JP7369558B2 - Laminated film for decorating 3D molded products - Google Patents

Description

The present invention relates to a laminated film for decorating three-dimensional molded products.

BACKGROUND OF THE INVENTION In molded products made from plastics, metals, and other various materials, the surface is generally decorated for the purpose of adding design to the surface or protecting the surface.

A film decoration method using a laminated film is known as one of such decoration methods. In this method, a layer for decorating a molded product is created as a film, and the layer is pasted onto the molded product to perform the decoration.

Some decorative films can impart a design to the surface of a molded product by closely adhering the film to the molded product, then peeling off the base film and thermally transferring the transfer layer. In such a decorative film, high-stretch areas and low-stretch areas coexist due to the uneven shape of the surface of the base material. In particular, in the case of a designed base layer containing aluminum or mica, there is a problem in that the orientation of the brightening agent is disturbed due to return after stretching due to stretching stress, and as a result, deterioration in appearance such as dusty skin is likely to occur.

Although Patent Document 1 discloses an intermediate layer that hides unevenness on the surface of a transfer substrate, it does not describe specific physical properties or performance.
Further, Patent Document 2 discloses that a bulk layer may be inserted in order to conceal irregularities on the surface of the base material and smooth the surface of the structure. However, although the thickness of the bulk layer is mentioned, sufficient stretchability cannot be obtained simply by increasing the thickness, and there is a risk that adhesion with adjacent layers may become insufficient due to stress strain during stretching.

Patent Document 3 discloses an invention in which the storage elastic modulus of a protective layer and a colored layer is set within a specific range in order to add a design to a decorated object having a complex shape with uneven surfaces without causing appearance defects such as cracking or shrinkage. is disclosed. However, although this method may be effective in reducing the appearance caused by cracking and shrinkage of the decorative layer due to coating shrinkage in highly stretched areas, it is unable to sufficiently absorb irregularities on the surface of the base material. There was a risk.

The decorative sheet disclosed in Patent Document 4 includes a surface layer 11, a first resin layer 12 containing at least one type of resin selected from olefin resin, styrene resin, and vinyl chloride resin; An adhesive layer 13 is arranged adjacent to and adhered to the base material, the adhesive layer 13 is made of a (meth)acrylic copolymer of a monomer mixture containing a (meth)acrylic acid ester, and is heated at 30°C, and an adhesive layer 13 having a storage modulus of 1.0×10 ³ to 1.0×10 ⁶ Pa at 1.0 Hz, in this order. The thickness of the adhesive layer is 50 μm to 1 mm.
However, although it may be effective in hiding surface irregularities, since the adhesive layer is acrylic, it has poor adhesion to non-polar substrates such as polypropylene, and has low storage modulus, resulting in poor heat resistance. There was a risk that it would be insufficient.

Patent No. 4872140 Patent No. 6005911 Patent No. 6167901 JP 2017-119403 Publication

In view of the above, an object of the present invention is to provide a laminated film for decorating a three-dimensional molded product, which is not affected by irregularities on the surface of the molded product base material and can impart an appearance with excellent design. be.

The present invention provides a base film layer (A), a clear coating layer (B), a design layer (C), a buffer layer (D) that satisfies the physical properties of the layer (X), and an adhesive layer (E). A laminated film for decorating a three-dimensional molded product, comprising :
The layer (X) has a storage modulus in the range of 1.0×10 ⁷ to 1.0×10 ⁹ Pa at 30°C, and 1.0×10 ⁵ to 1.0×10 ⁷ Pa at 90°C. It is made of resin that is in the range of
The adhesive layer (E) is made of thermoplastic resin,
The clear coating layer (B) is a layer formed of an active energy ray-curable coating composition,
The storage elastic modulus is a value measured on a sample having a film thickness of 50 μm after drying at 80° C. for 15 minutes .

The design layer (C) may be composed of a single layer or a plurality of layers, and at least one of the design layers may satisfy the physical properties of the layer (X).
The adhesive layer (E) may satisfy the physical properties of the layer (X) .
The layer (X) preferably contains at least one selected from urethane resin, olefin resin, polyester resin, acrylic resin, and epoxy resin.
The layer (X) preferably has a thickness of 10 to 50 μm.
The clear coating layer (B) is formed from an active energy ray-curable coating composition containing polyurethane acrylate (B1), a monomer/oligomer having an unsaturated double bond (B2), and a polymerization initiator (B3). It is preferable that the

The laminated film for decorating three-dimensional molded products of the present invention is a laminated film for decoration that can suppress the influence of unevenness on the surface of a molded product base material and can impart high designability to the surface after decoration.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows an example of the laminated structure of the laminated film for three-dimensional molded product decoration of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows an example of the laminated structure of the laminated film for three-dimensional molded product decoration of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows an example of the laminated structure of the laminated film for three-dimensional molded product decoration of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows an example of the laminated structure of the laminated film for three-dimensional molded product decoration of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows an example of the laminated structure of the laminated film for three-dimensional molded product decoration of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows an example of the laminated structure of the laminated film for three-dimensional molded product decoration of this invention. FIG. 4 is a diagram specifically showing a reading method for reading Tg from a chart in the Tg measuring method according to the present invention. It is a graph showing elongation changes due to film temperature and molding temperature range. FIG. 2 is a schematic diagram of a jig used in evaluating the appearance of a 200% stretched portion in Examples.

The present invention will be explained in detail below.
(Laminated film for decorating three-dimensional molded products)
The laminated film for decorating three-dimensional molded products of the present invention is a film used in decorative molding of three-dimensional molded products. That is, by adhering a film having a design property to various molded bodies, the molded body is given a design property or a surface protection function.
At that time, it is deformed into a shape along the surface of the three-dimensional shape and brought into close contact.

The laminated film for decorating three-dimensional molded products of the present invention has a layer (X) made of a resin that satisfies specific physical properties. The layer (X) exhibits a buffering effect by entering into the recesses and absorbing the irregularities on the surface of the molded product base material. That is, by covering the irregularities of the molded product, the surface of the buffer layer that is not on the molded product side can be made flat and smooth. By having such a layer (X), the influence of unevenness will not be exerted on the clear coating layer (B) or the design layer (C). Therefore, in the clear coating layer (B) and the design layer (C), appearance defects such as cracks and chipped skin can be reduced, and extremely good design properties can be obtained.

The laminated film for decorating three-dimensional molded products of the present invention has a storage modulus of 1.0×10 ⁷ to 1.0×10 ⁹ Pa at 30°C, and a storage modulus of 1.0×10 ⁵ to 1.0×10 9 Pa at 90°C. It has a layer (X) having physical properties in the range of 1.0×10 ⁷ Pa. This layer (X) may be a clear coating layer (B), a design layer (C), etc., which are essential components in the laminated structure of the laminated film for decorating three-dimensional molded products of the present invention.

Furthermore, it may have an adhesive layer (E) that satisfies the physical properties of the layer (X), or it may form a layer (Ce) that has the functions of both a design layer and an adhesive layer, and this layer It may also have the function as (X).

Furthermore, the laminated film for decorating a three-dimensional molded product of the present invention may have an adhesive layer (E), a mold release layer (F), etc., if necessary. These layers can be formed into various laminated forms as required. Furthermore, a layer having these functions may also function as layer (X).

Furthermore, instead of imparting the function of the layer (X) to a specific layer that is essential in existing laminated films for decorating three-dimensional molded products, the layer (X) is added as a separate buffer layer (D). ) may form a layer that satisfies the physical properties.

Hereinafter, specific aspects of the laminated structure will be described with reference to the drawings.
The first laminated structure shown in Figure 1 consists of a clear coating layer (B), a design layer (C), a buffer layer (D), and an adhesive layer (E) on a base film (A) in this order. It is a laminated film. In the first laminated structure, the film having such a structure is adhered to the three-dimensional molded product by the adhesive layer (E), and the base film layer (A) is peeled off after the decorative molding, so that the film can be decorated. I do. As a result, a decorative layer consisting of four layers: a clear coating layer (B), a design layer (C), a buffer layer (D), and an adhesive layer (E) is formed on the three-dimensional molded product.

