JP5938812B2 - Laminated body and method for producing the same - Google Patents

Description

  The present technology relates to a laminate in which a decorative layer is provided on a base, and a method for manufacturing the laminate.

  In various fields, a decorative layer is provided on a substrate. Using this decorative layer, the surface of the substrate can be designed so as to have a desired color and pattern.

  Various materials are used as a material for forming the decoration layer. Specifically, in order to improve the abrasion resistance of the decorative layer, a reactive resin such as an ultraviolet curable resin is used (for example, see Patent Documents 1 to 3). Moreover, in order to improve the peeling resistance of a decoration layer, the anchor layer is inserted between the base | substrate and the decoration layer (for example, refer patent document 4).

Japanese Patent Publication No. 01-015277 Japanese Patent No. 2629732 Japanese Patent Laid-Open No. 08-058021 JP 2014-051075 A

  Various studies have been made on the peel resistance and wear resistance of the decorative layer. However, in order to meet the increasing demand, there is still room for improvement in terms of its peel resistance and wear resistance.

  This invention is made | formed in view of this problem, The objective is to provide the laminated body which can improve the peeling resistance and abrasion resistance of a decoration layer, and its manufacturing method.

The laminate of the present invention includes a base, a decorative layer containing an ultraviolet curable resin, and an adhesive layer provided between the base and the decorative layer, including a thermosetting resin and having a thickness of 10 μm to 50 μm. The adhesive layer is adjacent to the decorative layer and has a porous structure .

The method for producing a laminate of the present invention includes preparing a first solution containing a thermosetting resin and an organic solvent, and having a weight of the organic solvent that is four times or more the weight of the thermosetting resin. By supplying the first solution and heating the first solution supplied on the substrate, an adhesive layer containing a thermosetting resin and having a thickness of 10 μm or more and 50 μm or less is formed. A decorative layer containing an ultraviolet curable resin is formed by supplying a second solution containing an ultraviolet curable resin to the substrate and irradiating the second solution supplied on the adhesive layer with ultraviolet rays .

According to the laminate of the present invention, the adhesive layer containing the thermosetting resin is provided between the base and the decorative layer containing the ultraviolet curable resin, and the thickness of the adhesive layer is 10 μm or more and 50 μm or less. At the same time, the adhesive layer adjacent to the decorative layer has a porous structure . Therefore, the peeling resistance and wear resistance of the decorative layer can be improved.
Moreover, according to the method for producing a laminate of the present invention, after supplying the first solution having a weight of the organic solvent four times or more to the weight of the thermosetting resin on the substrate, the first solution Is heated to form an adhesive layer containing a thermosetting resin and having a thickness of 10 μm to 50 μm. Moreover, after supplying the 2nd solution containing an ultraviolet curable resin on an adhesive layer, the decoration layer containing an ultraviolet curable resin is formed by irradiating the 2nd solution with an ultraviolet-ray. Therefore, the peeling resistance and wear resistance of the decorative layer can be improved.

It is sectional drawing showing the structure of the laminated body of one Embodiment of this invention. It is sectional drawing showing the 1st modification regarding the structure of the laminated body shown in FIG. It is sectional drawing showing the 2nd modification regarding the structure of the laminated body shown in FIG. It is sectional drawing showing the 3rd modification regarding the structure of the laminated body shown in FIG.

Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. The order of explanation is as follows.

1. Laminated body2. 2. Manufacturing method of laminate Action and effect Modified example

<1. Laminate>
First, the laminated body of one Embodiment of this invention is demonstrated.

  The laminated body demonstrated here is applicable to various uses, such as an industrial field and a commercial field. The use to which the laminate is applied is not particularly limited as long as the use requires that the surface of the substrate is decorated by the decoration layer.

  For example, the application to which the laminate is applied is an automobile, a household electrical appliance, a building material, a stationery, and the like, and other applications may be used.

[Overall structure of laminate]
FIG. 1 shows a cross-sectional configuration of the laminate. In addition, in FIG. 1, since the structure of a laminated body is shown typically, the thickness of the series of layers which comprise the laminated body can be arbitrarily set except the thickness of the contact bonding layer 2 mentioned later. .

  As shown in FIG. 1, the laminate includes a base body 1, an adhesive layer 2, and a decoration layer 3.

