JP2012071456A - Thermal transfer film and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermal transfer film wherein the base film can be easily peeled off by heating and also trimming property of the transfer coating film at the time of peeling is good, and furthermore, a protective layer obtained thereby is excellent in surface physical properties.SOLUTION: There are provided: a thermal transfer film having a transfer layer having a radical polymerizable resin composition layer and a decorative layer laminated in this sequence on the base film mainly consisting of polyvinyl alcohol resin. in which the radical polymerizable resin composition layer contains thermoplastic resin at 20 to 80 mass% and 10 to 70 mass% of polymerization compound having a (meth)acryloyl group of 100 to 1,500 in number average molecular weight, and in which the reaction rate of the (meth)acryloyl group is 5 to 30% after heated by attenuated total reflection (ATR) at 160°C for 10 minutes using FT-IR of the radical polymerizable resin composition layer; and a method for manufacturing the decorative article.

Description

  In the present invention, for example, a transfer layer including at least a protective layer is transferred and formed on the surface of various transfer substrates such as a synthetic resin substrate, a wood substrate, an inorganic substrate, and a metal substrate. This relates to a transfer film.

  Conventionally, as a decoration method of articles, a protective layer or the like is simply applied to the surface of various transferred substrates such as a synthetic resin substrate, a wood substrate, an inorganic substrate, a metal substrate, etc. by a dry method. A transfer method using a transfer film that can be formed is used. With this transfer method, a protective layer made of a resin composition having excellent surface properties such as hardness and solvent resistance is provided on a base film made of paper, a thermoplastic resin film, etc. in a peelable state, and further required A transfer film is prepared by providing a pattern layer, an adhesive layer, etc. (hereinafter referred to as a transfer layer together with the protective layer), and the transfer layer surface of the transfer film is placed on the surface of the substrate (transferred substrate). After the transfer layer is bonded to the transfer substrate by pressure bonding, the transfer layer is transferred and formed on the transfer substrate by peeling at the interface between the transfer layer and the substrate film and removing the substrate film. This is a method for producing a decorative product or the like for the purpose.

  As the protective layer, a thermosetting resin is used to impart excellent surface properties such as surface hardness, abrasion resistance, scratch resistance, solvent resistance, and chemical resistance to the surface of the product after transfer. Alternatively, a curable resin such as an active energy ray curable resin is generally used, and specifically, a two-component curable polyurethane resin that is a reaction product of a polyol compound and an isocyanate compound, Various materials using ionizing radiation curable acrylate resins having radically polymerizable double bonds have already been used. (For example, see Patent Document 1)

On the other hand, polyester-based resin films such as polyethylene terephthalate are widely used as the base film, and in particular, most are biaxially stretched because of good thickness accuracy and surface smoothness. Furthermore, a method of adjusting the peel strength by providing a plasma treatment or a melamine resin release layer on the peel surface is also known.
However, these polyester-based resin films have poor productivity because it is necessary to provide a melamine resin release layer on the release surface, and when a biaxially stretched film is used, shape followability during molding processing is poor. It was insufficient.

Patent Document 2 describes a method of obtaining a transfer film having a stable peel strength without using a melamine resin release layer or the like by using a vinyl alcohol polymer resin such as polyvinyl alcohol as a base film. Yes.
In paragraph 0011, a composition containing an acrylic resin as a main component is suitable for the transfer layer. Furthermore, it is described that various curable resins need to be selected when the surface of the transfer target after transfer requires scratch resistance or the like.
However, when a vinyl alcohol polymer resin is used as the base film, if a composition mainly composed of an acrylic resin is used for the transfer layer, the peel strength after transfer is stable and low, but the peel strength is too weak. Therefore, when a decorative layer is provided by gravure printing or the like, peeling or floating may occur when the film is rolled and stored or transported, or when the film is unwound for transfer processing. Furthermore, if the peel strength is too weak, when the substrate film is peeled after the film is pressure-bonded to the substrate to be transferred, the foil cut-off property (trimming property) of the transfer coating film at the transfer substrate terminal is poor, and the non-transfer portion In many cases, the coating film remains as a residue on the decorative molded product and lacks productivity. On the other hand, if the active energy ray curable resin or the thermosetting resin is appropriately selected, when the base film is peeled off, the peel strength is too high and the base film cannot be peeled at all, or the transfer layer is destroyed. May cause.

Japanese Patent Laid-Open No. 7-314995 JP 09-277458 A

  The problem to be solved by the present invention is a transfer film that uses a polyvinyl alcohol (hereinafter abbreviated as PVA) resin as a base film and a radically polymerizable resin composition layer as a protective layer, and can be easily heated. An object of the present invention is to provide a thermal transfer film that can peel a base film, has a good trimming property of a transfer coating film at the time of peeling, and is excellent in surface physical properties of a protective layer obtained.

In the range of 20 to 80% by mass of a thermoplastic resin and a number average molecular weight of 100 to 1500 based on the total solid content in the protective layer using the base film mainly composed of PVA resin. A total reflection method using a radical polymerizable resin composition layer containing 10 to 70% by mass of a polymerizable compound having a (meth) acryloyl group, and using FT-IR of the radical polymerizable resin composition layer It has been found that a thermal transfer film having a (meth) acryloyl group reaction rate of 5 to 30% after heating at 160 ° C. for 10 minutes by (ATR) solves the above problems.
In the present invention, the protective layer component uses the above-mentioned amount of the thermoplastic resin, so that the layer thickness can be maintained at room temperature even when it is uncured, and appropriate adhesion to the PVA substrate film is maintained. It can be easily peeled off from the substrate film when heated and transferred.
On the other hand, a polymerizable compound having a number average molecular weight of 100 to 1500 and having a (meth) acryloyl group flows in the transfer layer during film production / storage and heating, and moves to the vicinity of the interface between the PVA layer and the protective layer. And it discovered that it functions as a mold release layer in the interface with the PVA layer which is a base film because a (meth) acryloyl group carries out a polymerization reaction by heating. Therefore, the amount that can function as a release layer at the interface with the PVA layer within the general thermal transfer time is specified, and furthermore, the flow inside the transfer layer is possible at the time of film production / storage and at the general molding temperature. Specific molecular weight, and by controlling the reaction rate of (meth) acryloyl groups by heating, the base film can be easily peeled by heating, and good trimming properties can be secured. It has been found that a thermal transfer film having excellent surface properties can be obtained.

Specifically, the reaction rate of the (meth) acryloyl group after heating at 160 ° C. for 10 minutes by the total reflection method (ATR) using FT-IR of the radical polymerizable resin composition layer is 5 to 30%. By heating the thermal transfer film of the present invention so that the reaction rate of the (meth) acryloyl group contained in the radical polymerizable resin composition layer is 5 to 30%, the polyvinyl alcohol is further added. The peelability from the layer is easy, and the trimming property of the transfer coating film is improved.
The polymerizable compound having the (meth) acryloyl group penetrates and permeates the pattern layer / adhesive layer (decorative layer), and is also present near the interface between the substrate to be transferred and the decorative layer. It has also been found that there is an effect of improving the adhesion to the substrate to be transferred by curing by irradiation with an electron beam.

  That is, the present invention is a thermal transfer film having a transfer layer in which a radical polymerizable resin composition layer and a decorative layer are laminated in this order on a base film mainly composed of a PVA resin, the radical polymerizable resin The composition layer contains 20 to 80% by mass of a thermoplastic resin with respect to the total solid content, 10 to 70% by mass of a polymerizable compound having a (meth) acryloyl group having a number average molecular weight of 100 to 1500, and Provided is a thermal transfer film in which the reaction rate of (meth) acryloyl groups after heating at 160 ° C. for 10 minutes by total reflection method (ATR) using FT-IR of a radical polymerizable resin composition layer is 5 to 30%.

  Moreover, this invention is a manufacturing method of the said thermal transfer film, Comprising: The base film which has PVA resin which provided the radical polymerizable resin composition layer as a main component, and the base film which provided the decorating layer A method for producing a thermal transfer film which is aged after being laminated so that the radical polymerizable resin composition layer and the decorative layer are in contact with each other is provided.

  In the present invention, the above-described thermal transfer film is heated so that the reaction rate of the (meth) acryloyl group contained in the radical polymerizable resin composition layer is 5 to 30%. Provided is a method for producing a decorative article in which the thermal transfer film is attached to an adherend by vacuum forming to be integrated, and the base film is peeled off.