The second laminated structure shown in Figure 2 is a laminated film in which a clear coating layer (B), a design layer (C), and an adhesive layer (E) are laminated in this order on a base film layer (A). be. Note that here, the design layer (C) or the adhesive layer (E) may be one that satisfies the physical properties of the layer (X). As a result, a decorative layer consisting of three layers, the clear coating layer (B), the design layer (C), and the adhesive layer (E), is formed on the three-dimensional molded product.

The third laminated structure shown in FIG. 3 includes, on the base film layer (A), a clear coating layer (B), a design layer (C ¹ ), a design layer (C ² ), a buffer layer (D), This is a laminated film in which adhesive layers (E) are laminated in this order. In the third laminated structure, the film having such a structure is adhered to the three-dimensional molded product by the adhesive layer (E), and the base film layer (A) is peeled off after the decorative molding, so that the film can be decorated. I do. As a result, a decorative layer consisting of five layers: clear coating layer (B), design layer (C ¹ ), design layer (C ² ), buffer layer (D), and adhesive layer (E) is applied to the three-dimensional molded product. It is formed in

The fourth laminated structure shown in FIG. 4 has a clear coating layer (B), a design layer (C ¹ ), a design layer (C ² ), and an adhesive layer (E) on the base film layer (A). This is a laminated film laminated in this order. Here, it is sufficient that at least one layer among the design layer (C ¹ ), the design layer (C ² ), and the adhesive layer (E) satisfies the physical properties of the layer (X). By peeling off the base film layer (A) after decorative molding, a decoration consisting of four layers: a clear coating layer (B), a design layer (C ¹ ), a design layer (C ² ), and an adhesive layer (E) is formed. A decorative layer is formed on a three-dimensional molded product.

The fifth laminated structure shown in FIG. 5 is a film in which a clear coating layer (B) and a design layer (C) are laminated in this order on a base film layer (A). A film having such a structure is obtained by the design layer (C) having a function as an adhesive layer and satisfying the physical properties of the layer (X). Decoration is performed by adhering this laminated film to a three-dimensional molded product and peeling off the base film layer (A) after decorative molding. As a result, a decorative layer consisting of two layers, the clear coating layer (B) and the design layer (C), is formed on the three-dimensional molded product.

The sixth laminated structure shown in Fig. 6 has a clear coating layer (B), a buffer layer (D), a design layer (C), and an adhesive layer (E) on the base film layer (A) in this order. It is a laminated film. A film with such a structure is adhered to a three-dimensional molded product using an adhesive layer (E), and is decorated by peeling off the base film layer (A) after decorative molding, and is then decorated with a clear coating layer (B). ), a design layer (C), a buffer layer (D), and an adhesive layer (E), which are four decorative layers formed on a three-dimensional molded product.
Each layer constituting these laminated films for decorating three-dimensional molded products will be explained in sequence below.

(layer (X))
The laminated film for decorating a three-dimensional molded product of the present invention is characterized by including a layer (X) having the effect of erasing irregularities on the surface of a molded product base material. Any material may be used as long as it can flow into the recesses of the base material and hide the projections by having the layer (X).

The layer (X) has a storage modulus in the range of 1.0×10 ⁷ to 1.0×10 ⁹ Pa at 30°C, and 1.0×10 ⁵ to 1.0×10 ⁷ at 90°C. It is made of a resin having a range of Pa. The lower limit at 30° C. is more preferably 2.0×10 ⁷ Pa, most preferably 5.0×10 ⁷ Pa. The upper limit at 30° C. is more preferably 8×10 ⁸ Pa, most preferably 5.0×10 ⁸ Pa. The lower limit at 90° C. is more preferably 2.0×10 ⁵ Pa, most preferably 5.0×10 ⁵ Pa. The upper limit at 90° C. is more preferably 8×10 ⁶ Pa, most preferably 5.0×10 ⁶ Pa. By setting the storage modulus of the resin constituting the layer (X) within a specific range, it is possible to suitably hide irregularities, follow a three-dimensional shape, and exhibit good adhesion. Furthermore, since the storage modulus measured at 30°C and 90°C has the above-mentioned relationship, it is difficult to deform at room temperature and has the property of hiding unevenness, but when heated at 90°C, it shows moderate deformation. This allows it to cope with deformation during processing. In addition, in this specification, the storage elastic modulus of the resin is a value measured by the method described in detail in the following examples.

Note that the storage modulus is a property of the resin itself. Therefore, a single-layer film is separately prepared from a resin composition having the same composition as the resin composition constituting the layer (X), and the value of the storage modulus measured thereby is defined as the "storage modulus of the resin." The specific method for measuring the storage modulus is preferably the method described in Examples. In addition, when layer (X) contains components other than resin, it means the storage elastic modulus measured as a resin composition also containing components other than the above-mentioned resin.

In the present invention, the layer (X) may be included as an independent buffer layer (D), or the design layer (C) may have the function of the layer (X). It may also have an adhesive layer (E) that also functions as (X). Further, when the design layer is composed of a plurality of layers, the object of the present invention can be achieved as long as at least one layer has a function as a buffer layer. Furthermore, it may have a layer that serves as both a design layer and an adhesive layer, and this layer may satisfy the physical properties of layer (X).

Furthermore, in the laminated film for decorating three-dimensional molded products of the present invention, two or more layers may satisfy the physical properties as the layer (X).

The layer (X) is not particularly limited as long as it satisfies the physical properties described above, and its chemical composition is not limited. Therefore, as long as each layer described in detail below has the physical properties as layer (X), the resin type and composition described in detail below can be used as appropriate. This point will be explained in detail below when explaining the configuration of each layer.

(When having a buffer layer (D) functioning as layer (X))
Based on the above, first, in the present invention, the case where the buffer layer (D) is provided as an independent layer will be described in detail. In other words, the term "buffer layer (D)" here refers to the layer (X) that does not have any special function (for example, function as a design layer or adhesive layer) other than the layer (X) that satisfies the physical properties described above. etc.).

The buffer layer (D) preferably contains at least one selected from urethane resin, olefin resin, polyester resin, acrylic resin, and epoxy resin, and in particular, can be stretched to a higher degree than other resins, It is preferable to contain a urethane resin because it is difficult to cause cracks even when stretched. Such a urethane resin is not particularly limited, but one that has a low Tg, high elongation at high temperatures, and low tensile strength is preferred.
Moreover, specifically, it is preferable that Tg is 140 degrees C or less.

Further, the buffer layer (D) preferably has a thickness of 10 to 50 μm. If the thickness is less than 10 μm, there is a possibility that the unevenness cannot be completely hidden. In addition, if the thickness exceeds 50 μm, the flexibility of the laminated film may decrease and cracks may occur. The above thickness is more preferably 15 to 40 μm, and even more preferably 20 to 35 μm.

The buffer layer (D) preferably contains a resin having a softening temperature of 50 to 170°C. In addition, in this specification, the softening temperature is a value measured by the measuring method described later in Examples.

The above layer (X) may be provided at any position, but in order to prevent unevenness from affecting the design layer (C), it is provided between the design layer (C) and the adhesive layer (E). It is preferable.

(Concerning the case where a layer having other functions has the physical properties as layer (X))
In the laminated film for decorating three-dimensional molded products of the present invention, the layer (X) described above may not be an independent buffer layer (D) but may be a layer with other functions. That is, the essential layers and optional layers constituting the present invention will be described in detail below, and any one or more of these layers may satisfy the physical property (X) above.

Note that among these, it is particularly preferable that the design layer (C), the adhesive layer (E), and the layer (Ce) serving as both the design layer and the adhesive layer have the function as the layer (X). . In terms of layer structure, these layers have the physical properties of the above layer (X), which is particularly preferable in that the purpose of the present invention can be achieved without impairing other performances required for each layer. .

(About each layer constituting the laminated film for decorating three-dimensional molded products of the present invention)
Each layer constituting the laminated film for decorating three-dimensional molded products of the present invention will be specifically explained below.
In the following description of each layer, cases in which each layer has a function as a layer (X) and cases in which it does not will not be separately described. Therefore, the structure of each layer described in detail below is a description of preferred embodiments, and is not limited thereto.

(Base film layer (A))
The base film layer (A) also functions as a carrier film when manufacturing the laminated film of the present invention. That is, it is used as a base material for forming each layer when manufacturing the laminated film for decorating three-dimensional molded products of the present invention.