[Substrate]
The substrate 1 includes, for example, one or more of metals and resins (polymer compounds). That is, the substrate 1 may include only a metal, may include only a resin, or may include both.

  The case where the substrate 1 includes both a metal and a resin means that, for example, when the substrate 1 is a mixture of a metal and a resin, a portion of the substrate 1 is formed of metal and the other portion is formed of resin. In the case where the substrate 1 is, a case where the substrate 1 is a multilayer including one or more metal layers and one or more resin layers may be considered.

  The metal may be a simple substance or an alloy. Examples of the metal include iron, aluminum, titanium, brass, stainless steel, and copper. Among them, iron, aluminum, stainless steel, and the like are preferable. This is because the adhesion of the adhesive layer 2 to the substrate 1 is increased. In addition, although the kind of stainless steel is not specifically limited, For example, it is SUS304 etc.

  The resin may be a homopolymer or a copolymer. Examples of the resin include a copolymer of acrylonitrile, butadiene, and styrene, an acrylic resin, nylon, polyethylene, polystyrene, polycarbonate, and polyvinyl chloride. Of these, a copolymer of acrylonitrile, butadiene and styrene, polyethylene, polystyrene, and polycarbonate are preferable. This is because the adhesion of the adhesive layer 2 to the substrate 1 is increased.

  The base body 1 may have rigidity or may have flexibility. Specifically, when the substrate 1 includes a metal, the substrate 1 may be a rigid metal substrate or a flexible metal foil, for example. When the substrate 1 includes a resin, the substrate 1 may be, for example, a rigid resin substrate or a flexible resin film.

  The substrate 1 may be a single layer or a multilayer. As described above, the single layer or the multilayer may be applied to each of the adhesive layer 2 and the decorative layer 3. In the substrate 1 which is a multilayer, each layer constituting the substrate 1 may contain only a metal, may contain only a resin, or may contain both as described above.

  In addition, the base | substrate 1 may contain the functional layer of 1 layer or 2 layers or more as needed. This functional layer is a layer that exhibits a specific function according to the application to which the laminate is applied. The presence / absence, type, and number of layers of the functional layer can be arbitrarily set according to, for example, the application (required performance) to which the laminate is applied. The functional layer may be provided only on one side (upper surface or lower surface) of the substrate 1 or may be provided on both surfaces.

  For example, when the substrate 1 is a metal, the functional layer is an underlayer (surface treatment layer) for increasing the adhesion between the substrate 1 and the adhesive layer 2.

  The structure of the base | substrate 1 other than the above is not specifically limited. For example, the thickness and shape of the substrate 1 can be arbitrarily set.

[Adhesive layer]
The adhesive layer 2 is provided between the base 1 and the decorative layer 3 in order to improve the adhesion of the decorative layer 3 to the base 1. For example, the adhesive layer 2 covers the entire top surface of the substrate 1.

  Other layers may be interposed between the base 1 and the adhesive layer 2 as required, or other layers may not be interposed. This other layer is, for example, an adhesive layer other than the adhesive layer 2.

  In particular, no other layer is interposed between the base 1 and the adhesive layer 2, and the adhesive layer 2 is preferably adjacent to (in contact with) the base 1. This is because the adhesive function of the adhesive layer 2 is effectively exhibited, so that the adhesion between the substrate 1 and the adhesive layer 2 is improved.

  Between the adhesive layer 2 and the decoration layer 3, the other layers described above may be interposed as necessary, or other layers may not be interposed. In particular, no other layer is interposed between the adhesive layer 2 and the decorative layer 3, and the adhesive layer 2 is preferably adjacent to the decorative layer 3. This is because the adhesive function of the adhesive layer 2 is effectively exhibited, and thus the adhesion between the adhesive layer 2 and the decorative layer 3 is improved.

  The adhesive layer 2 includes any one or more of thermosetting resins, and the thermosetting resin is one or more of the thermosetting resins. It is. This is because the thermosetting resin has high adhesion to the base 1 without depending on the material of the base 1. This is because the thermosetting resin has high adhesion to the decorative layer 3 containing an ultraviolet curable resin described later. Thereby, the base body 1 and the decoration layer 3 are firmly bonded via the adhesive layer 2.