According to the present invention, it is possible to obtain a thermal transfer film in which the base film can be easily peeled off by heating, the transfer coating film has good trimming properties, and the surface properties of the resulting protective layer are excellent.
In the present invention, since a specific amount of the thermoplastic resin is added, even if it is uncured, the layer thickness can be maintained at room temperature, and appropriate adhesion to the PVA substrate film can be maintained.
In the present invention, the polymerizable compound having a (meth) acryloyl group is specified in such an amount that it can function as a release layer at the interface with the PVA layer during film production / storage and within a general thermal transfer time, and The molecular weight is specified so that it can flow inside the transfer layer at a general molding temperature, and the reaction rate of (meth) acryloyl groups during heating is specified. A thermal transfer film can be obtained which can be peeled off, has good trimming properties of the transfer coating film, and is excellent in surface physical properties of the resulting protective layer.
By setting the composition of the protective layer of the present invention, the polymerizable compound having a (meth) acryloyl group also moves to the interface with the decorative layer, and further moves to the vicinity of the contact surface of the decorative layer with the substrate to be transferred. To do. Therefore, even when an adhesive layer or the like is not provided, the polymerizable compound having a (meth) acryloyl group serves as an adhesive with the base material, and is cured with active energy rays after transfer, thereby transferring the base material to be transferred. A thermal transfer film having excellent adhesion to the film can be obtained.

(Base film)
The base film used in the present invention contains a PVA resin as a main component. The PVA used in the present invention may be an unmodified PVA, or an olefin such as ethylene and propylene, acrylic acid and acrylic acid esters, methacrylic acid and methacrylic acid esters, acrylamide derivatives in the main chain of the PVA, It may be a modified PVA obtained by copolymerizing one or more monomers such as methacrylamide derivatives, vinyl ethers, vinyl halides, allyl compounds, maleic acid and salts or esters thereof, and vinylsilyl compounds.

  In this invention, the polymerization degree of PVA is 500-3000, Preferably it is 700-2500, More preferably, it is 1000-2400. When the degree of polymerization of PVA is less than 500, the mechanical strength as a base film may be insufficient, and the film may be broken particularly during continuous printing or coating. On the other hand, when the degree of polymerization of PVA exceeds 3000, the production efficiency of PVA may decrease.

  Further, the saponification degree of PVA is generally 80 to 99.9%, but in the case of the present invention, it is preferably within the range of 80 to 95%. The polymerizable compound having a (meth) acryloyl group in the present invention is present at a high density on the surface of the PVA resin substrate, and after transferring the transfer layer, exhibits an appropriate peelability between the PVA substrate and the transfer layer. There is an effect to make. From this point of view, when the degree of saponification of PVA exceeds 95%, the affinity between the polymerizable compound having a (meth) acryloyl group and the PVA substrate is lowered, and the polymerization having the (meth) acryloyl group on the substrate surface is performed. The concentration of the reactive compound is lowered, and the peelability may be lowered after transfer. In addition, when forming into a three-dimensional shape by a vacuum forming method or the like, if the degree of saponification exceeds 95%, the crystallinity becomes high and the shape following property is inferior.

  Moreover, starch, a heat stabilizer, an ultraviolet absorber, an antioxidant, for the purpose of adding a plasticizer for the purpose of imparting flexibility to the PVA film, or adjusting the mechanical strength, coatability, stability, etc. Various additives such as a colorant and a filler may be included. The film thickness is not particularly limited, but if it is too thin, the film may be torn at the time of peeling after thermal transfer. On the other hand, if it is too thick, it may not be able to follow the shape of the substrate to be transferred. About -200 micrometers is preferable. More preferably, it is 20-100 micrometers.

The surface property of the transfer layer transferred to the substrate to be transferred tends to reverse the surface property of the substrate film used. Therefore, if a mirror-like surface with a smooth surface is used as the base film, the surface of the transfer layer after transfer can also have a smooth mirror finish. If one having an uneven embossed shape is used, these glossy state and embossed shape can be formed on the surface of the transfer layer after transfer. These may be appropriately selected according to the desired design.
The thermal transfer film of the present invention is transferred in a state where a polymerizable compound having a (meth) acryloyl group is present at a high concentration at the interface between the PVA resin substrate and the transfer layer. There is an effect to relax. That is, since the transfer surface of the decorative product obtained by transferring the thermal transfer film of the present invention onto the transfer substrate has a high concentration of a polymerizable compound having a (meth) acryloyl group on the outermost surface of the transfer surface, the active energy The transfer surface after linear curing is excellent in surface hardness and tends to be more glossy than the substrate film surface used.

(Transfer layer)
In the thermal transfer film of the present invention, the transfer layer is at least a radical polymerizable resin composition layer that is an outermost layer of a transfer body obtained by transferring to a transfer substrate, and the radical polymerizable resin composition layer. It is a layer having at least a decorative layer between the transfer substrate. The decorative layer is placed between the radical polymerizable resin composition layer and the substrate to be transferred on the base film mainly composed of PVA resin so as to be between the radical polymerizable resin composition layer and the substrate to be transferred. The layers are provided so as to be laminated in this order. In addition to the radical polymerizable resin composition layer and the decorative layer, an adhesive layer or a layer such as an intermediate layer for concealing unevenness on the surface of the substrate to be transferred may be provided.

(Transfer layer Radical polymerizable resin composition layer)
The radical polymerizable resin composition layer used in the present invention is a resin layer curable by radical polymerization reaction. Among these, a resin layer containing a resin curable by active energy ray irradiation is preferable because a coating film having excellent surface hardness after transfer can be obtained. The polymerizable resin composition layer is preferably transparent because the design of the decorative layer can be expressed well, but the color of the decorative layer of the transfer body basically obtained by the required characteristics and design of the transfer body It only needs to be visible through the pattern, and it does not need to be completely transparent. That is, from transparent to translucent ones are included. Moreover, it may be colored. Moreover, the base film provided with the radical polymerizable resin composition layer and the base film provided with the decorating layer, which will be described later, are in contact with the radical polymerizable resin composition layer and the decorating layer. The method of laminating is preferable, and in order to provide primary adhesion during lamination, it is more preferable to have a slight tack.

(Radical polymerizable resin composition)
In the present invention, the radically polymerizable resin composition layer has a (meth) acryloyl group in a range of 20 to 80% by mass of a thermoplastic resin and a number average molecular weight of 100 to 1500 with respect to the total solid content. The reaction rate of the (meth) acryloyl group containing 10 to 70% by mass of the compound and heated at 160 ° C. for 10 minutes by total reflection (ATR) using FT-IR of the radical polymerizable resin composition layer Is 5 to 30%.

(Thermoplastic resin)
Examples of the thermoplastic resin used in the present invention include acrylic resins, styrene resins, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, and polyester. These may be a homopolymer or a copolymer of a plurality of monomers.
Among these, acrylic resins are preferable because they have high Tg and are suitable for reducing the tackiness of the curable resin layer. Specific examples of these resins are methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, and (meth) acrylic acid. A monomer or a copolymer composed of a (meth) acrylic monomer such as ethylhexyl, (meth) acrylic acid, acrylonitrile, methacrylonitrile, etc., and a monomer having a polymerizable double bond copolymerizable with these if necessary, that is, For example, ethylene, butadiene, isoprene, vinyl acetate, vinyl propionate, vinyl butyrate, styrene, α-methylstyrene, vinyltoluene, divinylbenzene, N-cyclohexylmaleimide, N-ethylmaleimide, N-phenylmaleimide and the like as copolymerization components Added copolymer It's okay. Among these various acrylic resins, a homopolymer of methyl (meth) acrylate or a copolymer mainly composed of methyl (meth) acrylate is preferable in terms of excellent transparency, weather resistance and scratch resistance. .

The acrylic resin may preferably have a (meth) acryloyl group. The acrylic resin containing a (meth) acryloyl group used in the present invention is not particularly limited, and an acrylic resin obtained by a known method can be used.
Specifically, for example, a carboxyl group-containing polymerizable monomer such as acrylic acid or methacrylic acid or an amino group-containing polymerizable monomer such as dimethylaminoethyl methacrylate or dimethylaminopropylacrylamide is previously blended as the copolymer component. To obtain a copolymer having a carboxyl group or an amino group, and then reacting the carboxyl group or amino group with a monomer having a glycidyl group such as glycidyl methacrylate and a (meth) acryloyl group. In addition, a hydroxyl group-containing monomer such as 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate is previously blended and copolymerized as the copolymer component to obtain the copolymer having a hydroxyl group, and then the hydroxyl group and isocyanate ethyl Isocyanate groups such as methacrylate and (meth) acryloyl groups A method of reacting a monomer having a glycidyl group-containing polymerizable monomer such as glycidyl methacrylate in advance as a copolymerization component, and copolymerizing to obtain the copolymer having a glycidyl group; , A method of reacting a carboxyl group-containing polymerizable monomer of acrylic acid or methacrylic acid, introducing a carboxyl group at the end of the copolymer using thioglycolic acid as a chain transfer agent during the polymerization, , A method of reacting a monomer having a (meth) acryloyl group with a glycidyl group such as glycidyl methacrylate, a copolymer using a carboxyl group-containing azo initiator such as azobiscyanopentanoic acid as a polymerization initiator A carboxyl group is introduced into the glycidyl group such as glycidyl methacrylate and (meth) acrylate. Reacting the resulting product with the monomer having a Royle group.
Among them, a carboxyl group-containing monomer such as acrylic acid or methacrylic acid or an amino group-containing monomer such as dimethylaminoethyl methacrylate or dimethylaminopropylacrylamide is copolymerized, and the carboxyl group or amino group and glycidyl methacrylate are copolymerized. A method of reacting a monomer having a glycidyl group and a (meth) acryloyl group such as glycidyl group or a glycidyl group-containing polymerizable monomer such as glycidyl methacrylate in advance as a copolymerization component, and copolymerizing the glycidyl group The method of obtaining the above-mentioned copolymer and then reacting the glycidyl group with a carboxyl group-containing polymerizable monomer of acrylic acid or methacrylic acid is the simplest and preferred.

