Transfer-type curable resin sheet for coating and method for forming coating

Abstract

A transfer-type curable resin sheet for coating, which comprises a coating layer that contains a curable resin composition that can be cured by heat, moisture, or active energy rays, and a transfer layer that contains a thermoplastic resin, the surface of the coating layer on the opposite side from the surface on which the transfer layer is provided has a viscosity value at 23 DEG C of 300 N / cm < 2 > or more and 4000 N / cm < 2 > or less.

Description

Technical Field

[0001] The present invention relates to a transfer-type curable resin sheet for coating and a coating forming method using the transfer-type curable resin sheet for coating. Background Art

[0002] In the past, furniture, steel plates, vehicle bodies and other products have been painted to give them design, durability, weather resistance, scratch resistance and other functions. In the case of industrial painting of three-dimensional products, the painting is usually carried out by blowing with air or electrostatic force. In the painting by blowing, the loss generated during painting, CO2 discharged from the factory and the large-scale equipment investment are considered, and the replacement of the decoration technology using resin film is being studied recently.

[0003] The so-called decorative technology is a technology that, in various fields such as household electrical products, automobile interior decorations, and sundries, a resin film (decorative film) obtained by printing text and patterns using white, black, or colored ink is attached to the surface of the product for decoration, thereby presenting high functionality and design. For example, in Patent Document 1, as a decorative film, a coating film is proposed, which has a protective layer formed by an active energy ray-curing composition on a film substrate. In Patent Document 1, it is recorded that since the protective layer is formed by an active energy ray-curing composition having a specific composition, the chemical resistance and scratch resistance of the coating surface can be improved.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent No. 5394995 Summary of the invention

[0007] Problems to be solved by the invention

[0008] In the coating film disclosed in Patent Document 1, the base film itself has no adhesiveness, so in order to attach it to various products, an adhesive layer formed of an adhesive is usually formed on the surface opposite to the protective layer. However, if an adhesive is used for attachment, it is easy to peel off over time, and is not suitable for outdoor use requiring durability and weather resistance.

[0009] In addition, if a coating film as disclosed in Patent Document 1 is used, insert molding can be performed in a manner that the surface of the plastic raw material supplied from the injection mold is decorated with the coating film while molding, thereby forming a surface layer equivalent to coating on the surface of the plastic molded object. However, this method is based on injection molding, so it is difficult to apply to steel plate materials other than plastic materials.

[0010] In order to apply to steel plate materials, it is also possible to attach the film by vacuum forming, but in vacuum forming, if the film itself does not have adhesiveness or adhesion, it cannot be properly attached to the surface of various products. On the other hand, when adhesiveness or adhesion is given to the film itself, the film becomes soft and vulnerable to scratches.

[0011] Therefore, an object of the present invention is to provide a transfer-type curable resin sheet for coating, which can be appropriately adhered to various articles by vacuum forming or the like and has excellent scratch resistance.

[0012] Means for solving problems

[0013] As a result of intensive research, the inventors of the present application have found that the above-mentioned problems can be solved by forming a resin sheet into a transfer-type multilayer structure having a coating layer containing a curable resin composition and a transfer layer, and setting the viscosity value of the coating layer on the attachment side at 23° C. to a certain range, thereby completing the following invention. That is, the present invention provides the following [1] to [7].

[0014] [1] A transfer-type curable resin sheet for coating, comprising a coating layer and a transfer layer, wherein the coating layer comprises a curable resin composition that can be cured by heat, moisture or active energy rays, the transfer layer comprises a thermoplastic resin, and the coating layer has a viscosity value of 300 N / cm at 23°C on the side opposite to the side on which the transfer layer is provided 2 Above and 4000N / cm 2 the following.

[0015] [2] The transfer-type curable resin sheet for coating according to [1], wherein the transfer layer has MD and TD tensile elongations at break at 120° C. of 500% or more.

[0016] [3] The transfer-type curable resin sheet for coating according to [1] or [2], wherein the transfer layer has both MD and TD tensile elongations at break at 100°C of 500% or more.

[0017] [4] The transfer-type curable resin sheet for coating according to any one of [1] to [3], wherein the curable resin composition comprises a (meth)acrylic resin (A) having a weight average molecular weight of 100,000 to 1,000,000, which is solid and has a plurality of functional groups.

[0018] [5] The transfer-type curable resin sheet for coating according to [4], wherein the (meth)acrylic resin (A) is a (meth)acrylic polyol (A1), and the curable resin composition contains a blocked isocyanate (B).

[0019] [6] The transfer-type curable resin sheet for coating according to [4], wherein the (meth)acrylic resin (A) is a polymer (A2) having a (meth)acryloyl group, and the curable resin composition contains a radical polymerization initiator (C) that generates radicals by heat or active energy rays.

[0020] [7] A method for forming a coating, comprising attaching the transfer curable resin sheet for coating according to any one of [1] to [6] to a coating object, and then curing the coating layer to form the coating.

[0021] [8] The coating forming method according to [7], wherein the transfer layer is peeled off from the coating layer to remove the transfer layer from the coated object.

[0022] Effects of the Invention

[0023] According to the present invention, it is possible to provide a transfer-type curable resin sheet for coating, which can appropriately adhere a coating layer to various articles by vacuum forming or the like and has excellent scratch resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] [ Figure 1 ] is a schematic cross-sectional view showing an example of a transfer-type curable resin sheet for coating.

[0025] [ Figure 2 ] is a schematic cross-sectional view showing an example of a transfer-type curable resin sheet for coating.

[0026] [ Figure 3 ] is a schematic cross-sectional view showing an example of a transfer-type curable resin sheet for coating.

[0027] [ Figure 4 ] is a schematic cross-sectional view showing an example of a method for forming a coating on a coated object.

[0028] [ Figure 5 ] is a schematic diagram of the device for TOM molding.

[0029] [ Figure 6 ] is a schematic cross-sectional view showing an example of a method for forming a coating on a coated object. DETAILED DESCRIPTION

[0030] Hereinafter, the present invention will be described in more detail using embodiments.

[0031] The transfer-type curable resin sheet for coating of the present invention (hereinafter, sometimes referred to as "transfer-type resin sheet") is a multilayer sheet having a coating layer and a transfer layer. In the transfer-type resin sheet, the coating layer is formed on one side of the transfer layer, and they are integrated. The coating layer contains a curable resin composition that can be cured by heat, moisture or active energy rays. The transfer layer contains a thermoplastic resin.

[0032] The transfer resin sheet is attached to various articles (hereinafter also referred to as the coated body) for coating using the coating layer in a manner that the coating layer contacts the coated body. Then, the coating layer is cured to form a cured coating layer on the surface of the coated body, and the cured coating layer forms a coating. The transfer layer can be peeled off from the coating layer after the coating layer is cured, thereby being removed from the coated body.

[0033] Hereinafter, the coating layer and the transfer layer used for the transfer type resin sheet will be described in detail.

[0034] <Paint layer>

[0035] The coating layer constituting the transferable resin sheet of the present invention has a viscosity value at 23° C. on the surface opposite to the surface on which the transfer layer described below is provided (hereinafter also referred to as “viscosity value”) of 300 N / cm 2 Above and 4000N / cm 2 If the viscosity value is less than the lower limit, good adhesion to the adherend cannot be achieved. In addition, if the viscosity value exceeds the upper limit, the hardness of the cured coating film cannot be sufficiently increased, and excellent scratch resistance cannot be imparted.

[0036] From the above viewpoints, the viscosity value is preferably 500 N / cm 2 Above and 3000N / cm 2 Below, more preferably 700N / cm 2 Above and 2500N / cm 2 the following.

[0037] The coating layer is, for example, a layer used for the protection or beautification of an adherend, or for imparting a unique function other than this. The coating layer can be used as a colored layer as described later, or as a transparent layer. In addition, as a unique function of the coating layer, for example, a function as a heat-insulating coating can be cited. At this time, the coating formed by the coating layer can function as a heat-insulating coating. In this case, a heat-insulating material can be contained in the thermosetting resin composition so that the coating layer becomes a heat-insulating layer. In addition, surface unevenness can be set on the coating layer, thereby imparting surface properties such as matte and embossing. In addition, functions such as rust prevention, mildew prevention, heat insulation, and antistatic can also be presented by combining components that meet the target in the curable resin composition.

[0038] In addition, the surface of the paint layer opposite to the surface provided with the transfer layer becomes the sticking surface to be stuck to the to-be-coated body.

[0039] The coating layer used in the present invention comprises a curable resin composition that can be cured by heat, moisture or active energy rays. As active energy rays, ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays can be cited, and any energy species can be used as long as free radical active species can be generated. The curable resin composition is preferably a curable resin composition that can be cured by heat or active energy rays among them.

