive layer 6 may be directly laminated on the hard coat layer 7 partially. A specific silane coupling agent is added to the hard coat layer 7 for protecting the surface of the object to be transferred. That is, the transfer sheet 1 related to the present embodiment includes a base sheet 2, a hard coat layer 7 formed on the base sheet 2, a pattern layer 8 formed on the hard coat layer 7, And a silane coupling agent (specific silane coupling agent) having a specific structural formula of a molecular weight of 100 to 500 is added to the hard coat layer 7 to adhere the both layers. In the present embodiment, the hard coat layer 7 corresponds to the "first protective layer" in the present invention, and the design layer 8 corresponds to the "second protective layer" in the present invention. As shown in Fig. 2, when the pattern layer 8 is covered with the hard coat layer 7 in the transfer sheet 1, the pattern layer 8 can be sufficiently protected by the hard coat layer 7.

As the material of the pattern layer 8, a resin such as a polyvinyl resin, a polyamide resin, a polyacrylic resin, a polyurethane resin, a polyvinyl acetal resin, a polyester urethane resin, a cellulose ester resin, As the binder, a colored ink containing a pigment or dye of an appropriate color as a coloring agent may be used. In the case of metal color development, metal particles such as aluminum, titanium and copper, or pearl pigments coated with titanium oxide in mica may also be used.

As a method for forming the pattern layer 8, a normal printing method such as an offset printing method, a gravure printing method, or a screen printing method can be used. In particular, offset printing or gravure printing is suitable for multicolor printing and gradation representation. 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 used.

If the transfer sheet 1 on which the hard coat layer 7 and the pattern layer 8 are laminated is exposed to an environment of high humidity or high alcohol concentration, Or the alcohol penetrates, the design layer 8 may swell and the design shape may be damaged.

However, when the hard coat layer 7 to which the specific silane coupling agent is added is formed on the base sheet 2 like this constitution, a part of the specific silane coupling agent is formed on the surface side (the base sheet 2) so that the surface tension of the hard coat layer 7 is relaxed. A pattern layer 8 is formed on the hard coat layer 7 so as to face the specific silane coupling agent on the surface side of the hard coat layer 7. At this time, since the specific silane coupling agent is distributed on the surface of the hard coat layer 7 like the surfactant, the effect of the specific silane coupling agent is enhanced and the adhesion between the hard coat layer 7 and the pattern layer 8 is improved do. As a result, it is possible to decorate the article to be transferred (the article to be decorated) by the design layer 8, and to securely protect the design layer 8 by the hard coat layer 7. [ In this embodiment, a specific silane coupling agent is added only to the hard coat layer 7, but it may be added to both the hard coat layer 7 and the pattern layer 8.

Example

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. In the examples, "parts" and "%" are amounts based on weight unless otherwise specified.

Examples and Comparative Examples were evaluated based on the following criteria. In each of the following standards, " JIS " indicates the Japanese Industrial Standard, and a character string consisting of alphabets and numbers following the Japanese Industrial Standards indicates a classification class.

(1) Pencil Hardness

The pencil hardness of the hard coat layer disposed on the surface of the decorated molded article was measured in accordance with JIS K 5400.

(2) Adhesion (crosscut)

The adhesion between the first protective layer (the first hard coat layer and the hard coat layer) and the second protective layer (the second hard coat layer and the pattern layer) in the decorative molded article was measured. The adhesion was measured in accordance with the cross-cut method described in JIS K5600-5-6.

The adhesion between the first protective layer and the second protective layer was evaluated by any one of the following methods.

○: The edge of the cut is completely smooth, so no peeling of the eyes of any lattice occurs.

?: Small peeling was observed in the coating film at the intersection of the cuts, and the peeling occurred between the first protective layer and the second protective layer. Peeling is less than 5% of the cross-cut area.

X: Small peeling was observed at the intersection of the cuts, and the peeling occurred between the first protective layer and the second protective layer. Peeling is 5% or more of the cross cut area.

(3) Cracking property

The transfer sheet was placed in a mold, and injection molding of a polycarbonate / ABS alloy resin was performed. Then, the base sheet was removed to obtain a molded product of KEYDECK as a component of a personal computer. The surface area of the molded product of the obtained KEYDECK on which the first protective layer was present was 120 cm ² . Then, the surface of the first protective layer of the molded product was observed with naked eyes to confirm the presence or absence of cracks, and evaluated by any one of the following methods.

○: Crack was not confirmed.