By using 20 to 80% by mass of the thermoplastic resin, the layer thickness can be maintained at room temperature even when uncured, and appropriate adhesion to the PVA substrate film is maintained. -When transferred, it can be easily peeled off from the base film.
Among them, in particular, a thermoplastic resin having a weight average molecular weight of 150,000 or less is used because it is excellent in maintenance of the layer thickness, moderate adhesion to the PVA base film, and exfoliation from the base film during heating / transfer. It is preferable to use a thermoplastic resin having a weight average molecular weight of 100,000 or less. The thermoplastic resin having a weight average molecular weight of 150,000 or less moves together when the polymerizable compound having a (meth) acryloyl group flows in the transfer layer by heat applied during film production / storage and thermal transfer. It has been confirmed that it penetrates and penetrates the layer. Thereby, it is estimated that there also exists an effect which assists adhesiveness with a to-be-adhered base material.
Moreover, when the thermoplastic resin exceeds 80% by mass, peeling from the PVA base film is lightened and the coating film strength is increased, so that the trimming property is deteriorated and the surface physical properties after active energy ray curing are also reduced. . Further, when the thermoplastic resin is less than 20% by mass, peeling from the PVA base film becomes heavy and the coating film strength becomes weak, so that coating film destruction may occur at the time of peeling.

Even within the above range, when the thermoplastic resin increases, the PVA base film peels lightly, and the trimming properties and surface physical properties tend to decrease. On the other hand, when the polymerizable compound having a (meth) acryloyl group is increased, the peeling from the PVA base film becomes heavy, and the foil breakage and surface properties are improved. Due to the reaction of the (meth) acryloyl group, the coating film tends to become brittle. When an impact is applied to the peeled substrate film, the coating film may be peeled off. Thus, when peeling of the coating film of the peeled substrate film occurs, it is scattered around and the productivity is significantly reduced. In order to achieve both the peelability of the base film, the trimming properties including peeling of the coating film, and the surface properties of the decorative product to be obtained, a method using an acrylic resin having a (meth) acryloyl group as the thermoplastic resin is preferable. If the acrylic resin having a (meth) acryloyl group is in the range of 50 to 80% by mass, one having excellent trimming properties can be obtained. More preferably, the range of 60 to 80% by mass is preferable.

(Polymerizable compound having (meth) acryloyl group)
The polymerizable compound having a number average molecular weight of 100 to 1500 and having a (meth) acryloyl group used in the present invention is, for example, methyl acrylate, methyl methacrylate (hereinafter referred to as methyl (meth) acrylate together), for example. , Ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, di Cyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate, phenyl cellosolve (meth) acrylate, 2-methoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) Monofunctional monomers such as acrylate, 2-acryloyloxyethyl hydrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, trimethylsiloxyethyl methacrylate, N-vinylpyrrolidone, styrene, diethylene glycol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2,2′-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane, 2 , 2'-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane and other bifunctional monomers, trimethylolpropane tri (meth) acrylate, trimethylo And trifunctional monomers such as ethane ethane tri (meth) acrylate, tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate, and hexafunctional monomers such as dipentaerythritol hexaacrylate. A maleimide compound such as butylene glycol bis (maleimide acetate) can also be used. Moreover, since the surface hardness of the transfer surface is excellent after active energy ray curing, it is preferable to use a polyfunctional monomer having two or more (meth) acryloyl groups in one molecule.

It is also preferable to use an oligomer having a (meth) acryloyl group. Specific examples include a urethane (meth) acrylate, a polyester (meth) acrylate, a polyacryl (meth) acrylate, an epoxy (meth) acrylate, and a polyalkylene glycol poly (meth) acrylate having a number average molecular weight of 100 to 1500. , Polyether (meth) acrylate, etc., among which polyurethane (meth) acrylate, polyester (meth) acrylate and epoxy (meth) acrylate are preferably used.
Among these, urethane (meth) acrylate is preferable. Urethane (meth) acrylates include aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane-4,4′-diisocyanate, meta-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-meta-xylylene diene Polyisocyanates mainly composed of aralkyl diisocyanates such as isocyanate, tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate Cyanate, lysine isocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,4-diisocyanate cyclohexane, 1,3-bis (diisocyanate E) Aliphatic diisocyanates such as cyclohexane and 4,4'-dicyclohexylmethane diisocyanate, allophanate type polyisocyanates, biuret type polyisocyanates, adduct type polyisocyanates and isocyanurate type polyisocyanates which are aliphatic polyisocyanates obtained from aliphatic diisocyanates. And the like, and those obtained by reacting hydroxy group (meth) acrylates such as hydroxymethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, etc. can do. From the viewpoint of excellent surface hardness and weather resistance of the transfer surface after active energy ray curing, in particular, cycloaliphatic isocyanates such as isophorone diisocyanate and 1,4-diisocyanate cyclohexane, and polyfunctional (meth) acrylates such as pentaerythritol triacrylate. Urethane (meth) acrylate obtained by reacting is more preferable.

Two or more kinds of these polymerizable compounds having a (meth) acryloyl group may be used in combination. The reaction rate of the (meth) acryloyl group after heating at 160 ° C. for 10 minutes by total reflection method (ATR) using the FT-IR of the radical polymerizable resin composition layer is a polymerizable compound having a (meth) acryloyl group. Even if the composition of only one kind is less than 5% or more than 30%, by mixing two or more kinds, the reaction rate can be adjusted to 5 to 30%, and the base film can be easily peeled off. In addition, the trimability of the transfer coating film is improved.
Further, when the thermoplastic resin is an acrylic resin containing a (meth) acryloyl group, the reaction of the (meth) acryloyl group after heating at 160 ° C. for 10 minutes in combination with the polymerizable compound having the (meth) acryloyl group. The rate can be adjusted easily, the substrate film can be easily peeled off, and the trimming property of the transfer coating film becomes better.

  These polymerizable compounds having a (meth) acryloyl group have a number average molecular weight of 100 to 1500 and are more preferably liquid at normal temperature. When mixed with a thermoplastic resin to form a radically polymerizable composition layer, the coated surface can be given tackiness and contribute to the primary adhesion during lamination, and the transfer layer can be used during film production / storage and heating. It has been confirmed that it moves in the vicinity of the interface between the PVA layer and the protective layer and functions as a release layer at the interface with the PVA layer as the base film. In this invention, it is estimated that this function works effectively by containing 10-70 mass% of polymerizable compounds which have the said (meth) acryloyl group with respect to the total amount of solids. In addition, the polymerizable compound having the (meth) acryloyl group has been confirmed to permeate and permeate the decorative layer and also exist in the vicinity of the interface between the substrate to be transferred and the decorative layer. If cured by irradiating with an electron beam, there is also an effect of improving the adhesion to the substrate to be transferred.

(Photopolymerization initiator)
When the thermal transfer film of the present invention is cured with active energy rays, a photopolymerization initiator may be preferably used. Examples of photopolymerization initiators include, for example, acetophenone compounds such as diethoxyacetophenone and 1-hydroxycyclohexyl-phenyl ketone; benzoin compounds such as benzoin and benzoin isopropyl ether; 2,4,6-trimethylbenzoin diphenylphosphine oxide Acylphosphine oxide compounds such as benzophenone, o-benzoylbenzoic acid methyl-4-phenylbenzophenone and other benzophenone compounds; 2,4-dimethylthioxanthone and other thioxanthone compounds; 4,4'-diethylaminobenzophenone and other aminobenzophenones Compounds such as polyether-based maleimide carboxylic acid ester compounds, and the like, which can be used in combination. The usage-amount of a photoinitiator is 0.1-15 mass% normally with respect to the active energy ray curable resin to be used, Preferably it is 0.5-8 mass%. Examples of the photosensitizer include amines such as triethanolamine and ethyl 4-dimethylaminobenzoate. Furthermore, onium salts such as benzylsulfonium salt, benzylpyridinium salt, and arylsulfonium salt are known as photocationic initiators, and these initiators can also be used, and are used in combination with the above photopolymerization initiators. You can also

In the radical polymerizable resin composition layer, the reaction rate of (meth) acryloyl groups after heating at 160 ° C. for 10 minutes by total reflection method (ATR) using FT-IR is 5 to 30%.
As an ATR measuring device, IR-Prestige 21 manufactured by Shimadzu Corporation was used, and MIRACLE ATR (ZnSe prism, 45 ° reflection once) manufactured by PIKE was used. The (meth) reaction rate of acryloyl group, a peak near 1410 cm ^-1 is a C-H in-plane bending vibration of an alkene was calculated from the corrected height ratio of the peak around 1460 cm ^-1 derived from methylene. The radical polymerizable resin composition was applied to a base film such as PET with a bar coater, vacuum-dried at 60 ° C. for 30 minutes, and the solvent completely removed. The reaction rate of acryloyl group was set to 0%.