[0040] The curable resin composition may contain a resin having a functional group that can react with the resin itself or a curing agent and cure by heat, moisture or active energy rays. As the resin for the curable resin composition, curable resins can be mentioned, and specifically, as the resin cured by heat or active energy rays, (meth) acrylic resins, polycarbonate resins, polyester resins, epoxy resins can be mentioned, wherein, preferably (meth) acrylic resins. In addition, as the resin cured by moisture, moisture-curable resins can be used as described later.

[0041] Hereinafter, the case where at least a (meth)acrylic resin is used as a resin in the curable resin composition will be described in detail.

[0042] ((Meth)acrylic resin)

[0043] As the (meth) acrylic resin, there can be mentioned a (meth) acrylic resin having a plurality of functional groups. The functional group is a group that can react by heat or active energy rays. As the functional group, preferably there can be mentioned a functional group that reacts with a functional group (e.g., isocyanate group) contained in a curing agent described later, a functional group having a photopolymerizable unsaturated bond, etc., specifically, there can be mentioned a hydroxyl group, an amino group, a carboxyl group, a (meth) acryloyl group, a vinyl group, a glycidyl group, etc. The (meth) acrylic resin may have only one functional group, or may have two or more functional groups. Among them, the (meth) acrylic resin preferably has at least one of a hydroxyl group or a (meth) acryloyl group.

[0044] Therefore, the (meth)acrylic resin is preferably a (meth)acrylic polyol having a plurality of hydroxyl groups or a polymer having a plurality of (meth)acryloyl groups.

[0045] The (meth) acrylic resin is preferably an acrylic polymer obtained by polymerizing a monomer mixture containing a (meth) acrylic ester monomer and a functional group-containing monomer having the above-mentioned functional groups such as a hydroxyl group, an amino group, and a carboxyl group. Such acrylic polymers can contain functional groups in the acrylic polymer by using functional group-containing monomers. In addition, the monomer mixture may also contain monomers other than (meth) acrylic ester monomers and functional group-containing monomers such as styrene derivative monomers. It should be noted that the so-called (meth) acrylic- refers to methacrylic- or acrylic-, and other similar terms are the same.

[0046] Examples of the (meth)acrylate monomer include (meth)acrylate monomers not having the above-mentioned functional groups, such as (meth)acrylate alkyl esters having an alkyl group with an alkyl carbon number of 1 to 18, such as methyl (meth)acrylate and ethyl (meth)acrylate, (meth)acrylate alkyl esters having an aromatic ring, such as benzyl (meth)acrylate and phenoxydiethylene glycol (meth)acrylate, and 2-ethoxyethyl (meth)acrylate.

[0047] As the functional group-containing monomer, hydroxyl-containing monomer, amino-containing monomer, carboxyl-containing monomer, etc. can be mentioned. They can be used alone or in combination of two or more. As the functional group-containing monomer, among the above, hydroxyl-containing monomer is preferred. Moreover, the above-mentioned (meth) acrylic polyol can be obtained by polymerizing a monomer mixture containing a (meth) acrylate monomer and a hydroxyl-containing monomer.

[0048] The hydroxyl group-containing monomer is not particularly limited, and examples thereof include (meth)acrylate monomers having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, etc. The amino group-containing monomer is not particularly limited, and examples thereof include (meth)acrylate monomers having an amino group, such as 2-aminoethyl (meth)acrylate, etc. The carboxyl group-containing monomer is not particularly limited, and examples thereof include (meth)acrylic acid.

[0049] The styrene derivative monomer is not particularly limited, and examples thereof include styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-ethoxystyrene, p-chlorostyrene, m-chlorostyrene, and o-chlorostyrene.

[0050] In addition, as the (meth) acrylic resin, a copolymer obtained by block or graft polymerization of the above acrylic polymer and other monomers or polymers can also be used. In this case, as other monomers or polymers, acrylic acid, styrene, maleic acid, imide, silicone, fluorine monomers or polymers of these monomers can be cited.

[0051] Alternatively, the acrylic polymer may contain a (meth)acryloyl group by reacting a functional group of an acrylic polymer obtained by polymerizing a monomer mixture containing a (meth)acrylate monomer and a functional group-containing monomer with a (meth)acryloyl group-containing compound having a reactive group capable of reacting with the functional group and a (meth)acryloyl group.

[0052] As a polymer having a (meth)acryloyl group, it is preferred that the main chain is an acrylic skeleton having a structural unit derived from (meth)acrylate like the above-mentioned acrylic polymer, but the main chain does not necessarily need to have an acrylic skeleton as long as it has a (meth)acryloyl group. The main chain may not have an acrylic skeleton, and may have, for example, a urethane skeleton.

[0053] In the curable resin composition, as the above-mentioned (meth) acrylic resin, it is preferred to include a (meth) acrylic resin (hereinafter referred to as (meth) acrylic resin (A)) having a weight average molecular weight (Mw) of 100,000 or more and 1,000,000 or less, being solid, and having multiple functional groups. By making the weight average molecular weight of the (meth) acrylic resin (A) within the above range and being solid, it is easy to maintain the coating layer in a certain shape even before curing, and it is easy to properly form the coating layer on the transfer layer. In addition, it is also easy to impart viscosity and elongation to the coating layer. Since the coating layer has viscosity and elongation, it is easy to make it close to the coated body by vacuum forming, etc. without causing cracks, and the vacuum formability becomes good. In addition, if the weight average molecular weight is within the above range, it is easy to increase the hardness of the cured coating layer.

[0054] From the above viewpoints, the weight average molecular weight of the (meth)acrylic resin (A) is preferably 150,000 or more and 500,000 or less, and more preferably 180,000 or more and 450,000 or less.

[0055] It should be noted that, in this specification, the weight average molecular weight is measured by gel permeation chromatography (GPC) and can be obtained as a standard polystyrene conversion value. In addition, the so-called solid state means that it is solid at room temperature (23°C) and normal pressure (1 atmosphere). Similarly, the so-called liquid state means that it is liquid at room temperature (23°C) and normal pressure (1 atmosphere).

[0056] The glass transition temperature (Tg) of the (meth)acrylic resin (A) is preferably lower than 90° C., more preferably lower than 80° C., and further preferably lower than 60° C., and is preferably higher than 0° C., and more preferably higher than 10° C. When the glass transition temperature of the (meth)acrylic resin (A) is within the above range, it is easy to impart certain viscosity and elongation to the coating layer.

[0057] In addition, in this specification, the glass transition temperature is a value calculated|required by differential scanning calorimetry (DSC) based on JIS K7121.

[0058] The high molecular weight (meth)acrylic resin (A) is preferably at least one of a (meth)acrylic polyol having a plurality of hydroxyl groups (hereinafter, also referred to as a (meth)acrylic polyol (A1)) or a polymer having a (meth)acryloyl group (hereinafter, also referred to as a polymer (A2)).

[0059] The (meth)acrylic polyol (A1) can be obtained, for example, by polymerizing a monomer mixture containing a (meth)acrylic acid ester monomer and a hydroxyl group-containing monomer as described above.

[0060] The hydroxyl value of the (meth)acrylic polyol (A1) is preferably 20 mgKOH / g or more and 200 mgKOH / g or less, and more preferably 30 mgKOH / g or more and 150 mgKOH / g or less. By making the hydroxyl value within the above range, the curing property becomes good, and it is easy to make the coating layer have high hardness after curing. It should be noted that the hydroxyl value can be measured in accordance with JIS K1557-1:2007.

[0061] The polymer (A2) preferably has a (meth)acryloyl group in a prescribed ratio. Specifically, the (meth)acryloyl group equivalent is preferably 100 g / mol or more and 10,000 g / mol or less, and more preferably 500 g / mol or more and 8,000 g / mol or less. By making the (meth)acryloyl group equivalent within the above range, it is easy to make the curing property of the coating layer containing the polymer (A2) good, and make the coating layer have high hardness after curing. It should be noted that the so-called (meth)acryloyl group equivalent refers to the value obtained by dividing the weight average molecular weight of the polymer by the number of (meth)acryloyl groups in one molecule of the polymer.

[0062] The content of the (meth)acrylic resin (A) in the coating layer is not particularly limited, and is, for example, 18% by mass or more, preferably 19% by mass or more, and more preferably 20% by mass or more, based on the total amount of the curable resin composition. By containing a certain amount or more of the (meth)acrylic resin (A), the coating properties and curing properties of the curable resin composition can be improved.

[0063] The content of the (meth)acrylic resin (A) in the coating layer is not particularly limited, but is, for example, 60% by mass or less, preferably 55% by mass or less, and more preferably 50% by mass or less, based on the total amount of the curable resin composition. By reducing the content of the (meth)acrylic resin (A), the viscosity of the curable resin composition can be easily improved.

[0064] It should be noted that, in this specification, the total amount of the curable resin composition as a reference, when the curable resin composition contains a solvent such as a solvent, means that the total amount of the components other than the solvent is set to 100% by mass. That is, the total amount of the curable resin composition as a reference means the total amount of solid content of the curable resin composition as a reference.

[0065] The (meth)acrylic resin (A) may be used alone or in combination of two or more.