  The thermosetting resin may be, for example, a cured reaction product of a thermosetting resin using any one type or two or more types of curing agents. In this case, when the thermosetting resin is heated in the manufacturing process of the laminate, the thermosetting resin and the curing agent undergo a curing reaction, so that the thermosetting resin is formed.

  The kind of thermosetting resin is not particularly limited. If the adhesive layer 2 contains a thermosetting resin, the adhesion between the adhesive layer 2 and the substrate 1 is improved without depending on the type of the thermosetting resin, and the adhesive layer 2 and the decorative layer 3 This is because adhesion is also improved. Further, since the physical strength of the adhesive layer 2 itself is increased, the adhesive layer 2 is difficult to cleave.

  Although the kind of thermosetting resin is not specifically limited, For example, it is a urethane resin, a phenol resin, unsaturated polyester, a urea resin, a melamine resin, an epoxy resin, etc. Among these, urethane resin is preferable. A urethane resin is a general term for resins containing a urethane bond (—NH—C (═O) —O—). The type of this urethane resin is not particularly limited. This is because if it is a resin containing a urethane bond, the function as a thermosetting resin is sufficiently exhibited without depending on the type of the resin.

  In particular, the urethane resin is preferably a vinyl urethane resin, for example. This is because the reactivity is excellent, so that the curing reaction easily proceeds and sufficient adhesion is obtained. Moreover, since the cured reaction product has excellent physical strength, sufficient physical strength can be obtained.

  Although the kind of hardening | curing agent is not specifically limited, For example, it is an isocyanate resin. The isocyanate resin is a general term for resins containing an isocyanate group (—N═C═O). The kind of this isocyanate resin is not particularly limited. This is because a resin containing an isocyanate group (—NCO) exhibits a function as a curing agent without depending on the type of the resin.

  Among these, the isocyanate resin is preferably a reaction product of tolylene diisocyanate (TDI) and a polyester polyol, diphenylmethane diisocyanate (MDI), or the like. This is because the reactivity is excellent and the curing reaction is likely to proceed.

  For these reasons, it is preferable that the thermosetting resin contains, for example, a cured reaction product of a urethane resin and an isocyanate resin. In this cured reaction product, for example, the urethane resin is considered to be cross-linked through a polyisocyanate resin.

  The mixing ratio of the thermosetting resin and the curing agent is not particularly limited. This is because if the adhesive layer 2 contains a cured reaction product of a thermosetting resin and a curing agent, excellent adhesion and excellent physical strength can be obtained without depending on the above-described mixing ratio.

  In particular, the thickness of the adhesive layer 2 containing a thermosetting resin is about 10 μm to 50 μm, preferably about 10 μm to 30 μm. This is because the thickness of the adhesive layer 2 is optimized, so that the adhesion of the adhesive layer 2 to the substrate 1 is specifically improved.

  Specifically, when the thickness of the adhesive layer 2 is smaller than 10 μm, the adhesive layer 2 is too thin, and the adhesion of the adhesive layer 2 to the substrate 1 is insufficient. On the other hand, when the thickness of the adhesive layer 2 is larger than 50 μm, the adhesive layer 2 is too thick, so that the adhesion of the adhesive layer 2 to the substrate 1 is lowered. Therefore, in any case, the decorative layer 3 is easily peeled off from the base body 1 together with the adhesive layer 2 even though the adhesive layer 2 is used.

  On the other hand, if the thickness of the adhesive layer 2 is 10 μm to 50 μm, the thickness of the adhesive layer 2 interposed between the base 1 and the decoration layer 2 is optimized. The adhesion of the adhesive layer 2 to 1 is specifically improved. As a result, the decoration layer 3 is extremely strongly bonded to the substrate 1 via the adhesive layer 2.

  As described above, the appropriate thickness (= about 10 μm to 50 μm) of the adhesive layer 2 described here is such that the adhesive layer 2 (thermosetting resin) is interposed between the base 1 and the decorative layer 3 (ultraviolet curable resin). Special conditions that apply only when intervening.

  In addition, it is preferable that the contact bonding layer 2 has a porous structure so that it may mention later, for example. This is because the adhesiveness of the adhesive layer 2 to the substrate 1 is further improved, and the adhesiveness of the adhesive layer 2 to the decorative layer 3 is further improved.

  The configuration of the adhesive layer 2 other than the above is not particularly limited.