  In the radical polymerizable resin composition layer used in the present invention, the reaction rate of (meth) acryloyl groups after heating at 160 ° C. for 10 minutes is 5 to 30%. By setting it as this range, after pressure-bonding a film to a to-be-transferred base material, a PVA base film can be peeled easily and the trimming property of a transfer coating film becomes favorable. If the reaction rate is less than 5%, the peel strength when peeling the substrate film after pressure-bonding the film to the substrate to be transferred is not preferable because the protective layer may be destroyed. When the content exceeds 30%, the peel strength of the base film is too low, so that the trimability of the transfer coating film at the transfer base terminal deteriorates and the coating film of the non-transfer portion remains as a residue on the decorative molded product. This is not preferable. Specifically, the reaction rate of the (meth) acryloyl group contained in the radical polymerizable resin composition layer is 5% to 5% in a state where the thermal transfer film of the present invention is held at the time of film pressure bonding to the transfer substrate. After heating to be in the range of 30%, the thermal transfer film is attached to an adherend by vacuum forming and integrated, and the base film can be easily peeled off, and The trimming property of the transfer coating film is improved.

  The thickness of the radical polymerizable resin composition layer used in the present invention is preferably 1 to 50 μm and more preferably 5 to 40 μm from the viewpoint of surface protection of the substrate to be transferred and coating properties.

(Decoration layer)
A general-purpose printing ink or paint can be used for the decorative layer, and can be formed using gravure printing, offset printing, screen printing, inkjet printing, thermal transfer printing, and the like. It is preferable that the dry film thickness of a decoration layer is 0.5-15 micrometers, More preferably, it is 1-10 micrometers. A colored layer having no pattern and a colorless varnish resin layer can also be formed by coating.
In addition, the printed pattern for printing can be any printed pattern as long as it is a pattern or character that can wake up or print. A solid version may also be used.

As a coloring material used for printing ink or paint, printing can be performed using a known organic pigment or inorganic pigment, which is preferable.
Examples of the organic pigment include quinacridone pigments, phthalocyanine pigments, selenium pigments, perylene pigments, phthalone pigments, dioxazine pigments, isoindolinone pigments, methine / azomethine pigments, and diketopyrrolopyrrole pigments. Azo lake pigments, insoluble azo pigments, condensed azo pigments, and the like.
Examples of inorganic pigments include inorganic pigments such as carbon black, iron oxide and titanium oxide, metal powder pigments such as aluminum powder and bronze powder, and pearlescent pigments such as titanium oxide-coated mica.

  The resin for varnish contained in the ink is not particularly limited. For example, acrylic resin, polyurethane resin, polyester resin, vinyl resin (vinyl chloride, vinyl acetate, vinyl chloride-vinyl acetate copolymer resin), chlorine Known inks such as olefinic olefin resin, ethylene-acrylic resin, petroleum resin, and cellulose derivative resin can be used.

  In addition, the organic solvent contained in the ink can be used without particular limitation as long as it does not corrode the peelable film described later. Specific examples thereof include carbonization such as toluene, xylene, cyclohexane, n-hexane or mineral spirit. Hydrogen organic solvent, methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate or amyl acetate ester organic solvent, n-butyl ether, dioxane , Ether-based organic solvents such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether or diethylene glycol, acetone, methyl ethyl ketone, methyl iso Ketone-based organic solvents such as tilketone, methylaminoketone, diisobutylketone or cyclohexanone, nitrogen-containing systems such as N-methylpyrrolidone, and aromatic petroleum such as “Swazole 310, Swazole 1000, Swazol 1500” (manufactured by Cosmo Oil Co., Ltd.) Mention may be made of solvent systems. These organic solvents may be used alone or in combination of two or more.

  In addition to the base resin and the colorant, the printing ink or paint may contain a plasticizer, a surfactant, an antioxidant, an ultraviolet absorber, a matting agent, a solvent, and the like as necessary.

(Method for producing thermal transfer film)
The thermal transfer film of the present invention is obtained by subjecting the support film provided with the radical polymerizable resin composition layer and the arbitrary peelable film provided with the decorating layer to the polymerizable property by dry lamination (dry lamination method). The most preferable method is a method in which the resin layer and the decorative layer are stacked so as to face each other and bonded together by dry lamination (dry lamination method).
PVA, which is the main raw material of the base film, has low heat resistance, and under temperature conditions exceeding 130 ° C, it tends to cause problems such as film shrinkage and lamellar wrinkles. 30 to 120 ° C., more preferably 40 to 100 ° C.

  Since the radical polymerizable resin composition used in the present invention contains a certain amount of a polymerizable compound having a (meth) acryloyl group, the (meth) acryloyl group is formed inside the transfer layer immediately after the thermal transfer film is produced by the above-described method. Flow rearrangement of the polymerizable compound having Specifically, it has been confirmed that the polymerizable compound having the (meth) acryloyl group passes through the interface with the PVA resin base material and the decorative layer and moves to the surface of the decorative layer. In order to effectively promote this flow rearrangement, it is effective to cure the heat transfer film bonded by dry lamination by heat aging treatment, specifically, curing at 30 to 60 ° C. for 24 hours or more. It is preferable.

  There is no particular limitation on the method for providing the radical polymerizable resin composition layer on the PVA base film or the method for providing the decorating layer on an arbitrary peelable film. For example, a gravure printing method or an offset printing method. Various printing methods such as gravure offset printing method, flexographic printing method, screen printing method, gravure coating method, micro gravure coating method, roll coating method, rod coating method, kiss coating method, knife coating method, air knife coating method, comma Various known coating methods such as a coating method, a die coating method, a lip coating method, a flow coating method, a dip coating method, and a spray coating method can be appropriately used.

  The optional peelable film can be provided with a decorative layer, does not cause thermal alteration due to dry lamination, and on the other hand, if it is a film that can be peeled well from the decorative layer before thermal transfer processing There is no particular limitation. Specific examples include polyolefin resins such as polyethylene and polypropylene, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, ethylene- (meth) acrylic acid (ester) copolymers, and ethylene-unsaturated carboxylic acids. Olefin copolymer resin such as copolymer metal neutralized product (so-called ionomer resin), acrylic resin such as polyacrylonitrile, polymethyl methacrylate, polyethyl methacrylate, styrene resin such as polystyrene, AS resin, ABS resin, Polyvinyl resins such as polyvinyl acetal, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycar A film made of a thermoplastic resin such as a polyester resin such as bonate, polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, or the like, or plasma irradiation of the film, Examples thereof include those that have been surface-treated with a release agent such as a fluorine compound or a silicone compound.

  Formation of the decorative layer on the peelable film can be performed by gravure printing, offset printing, screen printing, ink jet printing, and the like, and gravure printing is preferable because it is easy to obtain a high-quality image. It is preferable that the dry film thickness of a decoration layer is 0.5-15 micrometers, More preferably, it is 1-10 micrometers.

  Before the transfer, in order to peel the peelable film from the decorative layer well, the maximum peel force between the decorative layer and the peelable film is measured, and the composition of the printing ink or paint used for the decorative layer is adjusted. Alternatively, it is preferable to select a material resin for the peelable film or to treat the surface of the peelable film with a release agent. The peel force is preferably adjusted so that the maximum peel force between the decorative layer and the peelable film is 5.8 mN / 24 mm or more and 40 mN / 24 mm or less, more preferably 7.5 mN / 24 mm or more and 30 mN / 24 mm or less.

(Thermal transfer film thickness)
The total film thickness of the thermal transfer film of the present application is not particularly limited because it depends on the thermal transfer method, but is preferably 20 to 200 μm and more preferably 30 to 150 μm from the viewpoint of shape followability to the transfer substrate.

(Adhesive layer)
In addition, an arbitrary layer can be further laminated as long as the effects of the present invention are not impaired. For example, it is preferable to provide an adhesive layer or a pressure-sensitive adhesive layer on the surface of the decorative layer that contacts the substrate to be transferred. The adhesive layer and the pressure-sensitive adhesive layer are layers provided for the purpose of increasing the adhesion force to the adherend, and may be either an adhesive or a pressure-sensitive adhesive, and can be appropriately selected from materials that adhere to the transfer substrate. is there.
In the thermal transfer film of the present invention, the polymerizable compound having a (meth) acryloyl group also moves to the interface with the decorative layer, and further moves to the vicinity of the contact surface of the decorative layer with the substrate to be transferred. The effect that the polymerizable compound having a (meth) acryloyl group plays the role of an adhesive with the base material is obtained. In order to make the most of this effect, the adhesive layer and the adhesive layer must be formed of a (meth) acryloyl group. A polymerizable compound having excellent compatibility or permeability is preferred. These can be appropriately controlled by the resin composition and the film thickness.