[0066] The curable resin composition preferably contains, as a resin, a plasticizer resin (a) having a weight average molecular weight of less than 100,000 in addition to the (meth)acrylic resin (A).

[0067] Plasticizing resin (a) can use a resin that can plasticize the curable resin composition before curing so as to adjust the viscosity value of the coating layer to a desired range. As plasticizing resin (a), preferably, it is compatible with (meth) acrylic resin (A) and has a functional group that can be cured by heat or active energy rays like (meth) acrylic resin (A). As the resin used for plasticizing resin (a), (meth) acrylic resin, polycarbonate resin, polyester resin, epoxy resin, polyether resin, polyolefin resin, resin from plant (castor oil, etc.) can be cited, among which (meth) acrylic resin or polycarbonate resin is preferred.

[0068] By making the curable resin composition contain a plasticizer resin (a) in addition to the high molecular weight (meth) acrylic resin (A), it is easy to make the viscosity, coating properties, curability of the coating layer, elongation, etc. of the curable resin composition good in a good balance. The weight average molecular weight of the plasticizer resin (a) is preferably 100 or more and 30,000 or less, and more preferably 300 or more and 20,000 or less.

[0069] In addition, it is desirable that the plasticized resin (a) is liquid in a state of 100% solid content. The plasticized resin (a) may or may not have a glass transition temperature. When the plasticized resin (a) has a glass transition temperature, it is not particularly limited, but is preferably below 0°C, more preferably below -20°C, and further preferably below -40°C. In addition, the lower limit of the glass transition temperature is not particularly limited, for example, it is above -120°C, preferably above -100°C.

[0070] When the glass transition temperature of the plasticizing resin (a) is set within the above range, it is easy to adjust the tensile elongation at break of the coating layer within a desired range, and it is also easy to develop tack.

[0071] The plasticizing resin (a) is preferably at least one of a (meth)acrylic polyol or polycarbonate diol having a plurality of hydroxyl groups (hereinafter also referred to as polyol (a1)) and a polymer having a (meth)acryloyl group (hereinafter also referred to as polymer (a2)).

[0072] The hydroxyl value of the (meth)acrylic polyol or polycarbonate diol (polyol (a1)) is preferably 20 mgKOH / g to 300 mgKOH / g, more preferably 50 mgKOH / g to 250 mgKOH / g. By making the hydroxyl value within the above range, the curing property becomes good, and it is easy to make the coating layer have high hardness after curing.

[0073] The (meth)acryloyl equivalent of the polymer (a2) having a (meth)acryloyl group is preferably 10 g / mol or more and 10000 g / mol or less, and more preferably 100 g / mol or more and 8000 g / mol or less. By making the (meth)acryloyl equivalent within the above range, the curing property becomes good, and it is easy to make the coating layer have high hardness after curing.

[0074] When the high molecular weight (meth)acrylic resin (A) is (meth)acrylic polyol (A1), (meth)acrylic polyol or polycarbonate diol (polyol (a1)) is preferably used. By using (meth)acrylic polyol or polycarbonate diol (polyol (a1)) and (meth)acrylic polyol (A1) together, it is easy to appropriately cure the curable resin composition by heating.

[0075] In addition, polymer (a2) is preferably used when the high molecular weight (meth) acrylic resin (A) is a polymer (A2) having a (meth) acryloyl group. By using polymer (a2) and polymer (A2) together, it is easy to properly cure the curable resin composition by irradiation with active energy rays, heating, etc.

[0076] The plasticizing resin (a) may be used alone or in combination of two or more.

[0077] The ratio of the total content of the plasticizer resin (a) and the blocked isocyanate (B) in the coating layer to the (meth) acrylic resin (A) (hereinafter also referred to as "(a+B) / A") is, for example, 0.8 or more, preferably 0.9 or more, and more preferably 1.0 or more. By making (a+B) / A a certain value or more, that is, containing a certain amount of the plasticizer resin (a) and the blocked isocyanate (B), the viscosity value of the curable resin composition can be made to be a certain value or more, and the adhesion and the like can be easily improved.

[0078] (a+B) / A is, for example, 5 or less, preferably 4.5 or less, and more preferably 4 or less. By setting (a+B) / A to a certain value or less, the hardness of the cured product of the curable resin composition can be set to a certain value or more, and excellent scratch resistance can be imparted.

[0079] In addition, when the curable resin composition contains a solvent such as a solvent, (a+B) / A is the above-mentioned mixing ratio based on the total solid content. The same applies to a / A described later.

[0080] (Blocked isocyanate (B))

[0081] The curable resin composition of the present invention may contain a curing agent that reacts with the above-mentioned curable resin to cure it. The curing agent is preferably a thermosetting agent that reacts with the curable resin by heating. As a thermosetting agent, when using (meth) acrylic polyol (A1), it is preferred to use blocked isocyanate (B). That is, in one embodiment, the curable resin composition of the present invention preferably contains (meth) acrylic polyol (A1) and blocked isocyanate (B).

[0082] The blocked isocyanate (B) is a compound obtained by blocking an isocyanate group with a protective group. When exposed to high temperature, the protective group (blocking part) undergoes thermal dissociation and detaches, and a curing reaction occurs between the generated isocyanate group and the above-mentioned (meth)acrylic polyol (A1), (meth)acrylic polyol or polycarbonate diol (polyol (a1)).

[0083] The blocked isocyanate (B) can be obtained, for example, by reacting a blocking agent with an isocyanate compound having two or more isocyanate groups in one molecule.

[0084] The isocyanate compound having two or more isocyanate groups in one molecule is not particularly limited, and examples thereof include toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, or modified products thereof.

[0085] Examples of the blocking agent include pyrazoles, phenols, oximes, lactams, and active methylene groups.

[0086] The amount of the blocked isocyanate (B) in the curable resin composition is preferably such that the ratio of the number of functional groups in the (meth)acrylic polyol (A1) to the number of isocyanate groups in the blocked isocyanate (B) (the number of functional groups / the number of isocyanate groups) is 0.4 or more and 2.5 or less, and preferably 0.6 or more and 1.4 or less.

[0087] The content of the blocked isocyanate (B) is not particularly limited, but is preferably 20% by mass or more and 50% by mass or less, and more preferably 25% by mass or more and 45% by mass or less, based on the total amount of the curable resin composition.

[0088] (Radical polymerization initiator (C))

[0089] The curable resin composition of the present invention may contain a radical polymerization initiator (C) that generates free radicals by heat or active energy rays. In the curable resin composition, when a polymer (A2) having a (meth)acryloyl group is used, a radical polymerization initiator (C) is preferably used. That is, in one embodiment, the curable resin composition of the present invention preferably contains a polymer (A2) having a (meth)acryloyl group and a radical polymerization initiator (C).

[0090] Examples of thermal radical polymerization initiators that generate free radicals by heat include azo compounds and organic peroxides. Examples of azo compounds include 2,2'-azobis(2,4-dimethylvaleronitrile) and azobisisobutyronitrile. Examples of organic peroxides include benzoyl peroxide, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.

[0091] Examples of the photoradical polymerization initiator that generates radicals using active energy rays include benzophenone compounds, alkylphenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, and thioxanthone.

[0092] As the radical polymerization initiator (C), a photoradical polymerization initiator is preferred.

[0093] The content of the radical polymerization initiator (C) in the curable resin composition is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 7% by mass or less, and further preferably 0.2% by mass or more and 5% by mass or less, based on the total amount of the curable resin composition. By making the content of the radical polymerization initiator (C) within these ranges, the curable resin composition can be cured with high curability by heating or irradiation with active energy rays.

[0094] When the curable resin composition is made into a curable resin composition that can be cured by moisture, the composition may contain a moisture-curable resin. As the moisture-curable resin, for example, a prepolymer having an isocyanate group at the end can be mentioned. The prepolymer having an isocyanate group at the end can be, for example, a prepolymer obtained by reacting a polyisocyanate with an active hydrogen-containing compound and / or an active hydrogen-containing polymer.

[0095] As the polyisocyanate used when preparing the prepolymer having an isocyanate group at the terminal, toluene diisocyanate, crude toluene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, carbodiimidized diphenylmethane diisocyanate, phenylene diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate and the like can be used, and polymethylene polyphenyl isocyanate is preferably used.

[0096] As the active hydrogen-containing compound and the active hydrogen-containing polymer, for example, the following can be used.

[0097] Active hydrogen-containing compounds such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, trimethylolethane, trimethylolpropane, castor oil, diglycerol, sorbitol, pentaerythritol, and dipentaerythritol, and active hydrogen-containing polymers having two or more terminal hydroxyl groups, an average molecular weight of 3,000 or less, an average functional group number of 2 or more, and preferably an average molecular weight of 200 to 1,000 and an average functional group number of 2 to 2.5, obtained by addition polymerization of the above active hydrogen-containing compounds with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, and tetrahydrofuran, either alone or as a mixture thereof, can be used. Other active hydrogen-containing polymers having an average molecular weight of 3,000 or less and an average number of functional groups of 1.5 or more, preferably an average molecular weight of 200 to 1,000 and an average number of functional groups of 2 to 2.5, such as polyester polyols, oil-modified polyester polyols, poly-ε-caprolactone polyols, polycarbonate diols, acrylic polyols, polyamines, polyamides, urea resins and melamine resins, may also be used in combination.