[Decoration layer]
For example, the decoration layer 3 covers the entire top surface of the adhesive layer 2 as shown in FIG.

  This decorative layer 3 contains any one type or two or more types of ultraviolet curable resins. This is because the ultraviolet curable resin has excellent physical strength, so that the physical strength of the decorative layer 3 is ensured. The decoration layer 3 may be, for example, an ultraviolet (UV) printing layer as will be described later. This is because the formation efficiency of the decoration layer 3 is improved.

  As will be described later, this ultraviolet curable resin is a cured reaction product of an ultraviolet curable resin. That is, in the manufacturing process of the laminate, when the ultraviolet curable resin is irradiated with ultraviolet rays, the ultraviolet curable resin undergoes a curing reaction, so that the ultraviolet curable resin is formed.

  The kind of ultraviolet curable resin is not specifically limited. This is because, if the decorative layer 3 contains an ultraviolet curable resin, the physical strength of the decorative layer 3 itself is ensured without depending on the type of the ultraviolet curable resin.

  Among them, the ultraviolet curable resin is preferably, for example, an acrylic ester curing reaction product (polyacrylic ester). This is because the adhesion between the decorative layer 3 and the adhesive layer 2 is remarkably improved, and the physical strength of the decorative layer 3 is also significantly improved.

  The kind of polyacrylic ester is not particularly limited. This is because a polyacrylic acid ester can provide excellent adhesion and excellent physical strength without depending on the type of ester. Examples of the polyacrylate ester include polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, 2-ethylhexyl polyacrylate, 2-dimethylaminoethyl polyacrylate, and 2-hydroxyethyl polyacrylate. , Other than this.

  The configuration of the decorative layer 3 other than the above is not particularly limited. For example, the thickness of the decoration layer 3 can be arbitrarily set. As an example, the thickness of the decoration layer 3 is about 8 μm to 40 μm.

[Additive]
In addition, each of the contact bonding layer 2 and the decoration layer 3 may contain any 1 type or 2 types or more of other materials, such as an additive, as needed. The presence / absence and type of the additive are determined depending on, for example, the application (required performance) to which the laminate is applied.

  Specifically, it is preferable that the decoration layer 3 that is the uppermost layer of the laminate includes, for example, any one type or two or more types of coloring materials. This is because by coloring the decoration layer 3 to have a desired color, a desired design can be applied to the surface of the laminate using the decoration layer 3. Of course, the number of colors of the coloring material may be one color or two or more colors.

  The kind of coloring material is not particularly limited. Examples of the coloring material include pigments and dyes.

  As an example, the types of coloring materials are as follows. An example of the white coloring material is titanium oxide. The black coloring material is carbon black or the like. The red (magenta) coloring material is, for example, iron oxide. The blue (cyan) coloring material is, for example, a copper phthalocyanine compound. The yellow coloring material is, for example, a nickel compound.

<2. Manufacturing method of laminate>
Next, the manufacturing method of a laminated body is demonstrated.

  In the following description, the description of the configuration and forming material of each layer in the laminate already described will be omitted as appropriate.

  When manufacturing a laminated body, the adhesive layer 2 and the decoration layer 3 are formed in this order on the base 1 so as to have the above-described configuration. In this case, the thickness of the adhesive layer 2 is about 10 μm to 50 μm.

  If a laminated body can be manufactured so that it may become an above-described structure, the detail regarding the manufacturing method of the laminated body will not be specifically limited. Especially, in order to make it easy to control the thickness of the adhesive layer 2, it is preferable to manufacture a laminate by, for example, a procedure described below.

  First, a first solution containing a thermosetting resin (hereinafter referred to as “thermosetting resin solution”) is prepared. When preparing this thermosetting resin solution, for example, a thermosetting resin, an organic solvent, and additives as necessary are mixed, and then the mixture is stirred.

  This thermosetting resin solution contains a large amount of an organic solvent. Specifically, the content (weight) of the organic solvent in the thermosetting resin solution is four times or more than the content (weight) of the thermosetting resin in the thermosetting resin solution. This is because the adhesive layer 2 can be easily formed so as to have the appropriate thickness (= about 10 μm to 50 μm).

  Especially, it is preferable that the weight of an organic solvent is 12 times or less with respect to the weight of a thermosetting resin. This is because if the weight of the organic solvent is excessive, the viscosity of the thermosetting resin solution becomes too low, and it may be difficult to form the adhesive layer 2 itself.