The film forming the base film layer (A) is not particularly limited, and includes conventionally known films such as soft vinyl chloride film, unstretched polypropylene film, unstretched polyester film, polycarbonate film, acrylic resin film, and fluorine film. An example is film. Among these, films formed of polyester and/or polyolefin are preferred, and unstretched polyester films are particularly preferred from the viewpoint of energy-saving low-temperature processability. The thickness of the base film layer (A) is preferably 0.01 to 0.5 mm, more preferably 0.02 to 0.3 mm. If it is outside this range, it is unfavorable in terms of its function as a carrier film and the economical efficiency during electromagnetic radiation curing.

(Clear coating layer (B))
The clear coating layer (B) used in the present invention is an energy ray-curable coating, and its specific composition is not particularly limited as long as it does not impair the physical properties of the laminated film. It can be made into an energy ray curable coating film. With this, a layer having excellent properties such as weather resistance and chemical resistance can be formed by performing vacuum forming in a state before curing and then irradiating it with energy rays.

From this point of view, the clear coating layer (B) is an active energy ray-curable type containing polyurethane acrylate (B1), a monomer/oligomer having an unsaturated double bond (B2), and a polymerization initiator (B3). Preferably, it is formed from a coating composition. As a result, stretching during use is facilitated, and vacuum forming can be easily performed, resulting in good conformity to three-dimensional shapes. It also has the advantage of being less likely to cause blocking.

Furthermore, the active energy ray-curable coating composition contains (B1) in 100 parts by weight of the total solid weight of (B1) and solid weight of (B2) ((B1)+(B2)). 50 to 99 parts by weight, (B2) is contained within the range of 1 to 50 parts by weight, and the total amount of solid content weight of (B1) and solid content weight of (B2) ((B1) + (B2) )) It is preferable that (B3) be contained in the range of 0.5 to 20 parts by weight per 100 parts by weight. As a result, it is possible to have blocking resistance and deep drawability (stretchability) before curing. Furthermore, it can have high scratch resistance, surface hardness, chemical resistance, and impact resistance after curing.
Below, (B1) to (B3) will be explained in detail.

(Polyurethane acrylate (B1))
Polyurethane acrylate (B1) is a compound that has a urethane bond in its molecule and a (meth)acrylate group in its molecule. By using this, the stretchability during decorative molding is improved, and vacuum molding can be easily applied, so that it is possible to better follow a three-dimensional shape.

The polyurethane acrylate (B1) is not particularly limited, and any known polyurethane acrylate can be used. for example,
i) A compound obtained by equivalently reacting a compound having two or more isocyanate groups in the molecule with a compound having one or more hydroxyl groups and one or more double bond groups in the molecule,
ii) After reacting the condensate of polyol with monobasic acid and/or polybasic acid and/or its acid anhydride with a compound having two or more isocyanate groups in the molecule, A compound obtained by reacting a compound with one or more hydroxyl groups and one or more double bond groups,
iii) Polyol is reacted with a compound having two or more isocyanate groups in the molecule, and then further reacted with a compound having one or more hydroxyl groups and one or more double bond groups in the molecule. Compounds that are
etc.

In i) to iii) above, the compounds having one or more hydroxyl groups and one or more double bond groups in the molecule include, for example, 2-hydroxy (meth)acrylate, 2-hydroxypropyl (meth)acrylate, Examples include 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and commercially available products such as Plaxel F(M)A series (trade name of Daicel Chemical Co., Ltd.). In addition, in ii) to iii) above, polyhydric alcohols include, for example, polyethylene glycol, polycarbonate diol, polytetramethylene glycol, trimethylolpropane, etc., and commercially available products include the Praxel Diol series (trade name of Daicel Chemical Co., Ltd.). ), Praxeltriol series (trade name of Daicel Chemical Co., Ltd.), and the like.

The polyol is not particularly limited, and known acrylic polyols, polyester polyols, polycarbonate polyols, and the like can be used. Furthermore, various low molecular weight diols such as ethylene glycol, butanediol, glycerin, pentaerythritol, and neopentyl glycol can also be used as necessary.

The polyol preferably has a polycarbonate diol skeleton in a proportion such that the polycarbonate concentration is 0.5 to 75 wt% (ratio to the total amount of polyurethane acrylate (B1)). The use of a material having a polycarbonate diol skeleton has the advantage of exhibiting toughness, preventing blistering during decorative molding, and maintaining the design appearance (preventing cracking).
More preferably, the amount of the polycarbonate diol is 2 to 70% by weight.

The above-mentioned polyisocyanate is not particularly limited as long as it is a compound having two or more isocyanate groups, and examples thereof include aromatic ones such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, etc. ; aliphatic compounds such as hexamethylene diisocyanate; alicyclic compounds such as isophorone diisocyanate; monomers thereof and multimers thereof such as bullet type, nurate type, and adduct type.

Commercially available polyisocyanates include Duranate 24A-90PX (NCO: 23.6%, trade name, Asahi Kasei Co., Ltd.), Sumidur N-3200-90M (trade name, Sumitomo Bayer Urethane Co., Ltd.), and Takenate D165N- Examples include 90X (trade name, manufactured by Mitsui Chemicals), Sumidur N-3300, Sumidur N-3500 (both trade names, manufactured by Sumitomo Bayer Urethane), Duranate THA-100 (trade name, manufactured by Asahi Kasei), etc. be able to. Moreover, blocked isocyanates obtained by blocking these can also be used if necessary.

The polyurethane acrylate (B1) may partially have urea bonds.
In order to have a urea bond, a polyamine compound may be used in part in the synthesis of polyurethane acrylate. Polyamine compounds that can be used are not particularly limited, and include, for example, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2,4-trimethylhexamethylene Diamine, 2-hydroxyethylethylenediamine, N-(2-hydroxyethyl)propylenediamine, (2-hydroxyethylpropylene)diamine, (di-2-hydroxyethylethylene)diamine, (di-2-hydroxyethylpropylene)diamine, Aliphatic polyamines such as (2-hydroxypropylethylene)diamine, (di-2-hydroxypropylethylene)diamine, piperazine; 1,2- and 1,3-cyclobutanediamine, 1,2-, 1,3- and 1 , 4-cyclohexane diamine, isophorone diamine (IPDA), methylenebiscyclohexane 2,4'- and/or 4,4'-diamine, norbornane diamine; alicyclic polyamines such as phenylene diamine, xylylene diamine, 2,4- Aromatic diamines such as tolylene diamine, 2,6-tolylene diamine, diethyltoluene diamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-bis-(sec-butyl)diphenylmethane; Examples include dimer diamine obtained by converting the carboxyl group of dimer acid into an amino group, and dendrimers having a primary or secondary amino group at the terminal.

The double bond equivalent of the polyurethane acrylate (B1) is preferably 130 to 600 g/eq, more preferably 150 to 300 g/eq. If the double bond equivalent is less than 130 g/eq, there may be a problem that the cured film has poor crack resistance and impact resistance. If the double bond equivalent exceeds 600 g/eq, problems may occur such as poor scratch resistance, surface hardness, and chemical resistance.

The polyurethane acrylate (B1) preferably has a weight average molecular weight of 3,000 to 200,000. If the weight average molecular weight is less than 3000, there is a risk that the problem of poor blocking resistance may occur. When the weight average molecular weight exceeds 200,000, the compatibility between the resulting polyurethane acrylate (B1) and the monomer/oligomer (B2) having an unsaturated double bond contained in the clear coating composition may decrease. In addition, when the weight average molecular weight exceeds 200,000, the viscosity of the clear coating composition tends to increase. In addition, if the clear paint composition is diluted with an organic solvent in order to improve this increase in viscosity, the solid content in the clear paint composition will be significantly reduced, which may cause problems such as deterioration of processability. There is. In addition, in this specification, the weight average molecular weight was measured by the method described below.

The polyurethane acrylate (B1) preferably has a urethane concentration of 300 to 2000 g/eq. If the urethane concentration is less than 300 g/eq, the compatibility between the obtained polyurethane acrylate (B1) and the monomer/oligomer (B2), etc. having an unsaturated double bond contained in the clear paint composition may decrease. . In addition, if the urethane concentration is less than 300 g/eq, the viscosity of the clear coating composition tends to increase. In addition, if the clear paint composition is diluted with an organic solvent in order to improve this increase in viscosity, the solid content in the clear paint composition will be significantly reduced, which may cause problems such as deterioration of processability. There is. If the urethane concentration exceeds 2000 g/eq, there may be a problem of poor blocking resistance and impact resistance.