[0098] The effective NCO content of the prepolymer having a terminal isocyanate group is, for example, 1 to 15% by mass, preferably 8 to 13% by mass.

[0099] The prepolymer having a terminal isocyanate group can be synthesized as follows: the above-mentioned polyisocyanate and a common polyol including the above-mentioned active hydrogen-containing polymer are subjected to a urethanization reaction under the condition of excess isocyanate at a temperature of 40°C to 90°C, preferably 55°C to 75°C, in a system shielded from moisture.

[0100] The above-mentioned carbamate reaction is usually carried out in an organic solvent. As the solvent, ketone solvents such as methyl ethyl ketone, ester solvents such as ethyl acetate, aromatic solvents such as toluene and xylene, and other solvents commonly used as paint solvents can be used. A catalyst can also be used in the carbamate reaction. As such a catalyst, for example, a tertiary amine catalyst such as triethylamine and dimethylaniline or a metal catalyst such as tin and zinc can be used. These are also catalysts when reacting with moisture in the air when forming a coating film.

[0101] (Pigment (D))

[0102] The curable resin composition may contain a pigment (D). By containing a pigment (D) in the curable resin composition, the coating layer can be colored to form a colored layer, or a glittering property can be imparted to the coating layer. Therefore, the design of the coating formed by the transfer resin sheet can be improved.

[0103] Examples of the pigment (D) include aluminum pigments such as aluminum flakes, iridescent pigments such as mica pigments, graphite pigments, and glass flake pigments, metal oxide pigments such as titanium oxide, iron oxide, and titanium yellow, inorganic pigments such as carbon black, clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white, and organic pigments such as azo pigments, quinacridone pigments, diketopyrrolopyrrole pigments, perylene pigments, perinone pigments, benzimidazolone pigments, reducing pigments, isoindoline pigments, isoindolinone pigments, metal chelate azo pigments, phthalocyanine pigments, indanthrone pigments, dioxane pigments, and indigo pigments, but are not limited thereto.

[0104] The content of the pigment component of the active ingredient of the pigment (D) in the coating layer, i.e., the pigment component other than the binder resin, dispersant, and additive is based on the total amount of the curable resin composition, for example, 0.1% by mass or more and 50% by mass or less, preferably 0.5% by mass or more and 40% by mass or less, more preferably 1% by mass or more and 30% by mass or less. By making the content of the pigment (D) more than these lower limits, the coating formed by the transfer resin sheet can be appropriately colored, or the coating can be appropriately given glitter, etc. In addition, by making the content of the pigment (D) less than the above-mentioned upper limit, the various properties such as the shape retention, curability, elongation, and viscosity of the coating layer can be prevented from being reduced by the pigment (D).

[0105] The curable resin composition may contain a colorant other than the pigment (D), and may contain a dye. As the dye, a known dye may be used, and examples thereof include azo dyes, anthraquinone dyes, indigo dyes, and stilbene dyes.

[0106] In addition, the curable resin composition may contain ingredients other than the above, for example, additives other than the above. As additives, adhesion imparting agents, urethane reaction catalysts, urethane reaction regulators, defoamers, surface regulators, wax additives, crosslinking agents, dispersants, inorganic fillers other than pigments, anti-aging agents, antioxidants, ultraviolet absorbers, rust inhibitors, etc. can be cited.

[0107] The coating layer may be composed of a single-layer structure or a multi-layer structure. In the case of a single-layer structure, the coating layer may include one layer made of the above-mentioned curable resin composition. In the case of a multi-layer structure, each layer may be made of the above-mentioned curable resin composition. In the case of a multi-layer structure, for example, adjacent layers may be stacked and composed of multiple layers made of the above-mentioned curable resin composition having different compositions from each other. In the case of a multi-layer structure, the coating layer may have, for example, a colored layer containing any one of a pigment or a colorant other than a pigment, and at least one layer of a transparent layer that does not contain a pigment and a colorant other than a pigment, but preferably has a colored layer and a transparent layer. In the case of having a colored layer and a transparent layer, the transparent layer and the colored layer may be sequentially arranged from the transfer layer side. By such a layer structure, when the transfer resin sheet is attached to an adherend, the colored layer and the transparent layer will be arranged in the order of the colored layer and the transparent layer from the adherend side.

[0108] By making the paint layer have a colored layer as described above, the adherend can be colored by the coating formed by the paint layer. In addition, by providing a transparent layer in addition to the colored layer, the colored layer can be protected or glossy.

[0109] The transparent layer is a transparent layer, and it is sufficient as long as it has a degree of transparency that allows the color of the colored layer to be visually recognized from the outside through the transparent layer. For example, the transmittance of light with a wavelength of 450nm can be 80% or more. The transparent layer can be a coating film that does not contain a colorant, but it can also contain a small amount of a colorant as long as it does not hinder its function. In addition, in the curable resin composition for the transparent layer, when a (meth) acrylic resin is used as the curable resin, it is sufficient to contain at least a high molecular weight (meth) acrylic resin, but in this case, it may contain a plasticizing resin or may not contain a plasticizing resin.

[0110] Of course, when the coating layer is a multilayer structure, it is not limited to a two-layer structure of a transparent layer and a colored layer, and may have various laminated structures. It may be provided with two or more colored layers and one or more transparent layers to form a structure of three or more layers, or it may be provided with an omission of the transparent layer and a structure of two colored layers. In addition, it is also possible to provide two or more transparent layers. In addition, it is also possible to provide a heat insulating layer between the transparent layer and the colored layer to form a structure of three or more layers.

[0111] The thickness of the coating layer is not particularly limited, and is, for example, about 5 μm or more and 1000 μm or less, and preferably 10 μm or more and 500 μm or less.

[0112] In addition, when a colored layer and a transparent layer are provided on the coating layer, the thickness of the colored layer is not particularly limited, and is, for example, 10 μm to 100 μm, preferably 15 μm to 50 μm. In addition, the thickness of the transparent layer is not particularly limited, and is, for example, 10 μm to 100 μm, preferably 15 μm to 50 μm.

[0113] The curable resin composition constituting the coating layer may be in an uncured or semi-cured state. The so-called uncured or semi-cured state refers to a state in which the coating layer is further cured by heating or irradiating the coating layer with active energy rays. It should be noted that the so-called semi-cured state refers to a state in which a part of the curable resin composition is cured, and the so-called uncured state refers to a state in which the curable resin composition is uncured.

[0114] <Transfer layer>

[0115] In the transfer resin sheet of the present invention, the transfer layer is a support when the coating layer is transferred to an adherend such as a car body. Preferably, the transfer layer has MD and TD tensile elongation at break at 120°C of 500% or more. If the MD and TD tensile elongation at break of the transfer layer are both 500% or more, when the transfer resin sheet is attached to the coated body by vacuum forming, the transfer resin sheet easily follows the shape of the coated body, and it is easy to prevent the occurrence of breakage, wrinkles, etc., and it is easy to make the transfer resin sheet appropriately close to the coated body.

[0116] From the viewpoint of achieving excellent vacuum formability and more appropriate adhesion of the transferable resin sheet to the coated body, the transfer layer preferably has MD and TD tensile elongations at break at 120° C. of 600% or more, more preferably 700% or more.

[0117] The upper limit of the tensile elongation at break at 120°C is not particularly limited, but the tensile elongation at break in MD and TD at 120°C may be, for example, 3000% or less.

[0118] It is preferred that the MD and TD tensile elongations at break of the transfer layer at 100° C. are both 500% or more. If the MD and TD tensile elongations at break of the transfer layer are both 500% or more, when the transfer resin sheet is attached to the coated body by vacuum forming or the like, the transfer resin sheet easily follows the shape of the coated body, and it is easy to prevent the occurrence of ruptures, wrinkles, etc., and it is easy to make the transfer resin sheet appropriately adhere to the coated body.

[0119] From the viewpoint of achieving excellent vacuum formability and more appropriate adhesion of the transferable resin sheet to the coated body, the transfer layer preferably has MD and TD tensile elongations at break at 100° C. of 600% or more, more preferably 700% or more.

[0120] The upper limit of the tensile elongation at break at 100°C is not particularly limited, but the tensile elongations at break in MD and TD at 120°C may be, for example, 3000% or less.

[0121] It should be noted that the transfer layer may have both MD and TD tensile elongations within the above ranges at at least one of 100° C. and 120° C. For example, when the vacuum forming temperature is high, the MD and TD tensile elongations within the above ranges may be at 120° C., and when the vacuum forming temperature is low, the MD and TD tensile elongations within the above ranges may be at 100° C.