  The thermosetting resin solution may contain a curing agent as described above. Although content (weight) of the hardening | curing agent in a thermosetting resin solution is not specifically limited, For example, it is about 0.2 to 0.6 times with respect to content (weight) of a thermosetting resin. It is preferable. This is because the thermosetting resin can be sufficiently cured using the curing agent.

  The weight of the organic solvent relative to the weight of the curing agent is not particularly limited. For example, the weight of the organic solvent is preferably 17.5 times or more and 26 times or less with respect to the weight of the curing agent. Is preferred. This is because the adhesive layer 2 can be easily formed so as to have the appropriate thickness described above.

  Although the kind of organic solvent is not specifically limited, For example, it is preferable that they are any 1 type or 2 types or more in toluene, acetone, ethylene glycol monobutyl ether, etc. This is because the adhesive layer 2 having a porous structure is easily formed because of excellent volatility (rapid drying).

  Among these, ethylene glycol monobutyl ether is more preferable. This is because the adhesive layer 2 having a porous structure is more easily formed because of its extremely high volatility.

  Subsequently, a thermosetting resin solution is supplied onto the substrate 1. In this case, for example, the thermosetting resin solution is applied to the upper surface of the substrate 1 using any one or two or more of a spray method, a printing method, a coating method, and the like. Examples of the printing method include a pad printing method and a silk printing method. In the application method, for example, a spin coat method or the like may be used, or an application tool such as a brush may be used.

  Subsequently, the thermosetting resin solution supplied onto the substrate 1 is heated. By this heat treatment, the thermosetting resin undergoes a curing reaction in the thermosetting resin solution, so that a cured reaction product (thermosetting resin) of the thermosetting resin is formed. When the thermosetting resin solution contains a curing agent, the thermosetting resin and the curing agent undergo a curing reaction, so that a cured reaction product (thermosetting resin) between the thermosetting resin and the curing agent is formed. . Therefore, the adhesive layer 2 containing a thermosetting resin is formed.

  The heating method and heating conditions are not particularly limited. For example, heat treatment is performed using any one type or two or more types of drying ovens. The heating temperature is, for example, 60 ° C to 180 ° C. The heating time is, for example, 10 minutes to 60 minutes. This heating condition can be arbitrarily set according to, for example, the type of the substrate 1.

  Here, the reason why the adhesive layer 2 preferably has a porous structure is as follows.

  If the thermosetting resin solution contains a large amount of organic solvent, the viscosity of the thermosetting resin solution will be sufficiently low. In this case, when a spray method or the like is used as a method for forming the adhesive layer 2, since fine particles of the thermosetting resin solution are deposited on the surface of the substrate 1, the adhesive layer 2 having a porous structure is formed. It becomes easy. Thereby, in the formation process of the decoration layer 3, when the ultraviolet curable resin solution mentioned later is supplied to the surface of the adhesive layer 2, the ultraviolet curable resin solution is easily impregnated in the adhesive layer 2 (porous structure). Become. Moreover, when the ultraviolet curable resin solution comes into contact with the surface of the adhesive layer 2, the adhesive layer 2 is partially dissolved (eroded) by the organic solvent contained in the ultraviolet curable resin solution. On the other hand, the decorative layer 3 is easily adhered. Therefore, the decorative layer 3 and the adhesive layer 2 are easily engaged with each other at the interface, so that the decorative layer 3 is extremely strongly bonded to the adhesive layer 2 by using a so-called anchor effect.

  In addition, when the viscosity of the thermosetting resin solution is sufficiently low, if a spray method or the like is used as a method for forming the adhesive layer 2, the deposition thickness of the fine particles of the thermosetting resin solution described above is reduced. It becomes easy to control the thickness of the adhesive layer 2 so as to have the appropriate thickness described above.

  In addition, as mentioned above, it is preferable to use ethylene glycol monobutyl ether as the organic solvent contained in the thermosetting resin solution. This is because the volatility (quick drying) is remarkably high, so that the adhesive layer 2 having a porous structure is easily formed.