△: 1 to 3 cracks were observed in 50 cm ² molded articles.

×: At least four cracks were observed in a molded article of 50 cm ² .

(4) Blocking resistance

The inner blocking of the first protective layer was measured in the transfer sheet. The measurement of the adhesion was carried out in accordance with the measurement method of blocking resistance described in 6.2.2 of JIS K5701-1. The anti-blocking property of the hard coat layer was evaluated by any one of the following methods.

A: When transfer sheets were taken out one by one from a plurality of overlapping transfer sheets, the transfer sheets were peeled off between the base sheet and the adhesive layer, and no peeling occurred between the first and second protective layers.

X: When transfer sheets were taken out one by one from a plurality of overlapping transfer sheets, the transfer sheet or a part of the transfer sheet was not peeled off between the base sheet and the adhesive layer, but between the first and second protective layers Peeling occurred.

(5) Alcoholic properties

The edible molded article was immersed in a methanol solution for 10 minutes and then air-dried for 60 minutes.

Next, the naturally dried decorative molded article was tested in accordance with the cross-cut method described in JIS K5600-5-6. The alcohol resistance of the first protective layer (hard coat layer) and the second protective layer (pattern layer) was evaluated by any one of the following.

○: The edge of the cut is completely smooth, and no peeling occurs in the eyes of any grid.

?: Small peeling was observed in the coating film at the intersection of the cuts, and the peeling occurred between the first protective layer and the second protective layer. The exfoliation was less than 30% of the cross-cut area.

X: Small peeling was observed at the intersection of the cuts, and the peeling occurred between the first protective layer and the second protective layer. The exfoliation was more than 30% of the area subjected to crosscutting.

(6) Abrasion resistance

The surface of the molded article was placed on a surface of a decorated molded article using a Taber friction tester (abrasion wheel: CS-10, load: 1 kg / arm, rotation speed: 500 rpm) manufactured by Yasuda Precision Machinery Co., Ltd. in accordance with JIS K7204 The first protective layer (hard coat layer) was rubbed. Then, the number of revolutions of the abrasive wheel until the first protective layer was abraded and penetrated was measured. The abrasion resistance of the first protective layer was evaluated by any one of the following.

○: It required more than 1000 rotations to penetrate.

△: It required 500 times or more and less than 1000 rotations to penetrate.

X: Less than 500 rotations were required to penetrate.

(Example 1)

As the base sheet, a polyester resin film having a thickness of 38 mu m was used. On the base sheet, a melamine resin-based releasing agent was applied by gravure printing to a thickness of 1 mu m to form a releasing layer. Thereafter, 200 parts of the following varnish A (100 parts of solid content), 5 parts of 1,6-hexane diisocyanate trimer (trade name: Colonate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 5 parts of a photopolymerization initiator , Manufactured by Ciba-Geigy Co., Ltd.) (5 parts) was formed by a gravure printing method. The thickness of the first protective layer was 4 mu m. And then heated at 150 DEG C for 20 seconds to half-bridge the first hard coat layer. Then, 200 parts of the following varnish A (100 parts of solid content), 1,6-hexane diisocyanate trimer (trade name: Colonate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.), 5 parts of a photopolymerization initiator (Second hard coat layer) prepared by blending 5 parts of a curing agent (trade name: CURER 184, manufactured by Chiba Kogyo Kogyo Co., Ltd.) and 1 part of vinyltrimethoxysilane (trade name: KBM-1003, Shin-Etsu Chemical Co., did. The thickness of the second protective layer was 0.7 mu m. Further, the second hard coat layer was crosslinked by heating at 150 캜 for 20 seconds. Finally, an adhesive layer made of an acrylic resin was printed and formed on the second protective layer by gravure printing to obtain a transfer sheet.

The varnish A was obtained as follows using a reactor equipped with a stirrer, a cooling tube, a dropping funnel, and a nitrogen inlet tube. 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, 1000 parts of butyl acetate, And 7.5 parts of 2'-azobisisobutyronitrile (hereinafter referred to as AIBN) were charged. Thereafter, in a nitrogen atmosphere, the temperature was elevated to about 90 ° C over about 1 hour, and the temperature was maintained for 1 hour. Next, the mixed solution was dropwise added to the system over about 2 hours under a nitrogen atmosphere by a dropping tank in which a mixed solution composed of 525 parts of GMA, 225 parts of MMA, 3.7 parts of lauryl mercaptan and 22.5 parts of AIBN was stored, did. After that, 10 parts of AIBN was added and kept warm for 1 hour. Thereafter, the temperature was raised to 120 캜 and kept at that temperature for 2 hours. After cooling to 60 DEG C, the nitrogen introduction pipe was replaced with an air introduction tube, 355 parts of acrylic acid (hereinafter referred to as AA), 2.0 parts of methoquinone and 5.4 parts of triphenylphosphine were added and mixed, , And the temperature was raised to 110 ° C. After maintaining the temperature at this temperature for 8 hours, 1.4 parts of methoquinone was added, cooled, and ethyl acetate was added so that the nonvolatile content became 50% to obtain a varnish A. The polymer contained in the 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).