[0122] The tensile elongation at break of the transfer layer at 100° C. and 120° C. is the elongation at the break point measured in a tensile test of the film constituting the transfer layer, and can be measured by a measurement method in accordance with JIS K7127.

[0123] The tensile elongation at break of the transfer layer at 100° C. and 120° C. can be appropriately adjusted by the type of resin constituting the transfer layer, the presence or absence of stretching of the resin film constituting the transfer layer, the degree of stretching, and the like.

[0124] The transfer layer is made of a thermoplastic resin. By using a thermoplastic resin as the transfer layer, the tensile elongation at break at at least one of 100°C and 120°C is increased, and when the transfer resin sheet is attached to the coated body, the transfer resin sheet easily follows the shape of the coated body. In addition, it is easy to prevent the occurrence of breakage, wrinkles, etc., and it is easy to make the transfer resin sheet properly fit to the coated body. As thermoplastic resins, specifically, cyclic polyolefin resins, polyolefin resins, polyester resins, polyamide resins, acrylonitrile butadiene styrene resins, polycarbonate resins, acrylic resins, fluororesins, vinyl chloride resins, polymethylpentene resins, tetrafluoroethylene resins, etc. can be cited. By using these resins, it is easy to increase the above-mentioned tensile elongation at break.

[0125] Cyclic polyolefin resin is a polymer comprising a structural unit from a cyclic olefin. As cyclic olefin, tetracyclododecene, norbornene, cyclic conjugated diene, etc. can be mentioned. Cyclic polyolefin resin can be a polymer of cyclic olefin, or a copolymer of cyclic olefin and alpha-olefin, or a hydride thereof. As the above-mentioned alpha-olefin, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, etc., can be mentioned as a chain alpha-olefin with a carbon number of more than 1 and less than 12, among which, preferably ethylene.

[0126] The polyolefin resin is a polyolefin resin other than a cyclic polyolefin resin, and specific examples thereof include polypropylene resin and polyethylene resin, etc. Among them, polypropylene resin is preferred.

[0127] The polypropylene resin may be homopropylene, or may be a copolymer of propylene and a small amount (e.g., 10% by mass or less) of other α-olefins such as random polypropylene. Other α-olefins include chain α-olefins having 1 to 12 carbon atoms such as ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene, and 1-decene.

[0128] Examples of polyethylene resins include low-density polyethylene (LDPE, density: less than 0.930 g / cm 3 ), medium density polyethylene (MDPE, density: 0.930g / cm 3 Above and less than 0.942g / cm 3 ), high-density polyethylene (HDPE, density: 0.942g / cm 3 Above), linear low-density polyethylene (LLDPE), etc.

[0129] The polyester resin is not particularly limited, and polybutylene terephthalate (PBT) resin can be cited. The polybutylene terephthalate resin can be a homopolymer formed by terephthalic acid units and 1,4-butanediol units, or a copolymer containing units from other copolymer components other than terephthalic acid units and 1,4-butanediol units. Other copolymer components can include glycol components and dicarboxylic acid components, and can be contained in a ratio of, for example, 30 mol% or less in all units constituting the copolymer.

[0130] The resin film may be a single-layer film composed of one single layer, or a multilayer film of two or more layers. In addition, in the resin film constituting the transfer layer, the resin contained in the resin film may be used alone or in combination of two or more resins. In the case of using two or more resins in combination, different types of resins may be used for each layer to form a multilayer film. In addition, a resin obtained by mixing two or more resins may be used to form a single-layer film, or may form one or more layers in a multilayer film.

[0131] As the resin used for the resin film, among the above, one or more resins selected from cyclic polyolefin resins, polyolefin resins, and polyester resins are preferred.

[0132] Among them, one or more resins selected from cyclic polyolefin resins, polypropylene resins, and PBT resins are more preferred. By using these resins, the solvent resistance of the transfer layer is easily increased, and even if the curable resin composition is diluted with a solvent and directly applied to the transfer layer, the transfer layer can be prevented from deteriorating. From these viewpoints, the resin used for the resin film is more preferably one or more resins selected from cyclic polyolefin resins and polypropylene resins, and more preferably a cyclic polyolefin resin.

[0133] In addition, in the case of a multilayer film, the following resin layers may be used: a resin layer (also referred to as the first layer) in which the resin contained is composed of at least one resin selected from a cyclic polyolefin resin, a polypropylene resin, and a PBT resin; and a resin layer (also referred to as the second layer) in which the resin contained is composed of a polyolefin resin such as a polyethylene resin. For example, a multilayer film in which the first layer as a skin layer is provided on one or both sides of the second layer is also preferred. Specifically, a multilayer film in which the first layer composed of a PBT resin is provided on one or both sides of the second layer composed of a polyethylene resin is preferred. In this case, it is more preferred that the first layer (skin layer) is provided on both sides of the second layer (core layer). It should be noted that in the case in which the first layer is provided only on one side of the second resin layer, the first layer may be arranged on the coating layer side.

[0134] Each layer in the transfer layer may contain additives in addition to the resin. As the additive, known additives that are formulated in the resin film may be used. Specific additives include nucleating agents, fluorescent whitening agents, antioxidants, stabilizers, ultraviolet absorbers, surfactants, lubricants, fillers, crosslinking agents, crosslinking accelerators, antistatic agents, flame retardants, dispersants, pigments, dyes, processing aids, and the like.

[0135] In addition, the resin film constituting the transfer layer can be a stretch film such as a uniaxial stretch film, a biaxial stretch film, or an unstretched film, but is preferably an unstretched film. In addition, when a stretch film is used, a stretch film with a low stretch ratio can be used. By using an unstretched film or a stretch film with a low stretch ratio in the resin film, it is easy to increase the tensile elongation at break. In addition, the resin film can be a T-die film extruded by a T-die, or a blown film.

[0136] The transfer layer may also be a layer obtained by subjecting at least one surface to a release treatment using a release agent such as a silicone release agent, a non-silicone (organic release agent) release agent, or a fluorine release agent. When the transfer layer is subjected to a release treatment, the release treatment surface preferably constitutes the surface on the coating layer side. By subjecting the transfer layer to a release treatment, it is easy to make the peelability from the coating layer good.

[0137] The thickness of the transfer layer is not particularly limited, and is, for example, 30 μm or more and 300 μm or less, and preferably 50 μm or more and 200 μm or less.

[0138] [Layer composition]

[0139] For example, Figure 1 As shown, the transfer type resin sheet 10 includes a coating layer 11 and a transfer layer 12. The coating layer 11 is formed on one surface of the transfer layer 12, and these are integrated. The coating layer 11 may be directly laminated on the transfer layer 12.

[0140] The transfer resin sheet 10 may be Figure 1 As shown in the figure, the coating layer 11 and the transfer layer 12 are formed, and other layers may also be provided. Figure 2 As shown, the transfer resin sheet 10 can be provided with a release film 13, and the release film 13 is attached to the surface of the coating layer 11. The release film 13 can use a known release film without particular limitation, and can be a release film made of a resin film, or a release film obtained by subjecting at least one surface of the resin film to a release treatment using a release agent such as a silicone-based release agent, a non-silicone-based (organic release agent), or a fluorine-based release agent. When the release film 13 is subjected to a release treatment, the release-treated surface can be arranged at a position in contact with the coating layer 11. The release film 13 can be peeled off from the coating layer 11 before the transfer resin sheet 10 is attached to the coated body, thereby being removed from the transfer resin sheet 10.

[0141] In addition, if Figure 3 As shown, the transfer resin sheet 10 may include a support layer 14, and the support layer 14 is attached to the surface of the coating layer 11. The support layer 14 may be formed using resin, rubber, etc. In addition, the support layer 14 may be a layer obtained by subjecting the surface in contact with the coating layer 11 to a release treatment similar to a release film.

[0142] (Method for producing transfer resin sheet)

[0143] The method for producing the transfer type resin sheet of the present invention is not particularly limited, and preferably, a coating liquid is prepared by diluting the curable resin composition with a solvent, applying it on a transfer layer composed of a resin film, etc., and drying it to produce it. The coating liquid is not particularly limited, and can be obtained, for example, by mixing various components constituting the curable resin composition, such as a curing resin, a curing agent, a free radical polymerization initiator, a pigment, and other additives in a solvent.

[0144] As the above-mentioned solvent, for example, ethyl acetate, butyl acetate, toluene, etc. can be cited. From the perspective of the availability and workability of the desired transfer resin sheet, ethyl acetate is preferred. The amount of the solvent used is not particularly limited, and is, for example, 50 parts by mass or more and 1000 parts by mass or less, preferably 100 parts by mass or more and 500 parts by mass or less, relative to 100 parts by mass of a curable resin such as a (meth) acrylic resin.

[0145] The method for applying the coating liquid to the transfer layer is not particularly limited, and the coating liquid can be applied to the transfer layer using a known coating device.

[0146] The drying temperature in the preliminary drying step is preferably 50° C. to 70° C., more preferably 55° C. to 65° C. The drying time in the preliminary drying step is preferably 10 minutes to 60 minutes, more preferably 15 minutes to 45 minutes.