  Subsequently, a second solution containing an ultraviolet curable resin (hereinafter referred to as “ultraviolet curable resin solution”) is prepared. When preparing this ultraviolet curable resin solution, for example, an ultraviolet curable resin, an organic solvent, and additives as necessary are mixed, and then the mixture is stirred. This additive is, for example, a polymerization initiator. In addition, the kind of organic solvent, mixing ratio, etc. are not specifically limited.

  In addition, you may contain a coloring material in a ultraviolet curable resin solution as needed. In this case, the decoration layer 3 may be formed using a single type (one color) of an ultraviolet curable resin solution so as to have a monochromatic design. Or, by using a plurality of ultraviolet curable resin solutions having different colors and controlling the supply range of the ultraviolet curable resin solution using an ink jet method or the like, the decoration layer can be designed to be multicolor (full color). 3 may be formed.

  Subsequently, an ultraviolet curable resin solution is supplied onto the adhesive layer 2. In this case, for example, the ultraviolet curable resin solution is applied to the upper surface of the adhesive layer 2 by using any one or two or more of a spray method and an inkjet method. Among these, it is preferable to form a so-called ultraviolet (UV) printed layer (adhesive layer 2) using an inkjet method. This is because the adhesive layer 2 can be easily formed in a short time.

  Subsequently, the ultraviolet curable resin solution supplied on the adhesive layer 2 is irradiated with ultraviolet rays. By this irradiation treatment, since the ultraviolet curable resin undergoes a curing reaction in the ultraviolet curable resin solution, a cured reaction product (ultraviolet curable resin) of the ultraviolet curable resin is formed. Therefore, the decoration layer 3 containing an ultraviolet curable resin is formed.

  The irradiation method and irradiation conditions are not particularly limited. For example, the irradiation process is performed using an ultraviolet (UV) lamp. The irradiation time is, for example, 1 second to 1 minute.

  Thereby, since the adhesive layer 2 and the decoration layer 3 are formed in this order on the base body 1, the laminate is completed.

<3. Action and Effect>
According to the laminate and the manufacturing method thereof, the adhesive layer 2 (thermosetting resin) is provided between the base 1 and the decoration layer 3 (ultraviolet curable resin), and the thickness of the adhesive layer 2 is 10 μm. ~ 50 μm. In this case, as described above, since the thickness of the adhesive layer 2 is optimized, the adhesion of the adhesive layer 2 to the substrate 1 is specifically improved. As a result, the decorative layer 3 is extremely strongly bonded to the substrate 1. Moreover, the physical strength of the decorative layer 3 is ensured by the ultraviolet curable resin contained in the decorative layer 3. This makes it difficult for the decorative layer 3 to be peeled off from the substrate 1 and makes the decorative layer 3 less likely to wear. Therefore, the peeling resistance and wear resistance of the decorative layer 3 can be improved.

  In particular, the substrate 1 is any one of iron, aluminum, titanium, brass, stainless steel, copper, a copolymer of acrylonitrile and butadiene and styrene, acrylic resin, nylon, polyethylene, polystyrene, polycarbonate, and polyvinyl chloride, or Two or more types are included, the decorative layer 3 (ultraviolet curable resin) contains a polyacrylate ester, and the adhesive layer 2 (thermosetting resin) contains a thermosetting reaction product of a urethane resin and an isocyanate resin. In this case, the peel resistance and wear resistance of the decorative layer 3 can be sufficiently improved.

  In this case, if the base material 1 (resin) contains one or more of a copolymer of acrylonitrile, butadiene and styrene, polyethylene, polystyrene and polycarbonate, the resistance of the decorative layer 3 is improved. Abrasion can be further improved.

  Further, if the adhesive layer 2 is adjacent to the base body 1 and the decorative layer 3, the base body 1 and the decorative layer 3 are firmly bonded via the adhesive layer 2, so that a higher effect can be obtained. Can be obtained.

  Further, if the adhesive layer 2 has a porous structure, the adhesiveness of the adhesive layer 2 to the substrate 1 is further improved, and the adhesiveness of the adhesive layer 2 to the decorative layer 3 is further improved, so that a higher effect can be obtained. Can be obtained.