The polyurethane acrylate (B1) preferably has a urea concentration of 500 to 1000 g/eq. If the urea concentration is less than 500 g/eq, the compatibility between the obtained polyurethane acrylate (B1) and the monomer/oligomer (B2), etc. having an unsaturated double bond contained in the clear paint composition may decrease. . In addition, if the urea concentration is less than 500 g/eq, the viscosity of the clear coating composition tends to increase. In addition, if the clear paint composition is diluted with an organic solvent in order to improve this increase in viscosity, the solid content in the clear paint composition will be significantly reduced, which may cause problems such as deterioration of processability. There is. If the urea concentration exceeds 1000 g/eq, there is a risk that the problem of poor blocking resistance may occur.

The polyurethane acrylate (B1) may be modified with fluorine and/or silicone. That is, the polyurethane acrylate (B1) may be synthesized by the method described above using a monomer containing fluorine or silicone units, or the polyurethane acrylate (B1) obtained by the method described above may have It may also be one in which a functional group is reacted with a compound containing fluorine and/or silicone.

(Monomer/oligomer with unsaturated double bond (B2))
Any known monomer/oligomer (B2) having an unsaturated double bond can be used, and for example, the following compounds can be used.

Examples of (meth)acrylates with two functional groups are 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and ethylene glycol. Di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol Di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate , 1,10-decanediol di(meth)acrylate, glycerin di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate, and the like. Among them, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, etc. can be preferably used.

Examples of (meth)acrylates having three functional groups include trimethylolmethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide modified tri(meth)acrylate, trimethylolpropane propylene oxide modified tri( meth)acrylate, pentaerythritol tri(meth)acrylate, glycerin propoxytri(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, and the like. Among them, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, etc. can be preferably used.

Examples of (meth)acrylates having 4 functional groups are dipentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethylene oxide-modified tetra(meth)acrylate, and pentaerythritol propylene oxide-modified tetra(meth)acrylate. , ditrimethylolpropane tetra(meth)acrylate, etc. Among them, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc. can be preferably used.

Examples of (meth)acrylates having four or more functional groups are pentaerythritol tetra(meth)acrylate, pentaerythritol ethylene oxide modified tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, Dipentaerythritol penta(meth)acrylate, ditrimethylolpropane penta(meth)acrylate, propionic acid modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane hexa(meth)acrylate, dipenta Examples include polyfunctional (meth)acrylates such as hexa(meth)acrylate, which is a caprolactone-modified product of erythritol. These monomers may be used alone or in combination of two or more.

Examples of the (meth)acrylic oligomer include epoxy (meth)acrylate, polyester (meth)acrylate, and urethane (meth)acrylate. Here, as the polyester acrylate prepolymer, for example, the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polycarboxylic acid and a polyhydric alcohol is esterified with (meth)acrylic acid, or It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a polycarboxylic acid with (meth)acrylic acid. The epoxy acrylate prepolymer can be obtained, for example, by reacting (meth)acrylic acid with the oxirane ring of a relatively low molecular weight bisphenol-type epoxy resin or novolac-type epoxy resin to esterify it. Urethane acrylate can generally be obtained by reacting a product obtained by reacting a polyester polyol, polyether polyol, or polycarbonate polyol with an isocyanate monomer or a prepolymer with an acrylate monomer having a hydroxyl group.
These (meth)acrylic oligomers may be used alone or in combination of two or more, or may be used in combination with the above-mentioned polyfunctional (meth)acrylate monomer.

As the monomer/oligomer (B2) having an unsaturated double bond, commercially available products such as UV 1700B manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd. can also be used.

(Polymerization initiator (B3))
In addition to the polyurethane acrylate (B1) and the monomer/oligomer having an unsaturated double bond (B2), the clear coating composition preferably further contains a polymerization initiator (B3). Examples of the polymerization initiator (B3) include, but are not limited to, electromagnetic radiation polymerization initiators whose polymerization is initiated by electromagnetic radiation such as ultraviolet rays (UV) and electron beams, radical polymerization initiators for thermosetting, and the like. .

Specifically, the electromagnetic radiation polymerization initiator includes, for example, benzoin compounds such as benzoin methyl ether; anthraquinone compounds such as 2-ethylanthraquinone; benzophenone compounds such as benzophenone; sulfide compounds such as diphenyl sulfide; Thioxanthone compounds such as 2,4-dimethylthioxanthone; Acetophenone compounds such as 2,2-dimethoxy-2-phenylacetophenone; Phosphinoxide compounds such as 2,4,6-trimethylbenzoindiphenylphosphinoxide; Examples include polymerization initiators for ultraviolet (UV) curing such as Irgacure (registered trademark)-184 and Irgacure-819 (both manufactured by BASF). One or more of these compounds can be used as a polymerization initiator.

Examples of the thermosetting radical polymerization initiator include t-amylperoxy-2-ethylhexanoate, bis(4-t-butylcyclohexyl)peroxydicarbonate, and Trigonox (registered trademark) 121-50. (manufactured by Kayaku Akzo Co., Ltd.) and other organic peroxides. One type or two or more types of organic peroxides may be used as the radical polymerization initiator for thermosetting.

(Amounts of (B1) to (B3))
50 to 99 parts by weight of (B1) and 1 to 50 parts by weight of (B2) in 100 parts by weight of the total weight of solid content of (B1) and solid content of (B2) ((B1) + (B2)) (B3) is contained within the range of parts by weight, and 0 parts by weight of (B3) per 100 parts by weight of the total solid content weight of (B1) and solid content weight of (B2) ((B1) + (B2)). The content is preferably in the range of .5 to 20 parts by weight.

If the content of the polyurethane acrylate (B1) is less than 50 parts by weight, it is not preferable in that blocking resistance decreases. If the content of the polyurethane acrylate (B1) exceeds 99 parts by weight, it is not preferable because the scratch resistance and surface hardness will be insufficient. The lower limit is more preferably 55 parts by weight or more, and even more preferably 65 parts by weight or more. The above upper limit is more preferably 98 parts by weight or less, and even more preferably 95 parts by weight or less.

If the content of the monomer/oligomer (B2) having an unsaturated double bond is less than 1 part by weight, it is not preferable because the scratch resistance and surface hardness will be insufficient. If the content of the monomer/oligomer (B2) having an unsaturated double bond exceeds 50 parts by weight, it is not preferable in that blocking resistance decreases. The lower limit is more preferably 2 parts by weight or more, and even more preferably 5 parts by weight or more. The above upper limit is more preferably 45 parts by weight or less, and even more preferably 35 parts by weight or less.

If the content of the polymerization initiator (B3) is less than 0.5 parts by weight, the clear layer cannot be sufficiently cured, and the resulting clear has good scratch resistance, surface hardness, chemical resistance, and impact resistance. There is a possibility that the physical properties of the coating film cannot be obtained. If the content of the polymerization initiator (B3) exceeds 20 parts by weight, unreacted polymerization initiator (B3) will remain in the clear coating, and the clear coating will deteriorate due to outdoor sunlight, etc. , weather resistance may deteriorate.

The clear coating composition preferably contains 0.5 to 20 parts by weight of a monomer having a thiol group and/or an amine group.
The monomer having a thiol group and/or amine group is not particularly limited, and examples include commonly used thiol compounds and amine compounds.

The above amine compounds include aliphatic polyamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, 1,2- and 1,3-cyclobutanediamine, 1, Alicyclic polyamines such as 2-, 1,3- and 1,4-cyclohexane diamine, isophorone diamine (IPDA), methylenebiscyclohexane 2,4'- and/or 4,4'-diamine, norbornane diamine: phenylene diamine , aromatic amines such as xylylene diamine, 2,4-tolylene diamine, 2,6-tolylene diamine, diethyltoluenediamine, 4,4-bis-(sec-butyl)diphenylmethane; and the carboxyl group of dimer acid. Dimer acid diamine converted into an amino group, a dendrimer having an amino group at the end, and a polyamine having a repeating amine structure can also be used, but are not limited to these.