[0147] The drying temperature in the formal drying process is preferably 85° C. to 130° C., more preferably 90° C. to 120° C. If the drying temperature is above these lower limits, the solvent can be easily removed from the coating liquid to prevent the solvent from being vaporized and generating bubbles when the coating layer is cured. In addition, by setting the drying temperature below the upper limit, it is possible to prevent the curable resin composition from being cured to a degree greater than necessary during drying.

[0148] The drying time in the formal drying process is preferably more than 10 minutes and less than 60 minutes, more preferably more than 15 minutes and less than 45 minutes. By setting the drying time to more than the above lower limit, the solvent can be easily removed from the coating liquid appropriately to prevent the solvent from being gasified and generating bubbles when the coating layer is cured. In addition, by being set to less than the above upper limit, it is possible to prevent the curable resin composition from being cured to a necessary degree during drying.

[0149] In addition, the dried transfer resin sheet can be initially cured as needed. The so-called initial curing refers to curing the curable resin composition constituting the coating layer to a semi-cured state. The initial curing can be performed by heating, by irradiation with active energy rays, or by moisture. It should be noted that when the initial curing is performed by heating, the initial curing can be performed under the conditions of a heating temperature of 135°C or more and 150°C or less and a heating time of 5 minutes or more and 10 minutes or less.

[0150] (How to use the transfer resin sheet)

[0151] The transfer resin sheet in the present invention is used to form a coating on various articles (coated objects). Specifically, after the transfer resin sheet is attached to various coated objects, the coating layer is cured and the cured coating layer is used as a coating. It should be noted that the transfer layer can be peeled off from the coating layer attached to the coated object, thereby being removed from the coated object.

[0152] As the coated body that utilizes transfer resin sheet to be coated, it is not particularly limited, and for example, electrification products etc. can be cited. In addition, vehicle interior decoration materials such as automobile and railway vehicle interior decoration materials, vehicle exterior decoration materials such as automobile and railway vehicle exterior decoration materials, and sundries etc. can also be cited. In addition, exterior decoration materials for heavy machinery, ships and aircraft, outer walls and roof materials of houses and buildings, as well as bridges, steel bars, factory equipment and wind power generation blades etc. can also be cited. Among them, vehicle exterior decoration materials such as automobile exterior decoration materials are preferred. As vehicle exterior decoration materials, for example, sunshade, skylight, car door, buffer, oil inlet panel, rear trunk lid, rear folding baffle etc. can be cited. When the transfer resin sheet is attached to the vehicle exterior decoration material, it can be attached to the exterior decoration material that has been installed to the vehicle body, and it can also be attached to the exterior decoration material before being installed to the vehicle body.

[0153] In addition, the material of the coated body is not particularly limited, and can be any material of resin materials, inorganic materials such as ceramics, and metal materials such as steel, among which metal materials such as steel are preferred. Metal materials such as steel are difficult to be coated at the same time as the coated body is molded by insert molding, and are difficult to be coated using a resin sheet, but by using the transfer resin sheet of the present invention, even such materials can be easily coated.

[0154] There is no particular limitation on the method of attaching the transfer resin sheet to the coated body. It can be done by manual pasting using a squeegee or the like, or by using a laminating device. In addition, it can also be done by press molding, insert injection, vacuum molding, etc. Among them, the method of attaching by vacuum molding is preferred. In the case of attaching by vacuum molding, the transfer resin sheet can be heated to, for example, 90°C or more and 130°C or less, preferably 100°C or more and 125°C or less, and vacuum molding is performed.

[0155] The transfer resin sheet can be attached to the coated body after being pre-shaped into a shape corresponding to the shape of the coated body by vacuum forming, pressure forming, compressed air forming, etc. In the case of pre-shaping, the curable resin sheet is preferably as follows: Figure 3 As shown, the pre-shaping is performed with the support layer 14 attached to the coating layer 11. The pre-shaping is performed by shaping the transfer type resin sheet into a certain shape using a jig. By pre-shaping the transfer type resin sheet with the support layer, the coating layer can be prevented from adhering to the jig.

[0156] Among the above, the pre-shaping is preferably performed by vacuum forming. In addition, the pre-shaped transfer resin sheet can be attached to the coated body after removing the support layer. At this time, the transfer resin sheet can be attached by manual pasting, can also be attached to the coated body using a laminating device, or can be attached by other methods.

[0157] As described above, the coating layer of the transfer resin sheet attached to the coated body can be cured. In the case where the curable resin composition can be cured by heat, the curing of the coating layer can be cured by heating. The heating temperature in the case of curing by heating is not particularly limited, as long as the coating layer can be cured, for example, it is 135°C or more and 170°C or less, preferably 140°C or more and 160°C or less. In addition, the heating time is, for example, 30 minutes or more and 90 minutes or less, preferably 60 minutes or more and 90 minutes or less.

[0158] In addition, when the curable resin composition can be cured by active energy rays, the coating layer can be cured by irradiating the active energy rays. As active energy rays, ultraviolet rays (UV) are preferably used from the aspects of curability and convenience. The irradiation amount of the active energy rays is not particularly limited, and is, for example, 200 mJ / cm 2 Above and 5000mJ / cm 2 Below, preferably 500mJ / cm 2 Above and 2000mJ / cm 2 the following.

[0159] In addition, when the curable resin composition can be cured by moisture, it can be cured by moisture.

[0160] As for the transfer type resin sheet, since the transfer layer has tensile strength, the vacuum forming property becomes good. Therefore, the transfer type resin sheet is preferably attached to the coated body by vacuum forming. In addition, it is also preferred to attach the transfer type resin sheet to the coated body after pre-forming by vacuum forming. Figure 4 , a method for forming a coating on a coated object by attaching a transfer resin sheet to the coated object by vacuum forming is described in more detail.

[0161] First, the object 20 to be coated may be prepared, such as Figure 4 The transfer type resin sheet 10 is attached to the object 20 by vacuum forming as shown in (a) and (b). At this time, the transfer type resin sheet 10 is attached to the object 20 in such a manner that the coating layer 11 contacts the object 20. In addition, the transfer type resin sheet 10 can be closely attached to the object 20 while being stretched and shaped along the shape of the object 20 by vacuum forming.

[0162] Here, the vacuum forming is preferably TOM forming. TOM stands for "Three Dimension Overlay Method". If TOM forming is applied, the transfer resin sheet 10 can be closely attached to and adhered to the surface of the object 20 having a complex shape.

[0163] exist Figure 5 , a schematic diagram of an apparatus for performing TOM molding is shown in FIG. A transfer resin sheet 10 is provided in a TOM molding apparatus 30, an upper box 31 is provided above the transfer resin sheet 10, and a lower box 32 is provided below the transfer resin sheet 10. In the lower box 32, a coated body 20 is arranged on an upper and lower lifting platform 35. The coating layer of the transfer resin sheet 10 is arranged on the lower side, and the transfer layer is arranged on the upper side.

[0164] In this state, the upper box 31 and the lower box 32 are decompressed, and the transfer resin sheet 10 is heated by a near infrared heater or the like. Next, the body 20 to be coated is raised by the upper and lower lifting platforms 35, and the body 20 to be coated and the transfer resin sheet 10 are pressed together. Then, compressed air is introduced only into the upper box 11 and maintained for a certain period of time, thereby allowing the transfer resin sheet 10 to be attached to the surface of the body 20 to be coated, thereby attaching the transfer resin sheet 10 to the body 20 to be coated. Of course, vacuum forming can also be applied by methods other than TOM forming.

[0165] When the transfer resin sheet 10 is attached to the object 20 to be coated, the following steps are performed: Figure 4As shown in (c), the coating layer 11 is cured, and the cured coating layer 11 is used to form a coating on the coated body 20. The coating layer 11 can be cured by heating, by irradiation with active energy rays, or by moisture. The details of the heating and active energy ray irradiation conditions are as described above.

[0166] Then, if Figure 4 As shown in (d), the transfer layer 12 can be peeled off from the coating layer 11, thereby removing the transfer layer 12 from the coated object 20. However, the transfer layer 12 can also be peeled off from the coating layer 11 before curing to remove it from the coated object 20. Figure 4 As shown in (d), the paint layer 11 can be so-called trimmed, that is, unnecessary portions can be cut off as appropriate.

[0167] Next, refer to Figure 6 An example of a coating method using a transfer resin sheet pre-shaped by vacuum forming is described in detail. Figure 6 As shown in (a), a transfer resin sheet 10 having a support layer 14 and attached to the surface of the coating layer 11 is prepared, and a jig 40 is further prepared. The surface 40A of the jig 40 may have a shape that matches the surface shape of the coated body 20. The jig 40 may be made of any material, and may be formed of a resin material or may be formed of a metal.