  Examples of the adhesive include acrylic resin, urethane resin, urethane-modified polyester resin, polyester resin, epoxy resin, ethylene-vinyl acetate copolymer resin (EVA), vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, natural rubber. , SBR, NBR, synthetic rubber such as silicone rubber, and the like, and solvent type or solventless type can be used.

  The pressure-sensitive adhesive is not particularly limited as long as it has tackiness at the temperature at which it is thermoformed. For example, solvents such as acrylic resin, isobutylene rubber resin, styrene-butadiene rubber resin, isoprene rubber resin, natural rubber resin, silicone resin, etc. Type adhesive, acrylic emulsion resin, styrene butadiene latex resin, natural rubber latex resin, styrene-isoprene copolymer resin, styrene-butadiene copolymer resin, styrene-ethylene-butylene copolymer resin, ethylene-vinyl acetate resin Solvent-free pressure-sensitive adhesives such as polyvinyl alcohol, polyacrylamide, and polyvinyl methyl ether.

  When the adhesive layer or the pressure-sensitive adhesive layer is provided on the thermal transfer film of the present invention, the adhesive layer or the pressure-sensitive adhesive layer is formed on the base film having the PVA resin provided with the radical polymerizable resin composition layer as a main component and the peelable film. A film in which a layer and a decorative layer are provided in this order can be obtained by a method in which the radical polymerizable resin composition layer and the decorative layer are overlapped and bonded by dry lamination.

(Thermal transfer method)
The thermal transfer film of the present invention can be used in a known transfer method. Specifically, if necessary, a pre-molded thermal transfer film is placed on the surface of the female mold, both molds are closed, and a molten resin is injected from the injection hole into the cavity (molded cavity) between the two molds. After cooling and solidifying, both molds are opened, the molded product and the thermal transfer film adhered thereto are taken out of the mold, only the base film is peeled off, and a decorative product in which a transfer layer is transferred and formed on a substrate to be transferred After the thermal transfer film is placed above the molded transfer substrate, the transfer layer faces the transfer substrate, and the film is heated above the softening temperature and then vacuumed. Then, at the same time as molding using the transferred substrate without using a mold, it is directly attached to the transferred substrate, such as vacuum forming simultaneous transfer method, wrapping simultaneous transfer method, etc. Specially designed for molding and transferring to three-dimensional shapes with deformation It can be suitably used a thermal transfer film of the present invention. Moreover, you may use the thermal transfer film of this invention for the transfer methods which extend to a transfer film and do not add a deformation | transformation, such as a hot stamp.

  Among these, the vacuum forming simultaneous transfer method is preferable. Specifically, after the thermal transfer film is held and heated so that the reaction rate of (meth) acryloyl groups contained in the radical polymerizable resin composition layer is 5 to 30%, the thermal transfer By pasting and integrating the film on the adherend by vacuum forming, the base film can be peeled cleanly and a decorative product can be obtained.

In many cases, an existing thermoforming machine used in a vacuum forming method, a compressed air vacuum forming method, or the like can be installed or externally attached with an infrared irradiation device as a heating means, and may be used. Infrared irradiators need to irradiate wavelengths that can only be absorbed by heat-generating substances, so halogen heaters with short wavelength peaks in the mid-infrared to near-infrared region, short-wave heaters, carbon heaters, mid-infrared heaters, etc. Is preferably used. The peak of the main wavelength of these infrared irradiation devices is preferably within 1.0 to 3.5 μm. When these infrared irradiation apparatuses are used, when the thermal transfer film of the present invention is set to 110 to 190 ° C., the reaction rate of the (meth) acryloyl group contained in the radical polymerizable resin composition layer is 5 to 30%. The material film can be easily peeled off and the transfer coating film has good trimming properties. Furthermore, it is more preferable to heat the thermal transfer film to 130 to 180 ° C. because the appearance of the decorative product becomes good.
Moreover, when indirectly heating from the PVA base film side using an infrared irradiation apparatus, the reaction rate of the (meth) acryloyl group contained in the said radical polymerizable resin composition also by the color tone of a decoration layer and the pigment to be used. Changes. For example, a metal design using an aluminum pigment tends to have a low reaction rate compared to a normal wood grain pattern, etc., and depending on the design properties of the decorative layer, the composition ratio of the radical polymerizable resin composition and It is necessary to appropriately adjust the heating temperature at the time of thermal transfer so that the reaction rate of the (meth) acryloyl group is 5 to 30%.

(Active energy ray irradiation)
The radically polymerizable resin composition layer of the decorative product to which the thermal transfer film of the present invention is transferred is cured with active energy rays or the like. As the active energy ray, it is usually preferable to use visible light or ultraviolet light. In particular, ultraviolet rays are suitable. As the ultraviolet light source, sunlight, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like is used. In addition, as a heating source when heat is used in combination, a known heat source such as hot air or near infrared light can be applied.
The irradiation amount at this time is preferably such an irradiation amount that the curable resin layer is completely cured, and specifically, a range of 250 mJ / cm ^{2 to} 3000 mJ / cm ² is preferable. In particular, the polymerizable compound having been moved to the interface between the decorative layer (meth) acryloyl groups sufficiently cured and in order to improve the adhesion to a transfer ^{substrate, 1000mJ / cm 2 ~3000mJ / cm} 2 The range of is more preferable.

(Transfer substrate)
The substrate to which the thermal transfer film of the present invention can be transferred is not particularly limited, and various shapes such as resin, metal, glass, wood and paper can be used, and the shape can be painted, plated, scratched, etc. It may be decorated by the regular decoration method.
In addition, when the material of the adherend surface of the substrate to be transferred and the material of the thermoplastic resin or ink binder used in the thermal transfer film of the present invention are materials that can be thermally bonded or heat-bonded, more adhesion is achieved. Excellent and preferable. For example, when the material of the adherend surface of the substrate to be transferred is an acrylic resin or a styrene resin, the thermoplastic resin used for the thermal transfer film is preferably an acrylic resin.

  Hereinafter, the present invention will be described with reference to examples. Unless otherwise specified, “part” and “%” are based on mass.

(Manufacture of thermoplastic resin P)
A four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas inlet tube was charged with 666 parts of methyl ethyl ketone and heated to 90 ° C. When this temperature was reached, 320 parts of methyl methacrylate, acrylic A mixture of 280 parts of butyl acid, 400 parts of methacrylic acid and 15 parts of 2,2′-azobis (2-methylbutyronitrile) was added dropwise over 4 hours, and maintained at the same temperature for 10 hours even after completion of the addition. The reaction continued.
The temperature of the reaction solution was lowered to 50 ° C., a solution in which 0.8 part of t-butylpyrocatechol was dissolved in 20 parts of methyl ethyl ketone was added, and 666 parts of glycidyl methacrylate and 60 parts of dimethylaminoethanol were added. The temperature was raised to 80 ° C., and a reaction was performed at the same temperature for 10 hours to obtain a thermoplastic resin P solution having a Tg of 50 ° C., an acrylic equivalent of 300 g / eq, and a mass average molecular weight of 60000.

Production Example 1 Production of Radical Polymerizable Resin Composition A1 As a polymerizable compound having a number average molecular weight of 100 to 1500 and having a (meth) acryloyl group, “Aronix M-305” (trade name, manufactured by Toagosei Co., Ltd.) , 12 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, number average molecular weight of about 300) and 5-6 functional urethane acrylate (manufactured by DIC, trade name “Unidic 17-813”, number average molecular weight of about 800) 48 parts and 40 parts of “Paraloid A-11” (trade name, manufactured by Rohm and Haas, acrylic resin, Tg = 100 ° C., weight average molecular weight 125,000) as a thermoplastic resin, a mixed solvent of toluene and methyl ethyl ketone (mixed) Ratio 1/1) after being dissolved so as to have a non-volatile content of 50%, as a photopolymerization initiator By dissolving manufactured by BASF Japan "Irgacure 184" 3 parts of (non-volatile content ratio) "Irgacure 819" 1 part (nonvolatile content ratio) was prepared paint radical polymerizable resin composition A1.

Production Example 2 Production of Radical Polymerizable Resin Composition A2 As thermoplastic resins, 20 parts of “Paraloid A-11” and “Paraloid B-60” (trade name, manufactured by Rohm and Haas Co., acrylic resin, Tg = 75 ° C., weight average molecular weight 50,000) A coating material for the radical polymerizable resin composition A2 was produced in the same manner as in Production Example 1, except that 20 parts were used.

Production Example 3 Production of Radical Polymerizable Resin Composition A3 As thermoplastic resin, 20 parts of “Paraloid A-11” and acrylic styrene resin “Acryt 7QX-154” (trade name, manufactured by Taisei Fine Chemical Co., Tg = 85 A coating material for the radical polymerizable resin composition A3 was produced in the same manner as in Production Example 1 except that 20 parts at 0 ° C. and a weight average molecular weight of 16,000) were used.

Production Example 4 Production of Radical Polymerizable Resin Composition A4 As the thermoplastic resin, radical polymerization was performed in the same manner as in Production Example 1 except that 40 parts of the thermoplastic resin P was converted to the resin solid content. A paint of resin composition A4 was produced.