The above thiol compounds include 1,4-bis(3-mercaptobutyryloxy)butane, ethylene glycol dimercaptopropionate, diethylene glycol dimercaptopropionate, 4-t-butyl-1,2-benzenedithiol, bis -(2-mercaptoethyl) sulfide, 4,4'-thiodibenzenethiol, benzenedithiol, glycol dimercaptoacetate, glycol dimercaptopropionate, ethylene bis(3-mercaptopropionate), polyethylene glycol dimercaptoacetate , polyethylene glycol di-(3-mercaptopyropionate), 2,2-bis(mercaptomethyl)-1,3-propanedithiol, 2,5-dimercaptomethyl-1,4-dithiane, bisphenofluorene bis( ethoxy-3-mercaptopropionate), 4,8-bis(mercaptomethyl)-3,6,9-trithia-1,11-undecanedithiol, 2-mercaptomethyl-2-methyl-1,3-propanedithiol , 1,8-dimercapto-3,6-dioxaoctane, thioglycerol bismercapto-acetate, etc.: trimethylolpropane (trismercaptopropionate) (TMPTMP), trimethylolpropane tris(3-mercaptobutylene) trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptoacetate), tris(3-mercaptopropyl)isocyanurate, 1 , 3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,2,3-trimercaptopropane, and Trifunctional thiol such as tris(3-mercaptopropionate)triethyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione: poly(mercaptopropylmethyl)siloxane (PMPMS ), 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol pentaerythritol tetrakis (3-mercaptoacetate), and pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercapto propionate), pentaerythritol tetrakis (3-mercaptobutyrate), and the like.

The clear coating layer (B) used in the laminated film for decorating three-dimensional molded products of the present invention is as described above, but more preferably the polyurethane acrylate (B1) has a double bond equivalent of 130 ～600g/eq
Molecular weight Mw: 3000-200000
Urethane concentration: 300-2000g/eq,
It is preferable that the coating composition be formed from a coating composition that is. It is preferable to use a material that satisfies these properties. By forming the clear coating layer (B) with such a clear coating composition, it is possible to provide blocking resistance, high scratch resistance, surface hardness, chemical resistance, and good impact resistance. This is preferable in this respect. Further, the polyurethane acrylate (B1) preferably has a urea concentration of 500 to 1000 g/eq.

Note that the weight average molecular weight in this specification was measured using HLC-82220GPC manufactured by Tosoh Corporation. The measurement conditions are as follows.
Column: TSKgel Super Multipore HZ-M 3 columns Developing solvent: Tetrahydrofuran Column inlet oven 40°C
Flow rate: 0.35 ml/min.
Detector: RI
Standard polystyrene: Tosoh Co., Ltd. PS Oligomer Kit

(Other ingredients)
In addition to the above-mentioned polyurethane acrylate (B1), a monomer/oligomer having an unsaturated double bond (B2), and a polymerization initiator (B3), the clear coating composition usually contains compounds that are added as coating materials. It may also be included as other ingredients. Other components include ultraviolet absorbers (UVA), light stabilizers (HALS), binder resins, crosslinking agents, pigments, surface conditioners, antifoaming agents, conductive fillers, solvents, and the like.

Furthermore, a solvent may be used to mix the components contained in the clear paint composition and to adjust the viscosity. Examples of the solvent include conventionally known organic solvents used in paints, such as esters, ethers, alcohols, amide, ketones, aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. One type of solvent or a combination of two or more types may be used. In addition, when using the above-mentioned solvent, if a volatile substance remains in the laminated film, the volatile substance may volatilize when decorating the base material, resulting in pinholes or blisters. Therefore, it is preferable to sufficiently reduce the volatile substances contained in the laminated film.

Furthermore, it is preferable that the clear coating composition further contains 0.5 to 60 parts by weight of an inorganic/organic filler having an average primary particle size of 100 nm or less. This makes it possible to improve blocking resistance, high scratch resistance, and surface hardness. The lower limit of the above blending amount is more preferably 1% by weight, and the upper limit is more preferably 50% by weight.

The above-mentioned inorganic fillers include silica, fine powder glass, alumina, calcium carbonate, kaolin, clay, sepiolite (magnesium silicate), talc (magnesium silicate), mica (aluminum silicate), xonotlite (calcium silicate), aluminum borate, and hydrochloride. Talcite, wollastonite (calcium silicate), potassium titanate, titanium oxide, barium sulfate, magnesium sulfate, magnesium hydroxide, yttria, ceria, silicon carbide, boron carbide, zirconia, aluminum nitride, silicon nitride, or their combinations. Examples include molten mixtures, nonmetallic inorganic materials, so-called ceramic fillers, obtained through molding, firing, and the like. Among these, silica, alumina, zirconia, or a eutectic mixture thereof is preferred from the viewpoint of cost and effectiveness.

Examples of the organic filler include beads of acrylic, styrene, silicone, polyurethane, acrylic urethane, benzoguanamine, and polyethylene resins.
In addition, as commercially available organosilica sol MIBK-ST, MEK-ST-UP, MEK-ST-L, MEK-AC-2140Z (manufactured by Nissan Chemical Industries), SIRMIBK15ET%-H24, SIRMIBK15ET%-H83, ALMIBK30WT%- H06 (CIK Nanotech) etc. can be used.

The clear paint composition may contain 0.5 to 20% by weight (solid content ratio in the paint) of a polyisocyanate compound having an isocyanate group. By blending a polyisocyanate compound, moldability (stretchability) and scratch resistance can be imparted, which is preferable. The lower limit of the above blending amount is more preferably 2% by weight, and the upper limit is more preferably 18% by weight.

The thickness of the clear coating layer is not particularly limited, but is preferably 3 to 60 μm.
The clear coating composition described above preferably has a low coating viscosity. Although it depends on the method of forming the coating film, it is preferably 50 mPa·s to 5000 mPa·s, more preferably 100 mPa·s to 3000 mPa·s. If the viscosity is lower than this, it will be difficult to ensure a sufficient film thickness, and workability will be poor. If the viscosity is higher than this, the clear paint will not fully penetrate into the unevenness of the film surface, and the pattern will not be faithfully transferred. Furthermore, since air remains, problems such as swelling occur during molding.

(Design layer (C))
The design layer (C) in the present invention is a layer that has a design appearance provided by a laminated film for decorating a three-dimensional molded product. As such a layer, a layer formed by applying a colored coating composition and then drying it can be used. Each of these will be explained below.

(Design layer (C) formed by colored paint composition)
The colored coating composition that can be used in forming the design layer (C) is not particularly limited, but preferably contains a urethane resin (C1) and a glittering material (C2). In addition to the above-mentioned components, the colored paint composition also contains ultraviolet absorbers (UVA), light stabilizers (HALS), binder resins, crosslinking agents, pigments, surface conditioners, antifoaming agents, conductive Other components such as fillers and solvents may also be included. The colored coating composition may be one that is cured by electromagnetic irradiation, or may be thermoplastic or thermosetting.

(Urethane resin (C1))
The urethane resin (C1) contained in the colored coating composition is not particularly limited, but preferably has a weight average molecular weight Mw of 10,000 or more and 200,000 or less, and 30,000 or more and 150,000 or less. is more preferable. If the weight average molecular weight Mw is less than 10,000, the flexibility of the design layer (C) will decrease, and if the weight average molecular weight Mw exceeds 200,000, it will be difficult to produce a colored coating composition and apply it to a film. becomes difficult.

The polyurethane resin (C1) preferably has a Tg of -30°C to 30°C. If the above Tg is less than -30°C, there may be a problem that the tackiness (blocking) of the coating film decreases after coating and drying. If it exceeds 30°C, the coating film hardness increases, resulting in poor molding and product This may cause a problem of deterioration of low-temperature physical properties.

In this specification, Tg means a value measured by the following steps using a differential scanning calorimeter (DSC) (thermal analyzer SSC5200 (manufactured by Seiko Electronics)). That is, a step of increasing the temperature from 20°C to 150°C at a temperature increase rate of 10°C/min (step 1), a step of decreasing the temperature from 150°C to -50°C at a temperature decreasing rate of 10°C/min (step 2), This is the value obtained from the chart at the time of temperature increase in step 3 in the step (step 3) of increasing the temperature from −50° C. to 150° C. at a temperature rate of 10° C./min. That is, the temperature indicated by the arrow in the chart shown in FIG. 7 was defined as Tg.