[0168] The transfer resin sheet 10 having the support layer 14 can be arranged on the jig 40 in such a manner that the support layer 14 side becomes the surface 40A side of the jig 40, as shown in FIG. Figure 6 As shown in (b), the transfer resin sheet 10 is closely attached to the fixture 40 by vacuum forming, and the transfer resin sheet 10 is stretched while being formed into a shape corresponding to the surface shape of the coated body 20. The conditions of vacuum forming are as described above. In addition, vacuum forming is preferably performed by TOM forming, but it can also be performed by methods other than TOM forming. It should be noted that the specific method of TOM forming is as described above, and the fixture 40 can be configured in the TOM forming device 30 instead of the coated body 20.

[0169] like Figure 6 The transfer resin sheet 10 pre-shaped as shown in (b) can be so-called trimmed, that is, unnecessary portions can be cut as appropriate.

[0170] In addition, next, Figure 6 As shown in (b) and (c), the pre-shaped transfer type resin sheet 10 is removed from the jig 40 , and the support layer 14 can be removed from the transfer type resin sheet 10 .

[0171] The transfer resin sheet 10 obtained by pre-forming and removing the support layer 14 is as follows: Figure 6 (c) is attached to the coated body 20. Here, the method of attaching the transfer type resin sheet 10 to the coated body 20 is not particularly limited, and it can be done by manual pasting using a squeegee or the like, or by pasting using a laminating device. Since the transfer type resin sheet 10 is pre-shaped in a shape corresponding to the surface shape of the coated body 20, it can be easily attached to the coated body 20 even by manual pasting or the like.

[0172] When the transfer resin sheet 10 is attached to the object 20 to be coated, the following steps are performed: Figure 6 As shown in (d), the coating layer 11 is cured, and a coating is formed on the coated body 20 using the coating layer 11. The coating layer 11 can be cured by heating, by irradiation with active energy rays, or by moisture. The details of the heating and irradiation conditions of active energy rays are as described above. In addition, the transfer layer 12 can be peeled off from the coating layer 11, thereby removing the transfer layer 12 from the coated body 20. The transfer layer 12 can also be removed before the coating layer 11 is cured, but it is preferably removed after the coating layer 11 is cured.

[0173] Example

[0174] Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.

[0175] The measuring method and the evaluation method in the present invention are as follows.

[0176] <Viscosity value of the coating layer>

[0177] The viscosity value of the coating layer was measured according to the following method. Specifically, the coating layer was placed in a probe initial adhesion tester (TA-500 manufactured by Yubiem Co., Ltd.) in such a way that the coating transfer curable resin was attached to the probe. The measurement was carried out under the following conditions, and the maximum load during peeling was evaluated as the viscosity value.

[0178] Probe diameter: 5mm, speed: 10mm / s, contact load: 100gf, contact time: 1s

[0179] <Tensile elongation at break of transfer layer>

[0180] The tensile elongation at break of the transfer layer was measured by the measuring method according to JIS K7127. Specifically, the film for the transfer layer was cut into a dumbbell shape with a width of 10 mm × a marking width of 25 mm, and then installed in a tensile testing machine. In Examples 1 to 8 and Comparative Examples 1 to 2, the film was stretched at a stretching speed of 100 mm / min in a constant temperature bath set at 120°C, and the tensile elongation was calculated by the following formula based on the displacement of the point at which the film broke. In addition, in Examples 9 to 12 and Comparative Examples 3 to 4, the film was stretched at a stretching speed of 100 mm / min in a constant temperature bath set at 100°C, and the tensile elongation was calculated by the following formula based on the displacement of the point at which the film broke. It should be noted that the clamp width was set to the same width as the marking width. The tensile elongation at break of the transfer layer was measured for both MD and TD.

[0181] Tensile elongation (%) = (displacement at break / marking line width) × 100

[0182] <Scratch resistance>

[0183] The measurement was performed by pencil scratching in accordance with JIS K5600-5-4.

[0184] Specifically, the measurement samples were prepared according to the following procedure. In Example 7, the transfer resin sheet prepared was attached to a sintered coated plate and then irradiated with ultraviolet light at 3000 mJ / cm 2 After curing under the conditions of , the transfer film was peeled off to prepare an evaluation sample. In the examples other than Example 7, after the transfer resin sheet was attached to the sintered coated plate, the transfer film was peeled off, and after the coating layer was transferred to the sintered coated plate, the sintered coated plate was placed in an oven at 160°C for 1 hour to be thermally cured.

[0185] The surface of the cured paint layer was scratched by holding a pencil at an angle of 45° and applying a load of 1 kg. After rubbing for 10 mm, the scratch condition was checked and the highest pencil hardness without scratch was used. The pencil used was "Mitsubishi Pencil Uni (Mitsubishi Pencil Co., Ltd.) certified by the Japan Paint Inspection Association".

[0186] <Adhesion>

[0187] The adhesion was evaluated according to the following method. First, water containing 0.5% of a polyalkyl ether surfactant was sprayed onto the sintered coated plate. Next, the transfer resin sheet was arranged so that the attachment surface overlapped with the sintered coated plate, and then the transfer layer was rubbed with a squeegee to press the transfer layer while draining the water. After the press bonding, the adhesion was evaluated based on the peeling behavior when the transfer layer was peeled off.

[0188] A: There was no lifting or peeling of the paint layer, and the film was attached smoothly.

[0189] B: Floating, peeling, etc. occurred in the coating layer, and smooth adhesion was not possible.

[0190] <Vacuum formability>

[0191] The transfer type resin sheets prepared in the respective Examples and Comparative Examples were evaluated for vacuum formability by TOM molding as shown below.

[0192] The coated body (test piece カーシェイプ made by ASONE) is placed on the upper and lower lifting platforms equipped in the TOM molding machine (manufactured by FUSE Vacuum Co., Ltd., trade name "NGF-0709-S") composed of an upper box and a lower box. Then, a curable resin sheet is set on the sheet clamp frame of the molding machine in a manner such that the coating layer is on the lower side and the transfer layer is on the upper side. Next, the vacuum degree in the upper and lower boxes is reduced in a manner such that the gauge pressure is less than 0.0 kPa, and the temperature of the transfer resin sheet is heated to 120°C. Among them, in Examples 9 to 12 and Comparative Examples 3 to 4, the temperature of the transfer resin sheet is heated to 100°C. Then, the coated body is raised, the coated body and the transfer resin sheet are pressed together, and then compressed air is introduced only into the upper box and maintained for 5 seconds. The upper and lower boxes are opened to atmospheric pressure to obtain a laminated body consisting of the coated body and the transfer resin sheet. The obtained laminated body was observed and the vacuum formability was evaluated according to the following criteria.

[0193] A: The transfer-type resin sheet follows the three-dimensional shape of the coating object and is in a uniform and close contact state.

[0194] B: The transfer resin sheet cannot completely follow the three-dimensional shape of the object to be coated, and the sheet is broken. Alternatively, wrinkles are formed throughout the sheet.

[0195] -: The transfer resin sheet was deformed and could not be fixed by the sheet fixture of the molding machine, so the evaluation could not be performed.

[0196] The components used in Examples and Comparative Examples and the films used in the transfer layer are as follows.

[0197] <(Meth)acrylic resin (A) and plasticizer resin (a)>

[0198] As acrylic polyol, reactive polymer containing an acryl group, and polycarbonate diol, those described in the following Table 1 were used.

[0199] [Table 1]

[0200]

[0201] <Blocked isocyanate (B)>

[0202] Hexamethylene diisocyanate blocked isocyanate (HDI), "Takenet B-882N" manufactured by Mitsui Chemicals, blocking agent type: 2-butanone oxime (MEKO), NV = 70%, solvent is naphtha, contains a small amount of urethanization catalyst

[0203] <Photoradical polymerization initiator (C)>

[0204] Acetophenone compound, "Omnirad 1173" manufactured by BASF (NV = 100 mass%)

[0205] <Pigment (D)>

[0206] Pigment dispersion: "NSP-UP 841B" manufactured by Nichiho Bic Co., Ltd., effective pigment concentration = 9 mass%, NV = 24 mass%

[0207] <Film for transfer layer>

[0208] Unstretched cyclic polyolefin film ("Decofit Q16CK" manufactured by Toray Industries, Inc., thickness 100 μm)

[0209] Unstretched multilayer polybutylene terephthalate film

[0210] Unstretched multilayer olefin film 1 ("Combini PP" manufactured by Okamoto Co., Ltd., thickness 100 μm)

[0211] Unstretched multilayer olefin film 2 ("Combini PE" manufactured by Okamoto Co., Ltd., thickness 100 μm)

[0212] Unstretched polyethylene terephthalate film ("KANERON KA-20" manufactured by Shinei Chemical Co., Ltd., thickness 100 μm)

[0213] Biaxially stretched polyethylene terephthalate film ("Cosmopil E7004" manufactured by Toyobo Co., Ltd.)