  Moreover, when forming the contact bonding layer 2 using the thermosetting resin solution containing a lot of organic solvents, the weight of the organic solvent is 4 times or more with respect to the weight of the thermosetting resin, Preferably it is 4 times. If it is 12 times or less, the adhesive layer 2 can be easily formed so as to have the appropriate thickness described above. Therefore, since the adhesive layer 2 having an appropriate thickness can be easily and stably formed, a higher effect can be obtained. In addition, regarding the ultraviolet curable resin solution, when the weight of the organic solvent is 17.5 times or more with respect to the weight of the curing agent, and preferably 17.5 times or more and 26 times or less, the above-described appropriate thickness is obtained. Thus, since the adhesive layer 2 can be formed more easily, a higher effect can be obtained.

  In addition, if the organic solvent contains ethylene glycol monobutyl ether or the like, or if the spray method is used as a method for supplying the thermosetting resin solution, it becomes easier to form the adhesive layer 2 having a porous structure. Can be obtained.

<4. Modification>
[First Modification]
In FIG. 1, the decoration layer 3 covers the entire top surface of the adhesive layer 2, but is not limited thereto.

  For example, as shown in FIG. 2 corresponding to FIG. 1, the decorative layer 3 may partially cover the upper surface of the adhesive layer 2. In this case, the decoration layer 3 may be divided | segmented into plurality, for example. Even in this case, since the base body 1 and the decoration layer 3 are bonded via the adhesive layer 2, the same effect can be obtained.

  In order to form the decoration layer 3 so as to partially cover the surface of the adhesive layer 2, for example, an inkjet method or the like is preferably used as a method for supplying the ultraviolet curable resin solution. This is because the ultraviolet curable resin solution is supplied only to a desired region, so that the decoration layer 3 can be formed to have a desired pattern shape.

[Second Modification]
Further, for example, as shown in FIG. 3 corresponding to FIG. 1, the decorative layer 3 may cover not only the upper surface of the adhesive layer 2 but also the side surfaces. In this case, the decorative layer 3 may cover only the side surface of the adhesive layer 2, or may cover not only the side surface of the adhesive layer 2 but also the side surface of the substrate 1. Even in this case, since the base body 1 and the decoration layer 3 are bonded via the adhesive layer 2, the same effect can be obtained.

[Third Modification]
For example, as shown in FIG. 4 corresponding to FIG. 1, the laminate may include a protective layer 4 on the decorative layer 3.

  The protective layer 4 includes, for example, any one type or two or more types of cured resins. Although the kind of this cured resin will not be specifically limited if it is resin formed by hardening reaction, For example, it is normal temperature curing type resin etc. Specifically, the room temperature curable resin is a cured reaction product of a main agent and a curing agent, such as a cured reaction product of an acrylic polyol and an isocyanate resin, a cured reaction product of a polyester polyol and an isocyanate resin, and a polyether. A cured reaction product of a polyol and an isocyanate resin. Although the kind of isocyanate resin is not particularly limited, for example, it is the same as that described for the adhesive layer 2 described above. Although the thickness of this protective layer 4 is not specifically limited, For example, it is about 15 micrometers or more. In this case, the thickness of the protective layer 4 can be arbitrarily set as long as it is about 15 μm or more.

  Since the protective layer 4 includes a cured resin having excellent physical strength, it plays a role of physically protecting the decorative layer 3. Therefore, in the laminated body provided with the protective layer 4, the decorative layer 3 is less likely to be worn, so that the wear resistance of the decorative layer 3 can be further improved. In addition, in the laminated body provided with the protective layer 4, the weather resistance etc. of the decoration layer 3 can also be improved.

Specific embodiments of the present invention will be described in detail. The order of explanation is as follows.

1. Fabrication and evaluation of laminate 1
1-1. Production 1-2. Evaluation 2 Fabrication and evaluation of laminate 2
2-1. Production 2-2. Evaluation

<1. Fabrication and Evaluation of Laminate 1>
First, in order to investigate the relationship between the presence / absence and thickness of the adhesive layer 2 and the peel resistance and wear resistance of the laminate, the laminate shown in FIG. 1 was prepared by the following procedure.

<1-1. Production>
(Experimental Examples 1-1 to 1-6)
First, a thermosetting resin (vinyl urethane resin), a curing agent (reaction product of tolylene diisocyanate and polyester polyol), and an organic solvent (ethylene glycol monobutyl ether) are mixed, and then the mixture is stirred. Thus, a thermosetting resin solution was prepared. In this case, the ratio of the weight of the organic solvent to the weight of the thermosetting resin (solvent ratio A: times) is quadrupled, and the ratio of the weight of the organic solvent to the weight of the curing agent (solvent ratio B: times). Was doubled.