(Shining material (C2))
The glittering material (C2) is not particularly limited, and is preferably at least one selected from the group consisting of aluminum, glass, inorganic pigments, and organic pigments. More specifically, metallic pigments using metallic bright materials such as coating aluminum, aluminum flakes, metals or alloys such as copper, zinc, nickel, tin, and aluminum oxide; mica-based pigments such as interference mica and white mica; Examples include pigments.
The above colored coating composition contains 0.5 to 60 parts by weight of (C2) in 100 parts by weight of the total weight of the solid content of (C1) and the solid content of (C2) ((C1)+(C2)). It is preferable to use a substance containing 100% of the total amount.

(Other ingredients)
Examples of binder resins and crosslinking agents that are other components contained in the colored coating composition include modified acrylic resins, polyester resins, epoxy resins, olefin resins, modified olefin resins, melamine resins, polyisocyanate compounds, and blocked isocyanate compounds. Examples include nato compounds and the like. In addition, the solvents contained in the colored coating composition include ester-based, ether-based, alcohol-based, amide-based, ketone-based, aliphatic hydrocarbon-based, alicyclic hydrocarbon-based, aromatic hydrocarbon-based, etc. Organic solvents commonly used in paints may be used alone or in combination of two or more. In addition, when using the above-mentioned solvent, if a volatile substance remains in the laminated film, the volatile substance may volatilize when decorating the base material, resulting in pinholes or blisters. Therefore, it is preferable to sufficiently reduce the volatile substances contained in the laminated film.

The design layer (C) may be composed of any one layer described above, or may be composed of a plurality of layers.
Further, it may include a design layer that also functions as layer (X). When the design layer (C) consists of a plurality of layers, the effects of the present invention can be obtained as long as at least one layer has the function of the layer (X). Note that having the function as a buffer layer here means that the storage elastic modulus of the resin constituting the layer is in the range of 1.0 × 10 ⁷ to 1.0 × 10 ⁹ Pa at 30 °C, and 1.0 × 10 9 Pa at 90 °C. This means that the condition of .0×10 ⁵ to 1.0×10 ⁷ Pa is satisfied.

Furthermore, the design layer (C) may have the following properties as an adhesive layer (E), or it may have the properties as an adhesive layer (E) and also have the properties as a layer (X). It may also have the following functions. In this case, the resin used in the adhesive layer (E) shown below may be used as the resin constituting the design layer (C), and the above-mentioned glitter material etc. may be further blended.

(Adhesive layer (E))
The adhesive layer (E) is used to adhere and adhere the laminated film to the surface of the substrate when decorating the substrate with the laminated film.

The adhesive contained in the adhesive layer (E) is not particularly limited as long as it is a conventionally known adhesive, but examples include Byron UR-3200 (manufactured by Toyobo Co., Ltd.) and UR-1361ET (manufactured by Toagosei Co., Ltd.). I can do it.
The adhesive may be formed by applying and drying the adhesive, or may be formed by laminating adhesive sheets.

The adhesive layer (E) contains at least one adhesive resin selected from the group consisting of urethane resin, acrylic resin, olefin resin, vinyl chloride/vinyl acetate resin, epoxy resin, and butyral resin, and has a softening temperature of 20 to 100°C. It is more preferable that it contains.

By using such an adhesive layer (E), it is possible to obtain suitable adhesion performance with the base material as detailed below, and also to cause appropriate deformation during the vacuum forming process, so that it remains in close contact with the base material. It is desirable to use the various resins mentioned above in terms of their ability to provide adhesion.

It is necessary to select the resin type mentioned above that has good adhesion to the molded product serving as the base material. That is, it is preferable to appropriately select and use a resin having good adhesiveness to the base material from among the above-mentioned resins. For example, it is preferable to use an olefin resin if the base material is polypropylene resin, an acrylic resin or vinyl chloride/vinyl acetate resin if the base material is ABS, and a urethane resin having a polycarbonate skeleton if the base material is polycarbonate.

The adhesive layer (E) contains an adhesive resin having a softening temperature of 20 to 100°C. In other words, even with the above-mentioned resins, if the softening temperature is less than 20°C, the surface tack becomes large and film blocking tends to occur, which is undesirable, while if it exceeds 100°C, it is not suitable for vacuum forming. Therefore, the object of the present invention cannot be achieved. The lower limit of the softening temperature is more preferably 25°C, and even more preferably 30°C. The upper limit of the softening temperature is more preferably 90°C, and even more preferably 80°C.
In addition, in this specification, the softening temperature of the adhesive layer (E) is a value measured by the method described in detail in the following examples.

Furthermore, when the adhesive resin is an amorphous polymer, the weight average molecular weight is within the range of 5,000 to 150,000. When the above-mentioned adhesive resin has a crystalline structure, the softening temperature is the melting temperature, so fluidity is ensured above the softening temperature (melting temperature); however, in the case of an amorphous polymer, the melting temperature It is necessary to ensure liquidity. Therefore, the weight average molecular weight Mw needs to be in the range of 5,000 to 150,000.

If the weight average molecular weight Mw is less than 5,000, the film forming property is poor when forming into a film, and if the weight average molecular weight Mw is more than 150,000, the permeability to the base material during molding is poor and it is difficult to ensure adhesion. It becomes difficult.
The lower limit is more preferably 6,000, and even more preferably 8,000. The above upper limit is more preferably 130,000, and even more preferably 100,000.
In addition, the weight average molecular weight of the adhesive resin is a value measured by the method detailed in the following examples.

Furthermore, in order to improve the adhesion, adhesion at the molding temperature, that is, the softening temperature is required, and this is measured by the inclined ball tack test (JIS Z0237) or the rolling ball tack test (PSTC-6). In order to obtain sufficient adhesion, it is preferably 300 mm or less, more preferably 250 mm or less in a rolling ball tack test.

The adhesive layer (E) may be a mixture of two or more types of adhesive resins that satisfy the above-mentioned properties. In order to obtain the properties required in the present invention, it may be desirable to combine two or more types.

The thickness of the adhesive layer (E) is preferably 0.004 to 0.1 mm. Outside this range, it is undesirable in terms of reduced adhesion to the molding substrate and poor coating and drying properties. The lower limit is more preferably 0.01 mm, and the upper limit is more preferably 0.06 mm.

The adhesive layer (E) preferably contains a curing agent. When containing a curing agent, it is preferable to use polyisocyanate as the curing agent. The polyisocyanate that can be used is not particularly limited, and for example, those exemplified as those that can be used in forming the clear coating layer (B) can be used.
When a curing agent is used, it is preferable to use an adhesive resin having a functional group reactive with the curing agent. Specifically, it is preferable to have a hydroxyl group. In this case, the hydroxyl value is preferably 1 to 100 mgKOH/g. The lower limit is more preferably 2 mgKOH/g, and even more preferably 5 mgKOH/g. The upper limit is more preferably 80 mgKOH/g, and even more preferably 50 mgKOH/g. If the hydroxyl value is low, a sufficient crosslinked film cannot be obtained, and if the hydroxyl value is high, the crosslinked film will have poor stretchability, or the reaction with isocyanate will be insufficient and unreacted hydroxyl value will remain, resulting in poor water resistance. performance may be degraded.

The amount of polyisocyanate as a curing agent should be appropriately determined depending on the OH equivalent of the resin in the adhesive layer (E) and the NCO equivalent of the polyisocyanate, and the ratio is about 1:0.8 to 1:1.2. It is preferable to mix with The amount is preferably 0.5 parts by weight to 10 parts by weight based on the total amount of the adhesive layer (E).

The adhesive layer (E) may contain components other than the adhesive resin, curing agent, and design-imparting components described above, within a range that does not impede the purpose of the invention. Such ingredients include ultraviolet absorbers (UVA), light stabilizers (HALS), curing catalysts, antioxidants, surface conditioners, leveling agents, anti-sagging agents, thickeners, antifoaming agents, conductive Fillers, solvents, etc. can be mentioned.