(Production Example 5) Production of Radical Polymerizable Resin Composition A5 As a polymerizable compound having a (meth) acryloyl group having a number average molecular weight of 100 to 1500, 10 parts of “Aronix M-305” and “Unidic 17 −813 ”A coating material for the radical polymerizable resin composition A5 was produced in the same manner as in Production Example 1, except that 22 parts and 68 parts of the thermoplastic resin P as the thermoplastic resin were converted into the resin solid content. did.

(Production Example 6) Production of Radical Polymerizable Resin Composition A6 As a polymerizable compound having a number average molecular weight of 100 to 1500 and having a (meth) acryloyl group, “Aronix M-240” (trade name, manufactured by Toagosei Co., Ltd.) , Polyethylene glycol diacrylate, number average molecular weight of about 300) 10 parts, "Unidic 17-813" 22 parts, and the thermoplastic resin P as a thermoplastic resin was converted into a resin solid content and 68 parts were used. In the same manner as in Production Example 1, a coating material for the radical polymerizable resin composition A6 was produced.

(Manufacture of base film B1 provided with a decorative layer)
As a base film, a biaxially stretched polypropylene film (hereinafter abbreviated as OPP film) made by Toyobo Co., Ltd. with a thickness of 50 μm is used, and urethane ink (trade name: AF-D series, manufactured by DIC Corporation) is gravured on the film. A wood grain pattern having a thickness of 3 μm was printed by a four-color printer to produce a base film B1 provided with a decorative layer.

(Manufacture of base film B2 provided with a decorative layer)
A decorative layer is provided as a decorative layer, except that a urethane pattern ink (manufactured by DIC, product name: AF-D series) is printed with a 3 μm thick metal pattern (silver) using a gravure 4-color printing machine. The base film B2 provided with a decorative layer was produced in the same manner as the base film B1.

  Below, the manufacturing method and evaluation result of the thermal transfer film of this invention and the decorating article obtained by transferring it are shown. In addition, evaluation was performed about the base film peelability, end surface adhesiveness, foil cutting property, the appearance of the decorative product, the adhesiveness of the decorative part, and the pencil hardness of the decorative part. Three-grade evaluations (◯, Δ, ×) were judged as passing.

(Measurement of reaction rate of (meth) acryloyl group after heating at 160 ° C. for 10 minutes)
As an ATR measuring device, IR-Prestige 21 manufactured by Shimadzu Corporation was used, and MIRACLE ATR (ZnSe prism, 45 ° reflection once) manufactured by PIKE was used. The (meth) reaction rate of acryloyl group, a peak near 1410 cm ^-1 is a C-H in-plane bending vibration of an alkene was calculated from the ratio of the peak around 1460 cm ^-1 derived from methylene. The radical-polymerizable resin composition (meth) acryloyl was coated with a coating of a radical-polymerizable resin composition on a substrate film such as PET with a bar coater, dried at 60 ° C. for 30 minutes, and completely removed of the solvent. The reaction rate of the (meth) acryloyl group in the radical polysynthetic resin composition layer after the heat treatment at 160 ° C. for 10 minutes was measured with a hot air dryer.

(Base film peelability)
After leaving the decorative product with the thermal transfer film transferred to room temperature for about 5 minutes, the base film was peeled off, and the base film peelability was evaluated according to the following criteria.
○: The base film can be easily peeled off.
(Triangle | delta): Although a base film can be peeled, there exists resistance and a peeling trace remains on the protective layer surface.
X: The peel strength of the base film is high and it is difficult to peel off, the transfer layer is broken, or the base film cannot be peeled off.

(End face adhesion)
The end face adhesion of the transfer part when the base film was peeled off from the decorative product to which the thermal transfer film was transferred was evaluated according to the following criteria.
○: The end of the transfer portion is closely adhered, and the end is not peeled off.
(Triangle | delta): The adhesiveness of the terminal of a transcription | transfer part is weak, and when a base film is peeled, a float will arise in the terminal part of a transcription | transfer part.
X: When the base film is peeled off, peeling occurs at the end of the transfer portion.

(Trimming)
The trimming property of the transfer coating film when the base film was peeled off from the decorative product to which the thermal transfer film was transferred was evaluated according to the following criteria.
○: In the decorative molded product terminal, the coating film of the non-transfer portion does not remain at all and is trimmed neatly.
(Triangle | delta): In the decorative molded product terminal, the coating film of a non-transfer part remains as a residue and is not trimmed neatly.
X: In the decorative molded product terminal, the coating film of the non-transfer portion remains as a residue, and the coating film is peeled off from the peeled substrate film and falls off.
Moreover, it was set as (double-circle) when the film-peeling property was (circle) and the coating film peeling did not occur even if it rubbed the coating film surface of the peeled base film by hand.

(Appearance of decorative items)
The appearance of the decorative product to which the thermal transfer film was transferred was evaluated according to the following criteria.
○: The printed pattern is clearly reproduced in the decorative molded product.
(Triangle | delta): In a decorative molded product, a wrinkle, a crack, etc. generate | occur | produce a little and the printed pattern is not reproduced clearly.
X: In the decorative molded product, wrinkles, cracks, etc. occur, and the printed pattern is not reproduced at all.

(Measurement of reaction rate of (meth) acryloyl group after molding)
After peeling the substrate film from the decorative product to which the thermal transfer film has been transferred, the reaction rate measurement of the (meth) acryloyl group after heating the radical polysynthetic resin composition layer on the surface of the decorative molded product at 160 ° C. for 10 minutes; Similarly, the reaction rate of the (meth) acryloyl group was measured by the total reflection method (ATR) using FT-IR.

(Adhesion of the transfer layer of decorative products)
The base film was peeled from the decorative product to which the thermal transfer film was transferred, and then UV irradiation was performed at an irradiation amount of 1200 mJ / cm ² to completely cure the radical polymerizable resin composition layer. Thereafter, the adhesion of the transfer layer was evaluated according to a cross-cut method (JIS K5600-5-6).
○: No change in coating state.
(Triangle | delta): A part of coating film peels by the cohesive failure inside a transfer layer.
X: The transfer layer completely peels off from the substrate to be transferred.

(Evaluation of pencil hardness of decorative products)
The base film was peeled from the decorative product to which the thermal transfer film was transferred, and then UV irradiation was performed at an irradiation amount of 1200 mJ / cm ² to completely cure the radical polymerizable resin composition layer. The surface hardness of the obtained transfer layer was evaluated according to the pencil hardness method (JIS K5600-5-4, weight 750 g).

Example 1
(Manufacture of thermal transfer film D1)
On the glossy surface of a PVA resin film (film thickness 30 μm) manufactured by Nippon Synthetic Chemical Co., Ltd. as a film substrate, the coating material of the radical polymerizable resin composition A1 obtained in Production Example 1 is applied to a solid film thickness of 30 μm with an applicator. Coating was carried out, followed by drying at 60 ° C. for 5 minutes to produce a radical polymerizable resin composition coated film C1. The film C1 was laminated at a heating roll temperature of 60 ° C. (nip pressure 0.2 MPa) so that the radically polymerizable resin composition coated surface side of the film C1 and the printed surface side of the base film B1 provided with the decorative layer were opposed to each other. , Rolled at a roll speed of 1.2 m / min) and then aged at 40 ° C. for 24 hours to produce a thermal transfer film D1.

(Manufacture of decorative items E1)
The OPP film of the thermal transfer film D1 was peeled off and set on a double-sided vacuum forming machine “FVF-0709” manufactured by Fuse Vacuum Co., Ltd. so that the decorative layer side was the surface side to be decorated of the substrate to be transferred. . The above-mentioned thermal transfer film D1 and the transfer object were simultaneously attached by vacuum forming at a heating temperature of 160 ° C. using an ABS resin transfer substrate to obtain a decorative product E1. In the above-mentioned ABS resin transfer substrate, the draw ratio of the thermal transfer film is 110 to 230%, the end face adhesion is a portion where the draw ratio is about 200%, the transfer layer adhesion and the pencil hardness are about 120%. Evaluation was carried out at the sites.

  Table 1 shows the evaluation results for the decorative product E1. The substrate film peelability is ○, the end face adhesion is ○, the trimming property is ○, the decorative product appearance is ○, the transfer layer adhesion is ○, the pencil hardness is 2H, and the surface hardness is excellent. It was. Further, the reaction rate of the (meth) acryloyl group after heating the radical polymerizable resin composition layer A1 at 160 ° C. for 10 minutes is 20%, and the reaction rate of the (meth) acryloyl group after molding the decorative product E1 is 22%. there were. The evaluation results are shown in Table 1.

(Example 2)
A decorative product E2 was obtained in the same manner as in Example 1 except that A2 was used as the radical polymerizable resin composition. The decorative product E2 was evaluated in the same manner as in Example 1. As a result, the substrate film peelability was good, the end face adhesion was good, the trimming property was good, the decorative product appearance was good, the transfer layer adhesion was good, and the pencil hardness. Was 2H, which was found to have excellent surface hardness. The reaction rate of the (meth) acryloyl group after heating the radically polymerizable resin composition layer A2 at 160 ° C. for 10 minutes was 22%, and the reaction rate of the (meth) acryloyl group after molding the decorative product E2 was 24%. . The evaluation results are shown in Table 1.