This transfer sheet was transferred onto the surface of the molded article by the simultaneous transfer molding method. Thereafter, the base sheet was peeled off, and ultraviolet rays were irradiated to completely cure the first protective layer and the second protective layer. The molding conditions were a resin temperature of 240 캜, a mold temperature of 55 캜, and a resin pressure of about 300 kg / cm ² . The molded article was molded from acrylic resin having a length of 95 mm, a width of 65 mm, a height of 4.5 mm, and a corner radius R of 2.5 mm or more. The irradiation conditions were 120 w / cm, 6 lamps, lamp height of 10 cm, and belt speed of 15 m / min. Various evaluations were carried out on the transfer sheet and the transferred molded article.

(Examples 2 to 9 and Comparative Examples 1 to 9)

Except that the resin material of the first protective layer, the resin material of the second protective layer, the kind and amount of the silane coupling agent, and the thicknesses of the first protective layer and the first protective layer were changed as shown in Table 1, , A transfer sheet was produced to obtain a transferred molded article, and the same evaluation was carried out. The evaluation results are shown in Table 1.

From the evaluation results shown in Table 1, the following points are evident. In Examples 1 to 9 in which 0.5 to 5.0 w% of the silane coupling agent was added to the second protective layer (second hard coat layer), the pencil hardness was " H " or higher, Excellent blocking ability.

On the other hand, in Comparative Examples 1 and 6 in which no silane coupling agent was added to the second protective layer, satisfactory results in adhesion, cracking resistance and blocking resistance were not obtained regardless of the thickness of the second protective layer.

In Comparative Example 2 in which the molecular weight of the silane coupling agent was more than 500, satisfactory results in adhesion and blocking resistance were not obtained. In Comparative Example 3 in which the molecular weight of the silane coupling agent was less than 100, There was no.

In Comparative Examples 4 and 5 in which the same silane coupling agent as in Examples 1 to 4 was added to the second protective layer, in Comparative Example 4 in which the amount of the silane coupling agent was insufficient, satisfactory results in adhesion and blocking resistance were not obtained , And in Comparative Example 5 in which the amount of the silane coupling agent was excessive, the second protective layer could not be painted itself.

Also, in Comparative Examples 7 to 9 in which a silane coupling agent containing an amino silane, a ureide silane, and an isocyanate silane as functional groups was added, the second protective layer could not be painted.

(Example 10)

As the base sheet, a polyester resin film having a thickness of 38 mu m was used. On the base sheet, a melamine resin-based releasing agent was applied by gravure printing to a thickness of 1 mu m to form a releasing layer. Thereafter, 200 parts of the varnish A (100 parts), 1,6-hexane diisocyanate trimer (trade name: Colonate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.) and 5 parts of a photopolymerization initiator (Irgacure 184 , Manufactured by Ciba-Geigy Kogyo Co., Ltd.) (5 parts) was formed by a gravure printing method. The thickness of the first protective layer was 0.5 mu m. The first protective layer was cured by heating at 150 ° C for 20 seconds. Thereafter, a second protective layer (pattern layer) made of polycarbonate (PC) / ABS ink and an adhesive layer made of an acrylic resin were successively printed on the first protective layer by gravure printing to obtain a transfer sheet.

Simultaneous molding and transfer were carried out using this transfer sheet to transfer the transfer sheet onto the surface of the molded article. Thereafter, the base sheet was peeled off, and ultraviolet rays were irradiated to completely cure the first protective layer. The molding conditions were a resin temperature of 240 캜, a mold temperature of 55 캜, and a resin pressure of about 300 kg / cm ² . The molded article was molded from acrylic resin having a length of 95 mm, a width of 65 mm, a height of 4.5 mm, and a corner radius R of 2.5 mm or more. The irradiation conditions were 120 w / cm, 6 lamps, lamp height of 10 cm, and belt speed of 15 m / min. Various evaluations were carried out on the transfer sheet and the transferred molded article (edible molded article).