Furthermore, a solvent may be used to mix the components contained in the adhesive layer (E) and adjust the viscosity. Examples of the solvent include conventionally known organic solvents used in paints, such as esters, ethers, alcohols, amide, ketones, aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. One type of solvent or a combination of two or more types may be used. In addition, when using the above-mentioned solvent, if a volatile substance remains in the laminated film, the volatile substance may volatilize and cause pinholes or blisters when decorating the base material. Therefore, it is preferable to sufficiently reduce the volatile substances contained in the laminated film.

Further, the adhesive layer (E) may satisfy the physical properties of the layer (X).

(Release layer (F))
The mold release layer (F) in the present invention can be any known material, and can be formed using, for example, a silicone mold release agent.
The peel strength between the release layer (F) and the clear coating layer (B) is preferably 0.05 to 8.0 N/25 mm, more preferably 0.1 to 5.0 N/25 mm. If it is less than 0.05 N/25 mm, the base film layer (A) may peel off during film production or decorative molding, resulting in poor workability, and if it exceeds 8.0 N/25 mm, the film may not be removed after forming. When peeling, there is a possibility that peeling becomes difficult.

(Elongation at break)
The laminated film for decorating three-dimensional molded products for vacuum forming of the present invention preferably exhibits sufficient stretchability, having an elongation at break of 30 to 500% at 40 to 130° C. before curing. When a laminated film for decorating a three-dimensional molded article is adhered to a molded body by injection molding, there is a problem that the design quality is deteriorated due to the high temperature treatment. On the other hand, although vacuum forming does not require treatment at high temperatures and does not have this problem, sufficient stretchability is required. That is, by having such a breaking elongation in the above temperature range, it becomes easily applicable to vacuum forming, and the effects of the present invention can be suitably obtained.

A value within such a numerical range can be achieved by adjusting the components of each layer forming the film. In the present invention, "having an elongation at break of 30 to 500% at 40 to 130°C" means that the temperature range in which the elongation at break shows 30 to 500% is within 40 to 130°C, and molding at that temperature is possible. , sufficient stretchability can be obtained. That is what it means.
FIG. 8 shows a state in which the material has an elongation at break of 30 to 500% at 40 to 130°C. That is, the elongation at break shown by the solid line in FIG. 8 is 30 to 500% within the range of 40 to 130°C, but the elongation at break is outside the range.

The elongation at break was measured using Autograph AG-IS manufactured by Shimadzu Corporation in a state including the base film (B) within a temperature range of 40 to 130°C at a tensile rate of 50 mm/min. This is the value obtained by measuring the elongation at the time the layer breaks. Depending on the properties of the film, the elongation at break may be within the above-mentioned range at any temperature within the range of 40 to 130°C.

(Manufacturing method of laminated film)
For each layer other than the base film layer (A) constituting the laminated film for decorating three-dimensional molded products of the present invention, a coating composition is prepared by dissolving the components constituting each layer in a solvent, and this is applied to the base film layer. It can be formed by coating and drying on (A).

The coating method for forming each of the above layers is not particularly limited, but for example, spray coating, using an applicator, die coater, bar coater, roll coater, comma coater, roller brush, brush, spatula, etc. Just apply it. In the above coating method, after the coating solution is applied, heating and drying can be performed to remove the solvent in the coating solution.

Furthermore, as described above, the adhesive layer (E) may be bonded by a lamination method instead of the coating and drying method. That is, it may be formed by preparing a film formed of the adhesive layer (E) and adhering it to the film by lamination.

(how to use)
When decorating a base material using the laminated film for decorating three-dimensional molded products of the present invention, it may be performed in the same manner as conventionally known methods, and is not particularly limited. That is, if necessary, the base film layer (A) is peeled off from the laminated film, and the laminated film is pressure-bonded so that the adhesive layer faces the base material surface and the laminated film is tightly attached to the base material surface. Let it be decorated. Thereafter, each layer is cured by electromagnetic wave irradiation or heating to obtain a coating film. Alternatively, the base film layer (A) may be peeled off after pressure bonding and curing. In addition, when the laminated film is brought into close contact with the surface of the base material, vacuum forming, heating by injection molding, molding, etc. can be performed.

When the laminated film of the present invention is applied to vacuum forming, it is preferable that adhesion be performed under vacuum conditions such that the pressure between the base material and the film is 70 kPa or less during forming. Molding under such a degree of vacuum prevents air from entering between the adhesive layer (E) and the molded body, which is preferable in that highly adhesive decoration can be performed.

Furthermore, the molding for decoration is preferably carried out at a temperature selected within the temperature range of 40 to 130° C. so that the elongation of the laminated film is 30 to 500%. This allows the laminated film to suitably handle high elongation, allowing for good vacuum forming.

The base materials that can be suitably decorated with the laminated film of the present invention are not particularly limited, but include, for example, automobile exteriors such as bumpers, front under spoilers, rear under spoilers, side underskirts, side garnishes, and door mirrors. Examples include parts, automobile interior parts such as instrument panels, center consoles, and door switch panels, housings of home appliances such as mobile phones and audio products, refrigerators, fan heaters, and lighting equipment, and washstands.

Hereinafter, the present invention will be explained by examples. In the examples, % in the compounding ratio means % by weight unless otherwise specified. The invention is not limited to the examples described below.

(Production method of polyurethane acrylate (B1))
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a material inlet was prepared. While purging the inside of the reaction vessel with air, add 200.0 g of polyhexamethylene carbonate diol (trade name "Duranol T6001", manufactured by Asahi Kasei Chemicals Co., Ltd., number average molecular weight = 1,000 as determined by terminal functional group determination), 1, 80.0 g of 4-butanediol and 120.0 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value: 102.9 mgKOH/g) were charged. Next, 238.1 g of methyl ethyl ketone (MEK) was charged as a solvent. After the inside of the system became homogeneous, 314.2 g of 4,4'-methylenebis-cyclohexyl diisocyanate was charged at 50°C, and the mixture was reacted at 80°C using dibutyltin laurylate as a catalyst. The viscosity of the reaction solution was adjusted by diluting the solvent, and the reaction was allowed to proceed until the absorption at 2,270 cm −1 due to free isocyanate groups as measured by infrared absorption spectroscopy disappeared. Cyclohexanone was added until the mass ratio of MEK and cyclohexanone was 1:1 to obtain a resin solution containing polyurethane. The resulting resin solution had a viscosity of 200 dPa·s/20°C, a solid content of 45%, and a double bond equivalent of 600 g/eq. Moreover, the weight average molecular weight of the polyurethane measured by GPC was 44,000.

<Preparation of clear paint solution>
In a container equipped with a stirrer, put polyurethane acrylate (B1) and monomer/oligomer (B2), and while stirring, add MEK in an amount such that the final coating has NV = 40%, and then add the polymerization initiator (B3). The mixture was stirred for 30 minutes to obtain a clear paint solution.

<Preparation of colored paint solution>
Put the urethane resin (C1), brightening agent (C2) and isocyanate (C3) into a container equipped with a stirrer, and while stirring, add MIBK in an amount that makes the final paint NV = 35%, stir for 30 minutes, A colored paint solution was obtained.

<Preparation of paint solution for forming buffer layer>
Put each resin shown in Table 1 into a container equipped with a stirrer, add MEK in an amount that makes the final paint NV = 35% while stirring, and stir for 30 minutes to obtain a buffer layer forming paint solution. Ta.

(storage modulus)
The storage modulus of each resin in Table 1 is determined by applying the sample to release-treated biaxially stretched PET using an applicator so that the film thickness after drying is 50 μm, drying at 80°C for 15 minutes, It was adjusted.
Measurement was performed using a dynamic viscoelasticity measuring device Rheogel E-4000 manufactured by UBM Co., Ltd., using a sine wave, chuck tension, mode: temperature dependence, sample width 5 mm, distance between chucks 10 mm, and film thickness: 50 μm.

Unmeasurable means that the membrane is too soft.
MAU-2600, MAU-2701 DO1, MAU-2600LV2, MAU-2600LV4, and MAU-2620H2 are polycarbonate-based urethane resins.
MAU-707 is a butyral-based urethane resin.
NL-2249 is a hydroxyl-terminated urethane resin.

<Preparation of adhesive paint solution>
Each resin was placed in a container equipped with a stirrer, and while stirring, MEK was added in an amount such that the final paint had NV=30%, and the mixture was stirred for 30 minutes to obtain an adhesive paint solution.