(Example 3)
A decorative product E3 was obtained in the same manner as in Example 1 except that A3 was used as the radical polymerizable resin composition. The decorative product E3 was evaluated in the same manner as in Example 1. As a result, the substrate film peelability was ○, the end face adhesion was ○, the trimming property was Δ, the decorative product appearance was ○, the transfer layer adhesion was ○, and the pencil hardness. Is H and has an excellent surface hardness. The reaction rate of the (meth) acryloyl group after heating the radical polymerizable resin composition layer A3 at 160 ° C. for 10 minutes was 28%, and the reaction rate of the (meth) acryloyl group after molding the decorative product E3 was 34%. . The evaluation results are shown in Table 1.

Example 4
A decorative product E4 was obtained in the same manner as in Example 1 except that A3 was used as the radical polymerizable resin composition, and B2 was used as the base film provided with the decorative layer. The decorative product E4 was evaluated in the same manner as in Example 1. As a result, the substrate film peelability was ○, the end face adhesion was ○, the trimming property was ○, the decorative product appearance was ○, the transfer layer adhesion was ○, and the pencil hardness. Is H and has an excellent surface hardness. The reaction rate of the (meth) acryloyl group after heating the radical polymerizable resin composition layer A3 at 160 ° C. for 10 minutes was 28%, and the reaction rate of the (meth) acryloyl group after molding the decorative product E4 was 24%. . From this result, in comparison with Example 3, the reaction rate of the (meth) acryloyl group after molding of the decorative product E4 is within a range of 5 to 30% by changing the decorative layer from a wood pattern to a metal pattern. Thus, it can be seen that the trimming property is improved. The evaluation results are shown in Table 1.

(Example 5)
A decorative product E5 was obtained in the same manner as in Example 1 except that A4 was used as the radical polymerizable resin composition layer. The decorative product E5 was evaluated in the same manner as in Example 1. As a result, the substrate film peelability was good, the end face adhesion was good, the trimming property was good, the decorative product appearance was good, the transfer layer adhesion was good, and the pencil hardness. Was 2H, which was found to have excellent surface hardness. The reaction rate of the (meth) acryloyl group after heating the radically polymerizable resin composition layer A4 at 160 ° C. for 10 minutes was 17%, and the reaction rate of the (meth) acryloyl group after molding the decorative product E5 was 19%. . The evaluation results are shown in Table 1.

(Example 6)
A decorative product E6 was obtained in the same manner as in Example 1 except that A5 was used as the radical polymerizable resin composition. The decorative product E6 was evaluated in the same manner as in Example 1. As a result, the substrate film peelability was good, the end face adhesion was good, the trimming property was good, the decorative product appearance was good, the transfer layer adhesion was good, and the pencil hardness. Was 2H, which was found to have excellent surface hardness. The reaction rate of the (meth) acryloyl group after heating the radical polymerizable resin composition layer A5 at 160 ° C. for 10 minutes was 9%, and the reaction rate of the (meth) acryloyl group after molding the decorative product E6 was 12%. . From this result, it can be seen that the trimming property is improved by using a high concentration of the thermoplastic resin P which is an acrylic resin having a (meth) acryloyl group as the thermoplastic resin, as compared with Example 5. The evaluation results are shown in Table 2.

(Example 7)
A decorative product E7 was obtained in the same manner as in Example 1 except that A5 was used as the radical polymerizable resin composition, and B2 was used as the base film provided with the decorative layer. The decorative product E7 was evaluated in the same manner as in Example 1. As a result, the substrate film peelability was ○, the end face adhesion was ○, the trimming property was ◎, the decorative product appearance was ○, the transfer layer adhesion was ○, and the pencil hardness. Was 2H, which was found to have excellent surface hardness. The reaction rate of the (meth) acryloyl group after heating the radical polymerizable resin composition layer A5 at 160 ° C. for 10 minutes was 9%, and the reaction rate of the (meth) acryloyl group after molding the decorative product E7 was 8%. The evaluation results are shown in Table 2.

(Example 8)
A decorative product E8 was obtained in the same manner as in Example 1 except that A6 was used as the radical polymerizable resin composition. The decorative product E8 was evaluated in the same manner as in Example 1. As a result, the substrate film peelability was good, the end face adhesion was good, the trimming property was good, the decorative product appearance was good, the transfer layer adhesion was good, and the pencil hardness. Was 2H, which was found to have excellent surface hardness. The reaction rate of the (meth) acryloyl group after heating the radical polymerizable resin composition layer A6 at 160 ° C. for 10 minutes was 19%, and the reaction rate of the (meth) acryloyl group after molding the decorative product E6 was 23%. . The evaluation results are shown in Table 2.

Example 9
A decorated product E9 was obtained in the same manner as in Example 1 except that A6 was used as the radical polymerizable resin composition, and B2 was used as the base film provided with the decorative layer. The decorative product E9 was evaluated in the same manner as in Example 1. As a result, the substrate film peelability was good, the end face adhesion was good, the trimming property was good, the decorative product appearance was good, the transfer layer adhesion was good, and the pencil hardness. Was 2H, which was found to have excellent surface hardness. The reaction rate of the (meth) acryloyl group after heating the radical polymerizable resin composition layer A6 at 160 ° C. for 10 minutes was 19%, and the reaction rate of the (meth) acryloyl group after molding the decorated product E9 was 18%. . The evaluation results are shown in Table 2.

Ｍ−３０５：アロニックスＭ−３０５の略である。
１７−８１３ ユニディック１７−８１３の略である。
Ａ１１：パラロイドＡ１１の略である。

M-305: Abbreviation for Aronix M-305.
17-813 An abbreviation for Unidic 17-813.
A11: Abbreviation for paraloid A11.

Ｍ−３０５：アロニックスＭ−３０５の略である。
１７−８１３ ユニディック１７−８１３の略である。
Ａ１１：パラロイドＡ１１の略である。

M-305: Abbreviation for Aronix M-305.
17-813 An abbreviation for Unidic 17-813.
A11: Abbreviation for paraloid A11.

(Production Example 7) Production of Comparative Polymerization Resin Composition A7 for Comparative Example “Aronix M-305”, which is a polymerizable compound having a (meth) acryloyl group and having a number average molecular weight of 100 to 1500, is made of toluene and methyl ethyl ketone. After dissolving in a mixed solvent (mixing ratio 1/1) so as to have a non-volatile content of 50%, 3 parts of “Irgacure 184” (non-volatile content ratio) and 1 part of “Irgacure 819” (non-volatile content ratio) are used as photopolymerization initiators. Was dissolved to prepare a coating of the radical polymerizable resin composition A7.

(Production Example 8) Production of radically polymerizable resin composition A8 for comparative example "Unidic 17-813" which is a polymerizable compound having a (meth) acryloyl group having a number average molecular weight of 100 to 1500 is changed to toluene and methyl ethyl ketone. 3 parts of “Irgacure 184” (nonvolatile content ratio) and 1 part of “Irgacure 819” (nonvolatile content ratio) as a photopolymerization initiator were dissolved in a mixed solvent (mixing ratio 1/1) to a non-volatile content of 50%. ) Was dissolved to produce a coating of the radical polymerizable resin composition A8.

(Production Example 9) Production of radical polymerizable resin composition A9 for comparative example 50 parts "Aronix M-305" which is a polymerizable compound having a (meth) acryloyl group having a number average molecular weight of 100 to 1500 and "Uni After dissolving 50 parts of Dick 17-813 "in a mixed solvent of toluene and methyl ethyl ketone (mixing ratio 1/1) to a non-volatile content of 50%, 3 parts of" Irgacure 184 "(non-volatile content ratio) as a photopolymerization initiator And 1 part (nonvolatile content ratio) of “Irgacure 819” were dissolved to prepare a coating material for the radical polymerizable resin composition A9.

(Production Example 10) Production of Comparative Polymerization Resin Composition A10 for Comparative Example 60 parts of “Unidic 17-813” which is a polymerizable compound having a (meth) acryloyl group having a number average molecular weight of 100 to 1500, After 40 parts of “Paraloid A-11” which is a thermoplastic resin is dissolved in a mixed solvent of toluene and methyl ethyl ketone (mixing ratio 1/1) so as to have a nonvolatile content of 50%, “Irgacure 184” 3 is used as a photopolymerization initiator. A coating material for the radical polymerizable resin composition A10 was produced by dissolving 1 part (nonvolatile content ratio) and 1 part (nonvolatile content ratio) of “Irgacure 819”.

(Production Example 11) Production of Resin Composition A11 for Comparative Example 100 parts of “Paraloid A-11”, which is a thermoplastic resin, are mixed in a mixed solvent of toluene and methyl ethyl ketone (mixing ratio 1/1) so that the nonvolatile content is 50%. The paint of comparative resin composition A11 was manufactured by dissolving.