[0214] [Example 1]

[0215] According to the formulation described in Table 2, 71 parts by mass of acrylic polyol (A1), 9 parts by mass of acrylic polyol (a1-(1)), and 20 parts by mass of blocked isocyanate (B) were mixed while being thoroughly stirred to prepare a coating liquid of a curable resin composition.

[0216] The coating liquid was applied to the smooth surface of an unstretched cyclic polyolefin film (manufactured by Toray Co., Ltd., "Decofit Q16CK") constituting the transfer layer by means of an applicator. Then, a pre-drying process was performed at a drying temperature of 60°C and a drying time of 30 minutes, and then a formal drying process was performed at a drying temperature of 90°C and a drying time of 30 minutes to obtain a transfer resin sheet having a coating layer with a thickness of 50 μm formed on the transfer layer. In the above drying process, the solvent was removed from the coating liquid, and as a result, the obtained coating layer had the formulation described in Table 3.

[0217] [Examples 2 to 5, 7 to 8, Comparative Examples 1 to 2]

[0218] A transfer type resin sheet was obtained in the same manner as in Example 1 except that the curable resin composition used in the coating liquid and the film used in the transfer layer were changed as shown in Table 2. In Example 5, a transfer type resin sheet was obtained by further mixing the pigment described in Table 1.

[0219] [Example 6]

[0220] A transfer-type curable resin sheet for coating was prepared by the same method as in Example 1 except that an unstretched multilayer polybutylene terephthalate film was used as the transfer layer film and the formulation of the curable resin composition used in the coating liquid was changed as shown in Table 2. The unstretched multilayer polybutylene terephthalate film was prepared according to the following procedure.

[0221] The raw material of the skin layer was prepared according to the following procedure. 100 parts by mass of polybutylene terephthalate resin (Mitsubishi Engineering Plastics Co., Ltd., trade name "Nobaduran 5010CS") and a crystal nucleating agent (bis(4-methylbenzylidene) sorbitol, T m =200°C (manufactured by Shin Nippon Rika Co., Ltd., trade name: Gel Or E-200) and 5 parts by mass were blended, melt-kneaded and pelletized at a barrel temperature of 250°C using a twin-screw extruder to prepare a nucleating agent masterbatch having a nucleating agent concentration of 5% by mass. Next, the polybutylene terephthalate described above was blended with the nucleating agent masterbatch and the resultant was used as a raw material. The amount of the nucleating agent added was 3 parts by mass relative to 100 parts by mass of the polybutylene terephthalate, i.e., the amount of the nucleating agent added was 1500 ppm.

[0222] A high-density polyethylene resin ("Nobatec HD" manufactured by Nippon Polyethylene Co., Ltd.) was used as a raw material for the core layer.

[0223] A three-layer T-mold film molding machine having three extruders with a screw diameter of 40 mm was used. The raw materials were fed into each extruder, and under the conditions of a molding temperature of 250°C, a chill roll temperature of 80°C, and an air chamber static pressure of 15 mmH2O, a multilayer unstretched polybutylene terephthalate film (multilayer PBT film, thickness 200 μm) consisting of two types of three layers, wherein the two skin layers were PBT resin layers with a thickness of 50 μm and the core layer was a polyethylene resin layer with a thickness of 90 μm was obtained.

[0224] [Example 9]

[0225] The tensile elongation at break of the transfer layer was measured at 100°C. A transfer resin sheet was prepared by the same method as in Example 1, except that an unstretched multilayer olefin film 1 ("Convini PP" manufactured by Okamoto Co., Ltd., with a thickness of 100 μm) was used as the transfer layer film and no formal drying process (drying temperature 90°C, drying time 30 minutes) was performed.

[0226] [Example 10]

[0227] The tensile elongation at break of the transfer layer was measured at 100°C. A transfer resin sheet was prepared by the same method as in Example 2, except that an unstretched multilayer olefin film 2 ("Convini PE" manufactured by Okamoto Co., Ltd., with a thickness of 100 μm) was used as the transfer layer film and no formal drying process (drying temperature 90°C, drying time 30 minutes) was performed.

[0228] [Example 11]

[0229] The tensile elongation at break of the transfer layer was measured at 100°C. A transfer resin sheet was prepared by the same method as in Example 3, except that an unstretched polyethylene terephthalate film ("Kaneron KA-20" manufactured by Shinei Chemical Co., Ltd., thickness 100 μm) was used as the transfer layer film and no formal drying process (drying temperature 90°C, drying time 30 minutes) was performed.

[0230] [Example 12]

[0231] The tensile elongation at break of the transfer layer was measured at 100°C. A transfer resin sheet was prepared by the same method as in Example 1, except that a biaxially stretched polyethylene terephthalate film ("Cosmopil E7004" manufactured by Toyobo Co., Ltd.) was used as the transfer layer film and the formulation of the curable resin composition used in the coating liquid was changed as shown in Table 3.

[0232] [Comparative Example 3]

[0233] A transfer resin sheet was prepared by the same method as in Comparative Example 1, except that an unstretched multilayer olefin film 1 ("Convini PE" manufactured by Okamoto Co., Ltd., with a thickness of 100 μm) was used as the transfer layer film, the tensile elongation at break of the transfer layer was measured at 100°C, and no formal drying process (drying temperature 90°C, drying time 30 minutes) was performed.

[0234] [Comparative Example 4]

[0235] A transfer resin sheet was prepared by the same method as in Comparative Example 2, except that an unstretched multilayer olefin film 1 ("Combini PE" manufactured by Okamoto Co., Ltd., with a thickness of 100 μm) was used as the transfer layer film, the tensile elongation at break of the transfer layer was measured at 100°C, and no formal drying process (drying temperature 90°C, drying time 30 minutes) was performed.

[0236] [Table 2]

[0237]

[0238] [Table 3]

[0239]

[0240] Table 4 below shows the content of each component based on the total solid content of the curable resin composition in Examples 1 to 8 and Comparative Examples 1 and 2. Among them, the amount of the active ingredient in the pigment in Example 5 was 2% by mass based on the total solid content of the curable resin composition.

[0241] [Table 4]

[0242]

[0243] In each of the above examples, since the viscosity value of the coating layer on the attachment side at 23°C is limited to a certain range, a transfer resin sheet with excellent scratch resistance and adhesion can be manufactured. In addition, in Examples 1 to 7, 9 to 11, since a transfer layer with a high tensile elongation at break at 120°C or 100°C is used, the vacuum formability is good and the transfer resin sheet is excellent.

[0244] The resin sheet follows the three-dimensional shape of the object to be coated and can be evenly adhered to the object, and appropriate coating can be formed by the resin sheet by vacuum forming.

[0245] In contrast, in Comparative Examples 1 and 3, the adhesive value of the coating layer on the attachment side at 23°C was low, so the adhesive force to the adherend was insufficient and it was not smoothly attached. In addition, in Comparative Examples 2 and 4, the adhesive value of the coating layer on the attachment side at 23°C was high and the hardness was insufficient, so the scratch resistance was poor.

[0246] Description of Reference Numerals

[0247] 10Transfer-type curable resin sheet for coating

[0248] 11 coating layers

[0249] 12 transfer layers

[0250] 13 Release film

[0251] 14 support layers

[0252] 20 Coated body

[0253] 30TOM molding device

[0254] 31 upper box

[0255] 32 lower box

[0256] 35 Up and down lifting platform

[0257] 40 clamps

Claims

1. A transfer-type curable resin sheet for coating, comprising a coating layer and a transfer layer, wherein the coating layer comprises a curable resin composition that can be cured by heat, moisture or active energy rays, and the transfer layer comprises a thermoplastic resin, The viscosity value of the surface of the coating layer opposite to the surface on which the transfer layer is provided at 23° C. is 300 N / cm 2 Above and 4000N / cm 2 the following. 2 . The transfer-type curable resin sheet for coating according to claim 1 , wherein the transfer layer has MD and TD tensile elongations at break at 120° C. of 500% or more. 3 . The transfer-type curable resin sheet for coating according to claim 1 , wherein the transfer layer has both MD and TD tensile elongations at break at 100° C. of 500% or more. The transfer curable resin sheet for coating according to any one of claims 1 to 3, wherein the curable resin composition comprises a (meth)acrylic resin (A) having a weight average molecular weight of 100,000 to 1,000,000, which is solid and has a plurality of functional groups.

5. The transfer-type curable resin sheet for coating according to claim 4, wherein the (meth)acrylic resin (A) is a (meth)acrylic polyol (A1), The curable resin composition includes a blocked isocyanate (B).

6. The transfer-type curable resin sheet for coating according to claim 4, wherein the (meth)acrylic resin (A) is a polymer (A2) having a (meth)acryloyl group. The curable resin composition contains a radical polymerization initiator (C) that generates radicals by heat or active energy rays. 7 . A method for forming a coating, comprising attaching the transfer-type curable resin sheet for coating according to claim 1 to an object to be coated, and then curing the coating layer to form a coating. 8 . The coating forming method according to claim 7 , wherein the transfer layer is peeled off from the paint layer to remove the transfer layer from the coated object.

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