<Adjustment of base film>
In the case of a mold release layer, a fluorine-based mold release agent was applied to one surface of the base film on which the coating layer was to be formed to form a mold release layer.

<Preparation of laminated film 1>
The above clear paint solution was applied onto the base film (A) using an applicator so that a clear paint layer (B) having a dry film thickness (hereinafter referred to as dry film thickness) of 20 μm was obtained. , and was dried at 80° C. for 15 minutes to form a clear coating layer (B). In addition, below, what is formed by forming a clear coating film layer (B) on a base film layer (A) is described as an (A+B) layer film.
Next, on the clear coating layer (B) of the (A+B) layer film, the colored paint solution was applied using an applicator so as to obtain a design layer (C) with a dry film thickness of 20 μm, and then , and was dried at 80° C. for 15 minutes to form a design layer (C).
Next, the buffer layer forming coating solution was applied onto the design layer (C) using an applicator so as to obtain a buffer layer (D) with a dry film thickness of 30 μm, and then heated at 80° C. for 15 minutes. It was dried for a minute to form a buffer layer (D).
When providing an adhesive layer, each adhesive paint solution is then applied onto the buffer layer (D) using an applicator so that an adhesive layer (E) with a dry film thickness of 20 μm is obtained, and heated at 80°C. was dried for 15 minutes to form an adhesive layer (E).
Moreover, when providing a release layer, it was provided between the base layer (A) and the clear layer (B).

[Example of manufacturing a molded object decorated with a laminated film]
The base material (molded product) was placed on a vertical lifting table installed in a double-sided vacuum forming apparatus (trade name NGF-0709, manufactured by Fuse Vacuum Co., Ltd.) consisting of an upper and lower box. Thereafter, the laminated film obtained above was set in the sheet clamp frame above the molded substrate (molded product) of the double-sided vacuum forming apparatus. Next, the vacuum level in the upper and lower boxes is reduced to 1.0 kPa, the laminated film is heated using a near-infrared heater until the temperature of the laminated film reaches 90°C, and the molded base material is raised. and the laminated film, and then compressed air of 200 kPa was introduced only into the upper box and held for 35 seconds. The upper and lower boxes were opened to atmospheric pressure to obtain a decorated molded body decorated with a laminated film. Further, from the clear coating layer (B) side of the decorated molded article, ultraviolet rays with an amount of light of 2000 mJ/cm ² were irradiated using a 120 W/cm high pressure mercury lamp, so that the clear coating layer (B) was coated with the clear coating layer (B). was cured to obtain a UV (ultraviolet) cured molded product.

The raw materials used in the table are as follows.
Novaclear SG007 (Mitsubishi Chemical): A-PET sheet UV 1700B (Nippon Gosei Kagaku Kogyo): Urethane acrylate oligomer silin TPO (BASF): 2, 4, 6-trimethylbenzoyl-diphenyl-phosphine oxide Alpaste 65-388 Aluminum (Toyo Aluminum): Aluminum paste R-271 hardening agent (NPAU): Isocyanate
E-1321 (Toagosei): PVC, vinyl acetate copolymer resin Xp012N35 (Mitsui Chemicals): Modified olefin resin MAU-2600 (Dainichiseika Industries): PC-based urethane resin

The obtained laminated films and molded bodies were evaluated based on the following criteria. The results are shown in the table.

(Appearance of 200% stretched part)
Using a trapezoidal jig (Fig. 9), each surface having an inclination of 45°, 60°, 75°, and 90°,
After forming the decorative laminated film into a test piece, the appearance of the portion corresponding to 200% stretching (75° plane) was visually confirmed.
◎: Appearance almost the same as the unstretched part is maintained ○: Appearance slightly degraded from the unstretched part is maintained ×: Appearance is noticeably deteriorated

(Elongation)
The measurement was carried out using Autograph AG-IS manufactured by Shimadzu Corporation, including the base material, at a temperature of 80° C. and at a tensile speed of 50 mm/min.
Elongation was determined when any layer broke.

(Moldability)
This was confirmed by TOM molding using a double-sided vacuum forming machine NGF-0709 manufactured by Fuse Vacuum Co., Ltd.
◎: Can be molded by following the base material up to the high-stretched part ○: Can be molded by following the base material up to the medium-stretched part △: Can be molded by following the base material up to the low-stretched part ×: Cannot be molded

(Adhesion)
Cross-cut cellotape (registered trademark) peeling test 2mm 100 Muscat ○: No peeling △: ~50% peeling ×: ~100% peeling

(water resistance)
After immersion at 40°C for 240 hours, the appearance (wrinkles, cracks) was checked.
Cross-cut Cellotape Peeling Test 2mm 100 Muscat ○: No peeling △: ~50% peeling ×: ~100% peeling

(Impact resistance after molding)
Using a DuPont impact tester, a 500 g weight was dropped from a height of 20 cm to check for cracks in the coating film.
○: No cracks △: Slight cracks on the paint film ×: Significant cracks on the paint film

(Heat resistance after molding)
After 400 hours at 80°C, the appearance (wrinkles, cracks) was checked.
◎: No change in paint film ○: Slight change in paint film appearance (wrinkles, cracks)
△: Obvious change in paint film appearance (wrinkles, cracks)
×: Significant change in paint film appearance (wrinkles, cracks)

(Softening temperature)
The softening temperature was confirmed by TMA (penetration mode).
<Analyzer>
SII Nanotechnology Co., Ltd.
"TMA/SS7100C"
<Analysis conditions>
Load 10mN
Temperature increase 5℃/min
Regarding the measurement temperature range, the melting point and glass transition temperature were confirmed using DSC, and for samples that were clearly soft, the measurement was started from around 0°C, and for other samples, the measurement was started from room temperature.

(molecular weight)
The molecular weight was confirmed by GPC.
<Analyzer>
Tosoh Corporation
"High-speed GPC HLC-8220GPC"
<Analysis conditions>
Eluent THF (contains antioxidant)
Flow rate 0.35ml/min
Injection volume 10μl
Temperature control section 40℃
Detector RI
Standard polystyrene: Calculated molecular weight is based on polystyrene equivalent.

The laminated film for decorating a three-dimensional molded product of the present invention can be suitably used when decorating a molded product having an uneven surface with a three-dimensional shaped surface.

(A) Base film layer (B) Clear coating layer (C) Design layer (D) Buffer layer (E) Adhesive layer

Claims (6)

3, which has a base film layer (A), a clear coating layer (B), a design layer (C), a buffer layer (D) that satisfies the physical properties of the layer (X), and an adhesive layer (E) in this order. A laminated film for decorating dimensional molded products,
The layer (X) has a storage modulus in the range of 1.0×10 ⁷ to 1.0×10 ⁹ Pa at 30°C, and 1.0×10 ⁵ to 1.0×10 ⁷ Pa at 90°C. It is made of resin that is in the range of
The adhesive layer (E) is made of thermoplastic resin,
The clear coating layer (B) is a layer formed of an active energy ray-curable coating composition,
The storage modulus is a value measured on a sample with a film thickness of 50 μm after drying at 80° C. for 15 minutes.
A laminated film for decorating three-dimensional molded products. 2. The laminated film for decorating a three-dimensional molded product according to claim 1 , wherein the design layer (C) is composed of a single layer or a plurality of layers, and at least one of the design layers satisfies the physical properties of the layer (X). The laminated film for decorating a three-dimensional molded product according to claim 1 or 2 , wherein the adhesive layer (E) further satisfies the physical properties of the layer (X) . The laminated film for decorating a three-dimensional molded product according to claim 1, 2 or 3 , wherein the layer (X) contains at least one selected from urethane resin, olefin resin, polyester resin, acrylic resin and epoxy resin. The laminated film for decorating a three-dimensional molded product according to claim 1, 2 , 3 or 4, wherein the layer (X) has a thickness of 10 to 50 μm. The clear coating layer (B) was formed from an active energy ray-curable coating composition containing polyurethane acrylate (B1), a monomer/oligomer having an unsaturated double bond (B2), and a polymerization initiator (B3). The laminated film for decorating three-dimensional molded products according to claim 1, 2, 3, 4, or 5 .