(Comparative Example 1 Example in which the base film is not PVA)
The heat transfer film HD1 and the heat transfer film HD1 were produced in the same manner as in Example 1 except that an easily moldable PET film “A1532” (trade name, film thickness 125 μm) (hereinafter abbreviated as PET film) manufactured by Toyobo Co., Ltd. was used as the base film. A decorative product HE1 was obtained. Next, an attempt was made to peel off the PET film as the base film, but the peel strength was remarkably high, and the transfer layer was destroyed. The reaction rate of the (meth) acryloyl group after heating at 160 ° C. for 10 minutes in the radical polymerizable resin composition layer A1 was 20%, but the reaction rate after molding the decorative product HE1 was not measurable. From this result, it can be seen that PVA is preferable as the base film. The evaluation results are shown in Table 3.

(Comparative Example 2 Example 1 in which reaction rate of (meth) acryloyl group is out of range and does not contain thermoplastic resin)
The production of the thermal transfer film HD2 was attempted in the same manner as in Example 1 except that A7 was used as the radical polymerizable resin composition, but the radical polymerizable resin composition A7 was too flexible due to the composition of only the monomer component. The printed layer could not be laminated. The reaction rate of the (meth) acryloyl group after heating the radical polymerizable resin composition layer A7 at 160 ° C. for 10 minutes was 35%. Since lamination was not possible, the thermal transfer film HD2 and the decorative product HE2 were not obtained, and the reaction rate of the (meth) acryloyl group after molding the decorative product HE2 could not be measured. The evaluation results are shown in Table 3.

(Comparative Example 3 Example 2 where reaction rate of (meth) acryloyl group is out of range and does not contain thermoplastic resin)
A thermal transfer film HD3 was obtained in the same manner as in Example 1 except that A8 was used as the radical polymerizable resin composition. Since the curing of the radical polymerizable resin transfer layer was accelerated too much, the film flexibility necessary for molding could not be obtained, and the entire transfer layer was destroyed. The reaction rate of the (meth) acryloyl group after heating the radical polymerizable resin composition layer A8 at 160 ° C. for 10 minutes was 38%. When the reaction rate of the (meth) acryloyl group of the radically polymerizable resin composition in the part of the decorative product HE3 that was partially transferred was measured, it was 44%. The evaluation results are shown in Table 3.

(Comparative Example 4 Example not containing thermoplastic resin)
A thermal transfer film HD4 and a decorative product HE4 were obtained in the same manner as in Example 1 except that A9 was used as the radical polymerizable resin composition. The PVA film could be easily peeled off from the decorative product HE4, and the adhesion after UV irradiation with a dose of 1200 mJ / cm ² was good, and the pencil hardness was 2H. The reaction rate of the (meth) acryloyl group after heating the radical polymerizable resin composition layer A9 at 160 ° C. for 10 minutes was 19%, and the reaction rate of the (meth) acryloyl group after molding the decorative product HE4 was 25%. . However, the end face adhesion is insufficient, and the transfer film in the terminal of the decorative molded product has poor foil breakage, and the coating of the non-transfer part remains as a residue, and further, the decorative layer is cracked, The printed pattern was not reproduced at all. From this result, it can be seen that the thermoplastic resin is an essential component. The evaluation results are shown in Table 3.

(Comparative Example 5 Example in which reaction rate of (meth) acryloyl group is out of range)
A thermal transfer film HD5 and a decorative product HE5 were obtained in the same manner as in Example 1 except that A10 was used as the radical polymerizable resin composition. The reaction rate of the (meth) acryloyl group after heating the radical polymerizable resin composition layer A10 at 160 ° C. for 10 minutes was 33%, and the reaction rate of the (meth) acryloyl group after molding the decorative product HE5 was 40%. . Although the PVA film could be easily peeled off from the decorative product HE5, the printed layer was cracked, resulting in a decorative product with poor appearance. Furthermore, the end face adhesion was poor, and the end of the transfer part was peeled off when the PVA film was peeled off. As a result of evaluating the adhesion after performing UV irradiation at an irradiation amount of 1200 mJ / cm ² , a part of the transfer layer was peeled off from the transferred substrate. The transfer layer was torn due to insufficient adhesion of the transfer layer, and the pencil hardness was determined to be B. From this result, it is understood that the reaction rate of the radical polymerizable resin composition needs to be 5 to 30%. The evaluation results are shown in Table 3.

(Comparative Example 6 Example in which the number average molecular weight is in the range of 100 to 1500 and does not contain a polymerizable compound having a (meth) acryloyl group)
A thermal transfer film HD6 and a decorative product HE6 were obtained in the same manner as in Example 1 except that the comparative resin composition A11 was used instead of the radical polymerizable resin composition. From the decorative product HE6, the PVA film can be easily peeled off, and a decorative product with a good appearance was obtained, but the end face adhesion was poor, and the end of the transfer part was peeled off when the PVA film was peeled off, and in the decorative molded product terminal The non-transferred part of the coating film remained as a residue, and most of the film was not trimmed cleanly, and it was peeled off from the PVA film from which the coating film was peeled off. Furthermore, as a result of evaluating the adhesion of the transfer layer, peeling at the interface between the transfer substrate and the transfer layer was not observed, but the transfer layer was destroyed (cohesive failure in the protective layer and decoration with the protective layer). Since peeling between the layers occurred, it was determined to be Δ. The pencil hardness was 2B, indicating that the surface hardness was insufficient. From this result, it can be seen that a polymerizable compound having a (meth) acryloyl group having a number average molecular weight of 100 to 1500 is an essential component. The evaluation results are shown in Table 3.

Ｍ−３０５：アロニックスＭ−３０５の略である。
１７−８１３ ユニディック１７−８１３の略である。
Ａ１１：パラロイドＡ１１の略である。

M-305: Abbreviation for Aronix M-305.
17-813 An abbreviation for Unidic 17-813.
A11: Abbreviation for paraloid A11.

(Reference example)
The distribution of the radical reactive diluent in the radical polymerizable composition layer of the thermal transfer film of the present invention was analyzed.
As a typical example, after the thermal transfer film D1 obtained in Example 1 of the present application was heated at 140 ° C. × 5 minutes, 160 ° C. × 5 minutes, 180 ° C. × 5 minutes, the PVA film was peeled off, and the peeled PVA film was immersed in acetone. GC / MS analysis was performed using a gas chromatography / mass spectrometry apparatus “JMS-K9” manufactured by JEOL Ltd. The measurement conditions are column: DB-5MS, column temperature: 40 ° C. (3 min) -15 ° C./min-300° C., injection temperature: 300 ° C., carrier gas flow rate: 1.0 ml / min, ionization: EI.
As a result, although the composition of the radical polymerizable resin composition A1 is Aronix M-305 / Unidic 17-813 / Paralloid A11 = 12/48/40, the peak area derived from pentaerythritol triacrylate is other than that. Estimated 3-6 times the peak area, the other peaks were identified as unidic 17-813, low molecular weight impurities and polymerization initiators contained in Paraloid A11. The peak ratio derived from pentaerythritol triacrylate increased as the heating temperature increased. Therefore, it can be confirmed that pentaerythritol triacrylate, which is a radical reactive diluent, flows by heat transfer inside the transfer layer during heating and moves to the vicinity of the interface between the polyvinyl alcohol layer and the protective layer.

Claims (5)

A thermal transfer film having a transfer layer in which a radical polymerizable resin composition layer and a decorative layer are laminated in this order on a base film mainly composed of a polyvinyl alcohol resin, wherein the radical polymerizable resin composition layer is And 20 to 80% by mass of a thermoplastic resin with respect to the total solid content, 10 to 70% by mass of a polymerizable compound having a (meth) acryloyl group having a number average molecular weight of 100 to 1500, and the radical polymerizable resin A thermal transfer film, wherein the reaction rate of acryloyl groups after heating at 160 ° C. for 10 minutes by total reflection method (ATR) using FT-IR of the composition layer is 5 to 30%. The thermoplastic resin is an acrylic resin, and the polymerizable compound having a (meth) acryloyl group is a polymerizable compound having two or more (meth) acryloyl groups in one molecule. Thermal transfer film. The thermal transfer film according to claim 2, wherein the thermoplastic resin is an acrylic resin having a (meth) acryloyl group. It is the manufacturing method of the thermal transfer film in any one of Claims 1-3, Comprising: The base film which provided the base material film which has as a main component the polyvinyl alcohol resin which provided the radical polymerizable resin composition layer, and the decoration layer A method for producing a thermal transfer film, comprising: laminating a material film so that the radical polymerizable resin composition layer and the decorative layer are in contact with each other and then aging. The reaction rate of the (meth) acryloyl group contained in the radical polymerizable resin composition layer is in a range of 5 to 30% in a state where the thermal transfer film according to any one of claims 1 to 3 is held. A method for producing a decorative product, characterized in that after the substrate is heated, the thermal transfer film is attached to and integrated with a substrate to be transferred by a vacuum forming method, and the substrate film is peeled off.