(Examples 11 to 19 and Comparative Examples 10 to 18)

A transfer sheet was produced in the same manner as in Example 1 except that the resin material of the first protective layer, the kind and amount of the silane coupling agent, and the resin material of the second protective layer were changed as shown in Table 2, A decorative molded article) was obtained and evaluated in the same manner. The evaluation results are shown in Table 2.

From the evaluation results shown in Table 2, the following points are apparent. In Examples 10 to 19 in which 0.5 to 5.0 w% of the silane coupling agent was added to the polymer in the first protective layer (hard coat layer), the pencil hardness was " 2B " or more and the alcohol resistance, abrasion resistance, Excellent blocking resistance.

On the other hand, in Comparative Example 10 in which the silane coupling agent was not added to the first protective layer, satisfactory results in alcohol resistance and adhesion were not obtained.

In Comparative Example 11 in which the molecular weight of the silane coupling agent was more than 500, satisfactory results in adhesion and blocking resistance were not obtained. In Comparative Example 12 in which the molecular weight of the silane coupling agent was less than 100, the first protective layer could be painted itself There was no.

In Comparative Examples 13 to 15 in which the same silane coupling agent as in Examples 10 to 13 was added to the first protective layer, in Comparative Example 13 in which the amount of the silane coupling agent was insufficient, satisfactory results were not obtained in terms of adhesion and blocking resistance , And in Comparative Example 14 in which the amount of the silane coupling agent was excessive, the first protective layer could not be painted itself. In Comparative Example 15, the amount of the silane coupling agent may be approximately equal to that of Examples 11 and 13, and when the second protective layer (pattern layer) is made of an ABS resin alone, satisfactory results are obtained in terms of abrasion resistance and adhesion I could not.

Also, in Comparative Examples 16 to 18 in which a silane coupling agent containing an amino silane, a ureide silane, and an isocyanate silane as functional groups was added, the first protective layer could not be painted.

The present invention can be applied to a transfer sheet for transferring a protective layer to a surface of a component such as a car, a household electric appliance, a cellular phone, a personal computer, and the like.

1 transfer sheet
2 base sheet
3 transfer layer
4 First hard coat layer (first protective layer)
5 Second hard coat layer (second protective layer)
6 adhesive layer
7 Hard coat layer
8-pattern floor
10 Pivotal Goods

Claims (6)

A base sheet,
A first protective layer formed on the base sheet,
And a second protective layer formed on the first protective layer,
Wherein the first protective layer and the second protective layer are both hard coat layers for protecting the surface of the object to be transferred,
Wherein the hard coat layer constituting the first protective layer and the second protective layer both comprise acrylate as a main component,
Wherein a silane coupling agent represented by the following formula having a molecular weight of 100 to 500 is added to at least one of the first protective layer and the second protective layer to adhere the both layers.

(Wherein R is an alkyl linear chain containing at least one of an epoxy group, a vinyl group, a methacryl group, a mercapto group and a styryl group, D is any one of OMe, OEt, OEtOMe and OEtOEt, Methyl group, and Et represents an ethyl group.) The method according to claim 1,
Wherein the hard coat layer constituting the first protective layer and the second protective layer comprises a varnish mainly comprising glycidyl methacrylate and methyl methacrylate. The method according to claim 1 or 2,
Wherein the added amount of the silane coupling agent is 0.5 to 5.0 w% of the resin component in the added protective layer. The method according to any one of claims 1 to 3,
Wherein the thickness of the protective layer to which the silane coupling agent is added is 0.5 to 5 占 퐉. The method according to any one of claims 1 to 4,
Wherein the base sheet is a resin sheet, a metal foil sheet, a cellulose sheet, or a composite of two or more of them. A step of forming a first protective layer containing acrylate as a main component on a base sheet,
And forming a second protective layer containing acrylate as a main component on the first protective layer,
A silane coupling agent represented by the following formula having a molecular weight of 100 to 500 is added to a protective layer in an uncured state in at least one of the first protective layer and the second protective layer at the time of lamination,
Wherein the hard coat layer for protecting the surface of the article to be transferred is formed by both the first protective layer and the second protective layer.

(Wherein R is an alkyl linear chain containing at least one of an epoxy group, a vinyl group, a methacryl group, a mercapto group and a styryl group, D is any one of OMe, OEt, OEtOMe and OEtOEt, Methyl group, and Et represents an ethyl group.)

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