  Subsequently, after applying the thermosetting resin solution to the upper surface of the substrate 1 (brass), the thermosetting resin solution is heated using a drying furnace (heating temperature = 70 ° C. to 100 ° C., heating time = 20 minutes). Thus, the adhesive layer 2 containing a cured reaction product (thermosetting resin) of the thermosetting resin and the curing agent was formed so as to have the thickness shown in Table 1. In this case, the thickness of the adhesive layer 2 was adjusted by changing the application amount of the thermosetting resin solution.

  Subsequently, after mixing an ultraviolet curable resin (acrylic ester such as methyl acrylate and ethyl acrylate), a polymerization initiator, a coloring material (carbon black), and an organic solvent (hexamethylene diacrylate). The mixture was stirred to prepare an ultraviolet curable resin solution. This ultraviolet curable resin solution is a so-called black ultraviolet (UV) ink.

  Subsequently, an ultraviolet curable resin solution is applied to the upper surface of the adhesive layer 2 using an inkjet method, and then the ultraviolet curable resin solution is irradiated with ultraviolet rays using a UV lamp, thereby curing the ultraviolet curable resin. A decorative layer 3 containing (ultraviolet curable resin) was formed. In this case, the irradiation time = 1 minute in the ultraviolet irradiation step.

  Thereby, since the adhesive layer 2 and the decoration layer 3 were formed in this order on the base body 1, the laminate was completed.

(Experimental Example 1-7)
Except that the adhesive layer 2 was not formed, a laminate was prepared by the same procedure as in Experimental Examples 1-1 to 1-6.

(Experimental Examples 1-8 to 1-19)
As shown in Table 2, a laminated body was produced by the same procedure as in Experimental Example 1-3, except that the material of the substrate 1 was changed.

  The structure of a series of laminated bodies produced here is as shown in Table 1 and Table 2.

<1-2. Evaluation>
When the peel resistance and wear resistance of the laminate were examined, the results shown in Table 1 and Table 2 were obtained.

  In order to investigate the peel resistance, after carrying out a cross-cut test in accordance with JIS K5400-8.5 (JIS D0202), the state of the decorative layer 3 is visually observed and the peeling of the decorative layer 3 is checked. The presence or absence was judged.

  In order to investigate the wear resistance, a friction test was performed according to JIS L 0849 type II, and the surface state of the decorative layer 3 was evaluated in five stages (5 is the best, 1 is the worst). Moreover, after performing the pencil hardness test based on old JIS K5400, the surface of the decoration layer 3 was observed visually and the presence or absence of the generation | occurrence | production of a damage | wound was determined. When carrying out this pencil hardness test, Unipencils (2H, 6H) manufactured by Mitsubishi Pencil Co., Ltd. were used.

  When the adhesive layer 2 containing a thermosetting resin is not provided between the base 1 and the decorative layer 3 containing an ultraviolet curable resin (Experimental Example 1-7), the decorative layer 3 is peeled off from the base 1. The surface of the decorative layer 3 was scratched.

  When the adhesive layer 2 including a thermosetting resin is provided between the base 1 and the decorative layer 3 including the ultraviolet curable resin, the peeling state of the decorative layer 3 and the thickness of the adhesive layer 2 and There was a big difference in the wear situation.

  Specifically, even when the adhesive layer 2 is interposed between the substrate 1 and the decorative layer 3, the thickness of the adhesive layer 2 is smaller than 10 μm (Experimental Example 1-1) and the thickness of the adhesive layer 2 Is larger than 50 μm (Experimental Example 1-6), the decorative layer 3 is peeled off from the base 1 and the decorative layer 3 is removed as in the case where the adhesive layer 2 is not provided (Experimental example 1-7). The surface was scratched. When the peeling state of the decorative layer 3 was examined, the decorative layer 3 was not peeled off from the adhesive layer 2 but the adhesive layer 2 was peeled off from the substrate 1.

  On the other hand, when the thickness of the adhesive layer 2 is 10 μm to 50 μm (Experimental Examples 1-2 to 1-5), the decoration layer 3 does not peel from the base body 1 and the surface of the decoration layer 3 is not peeled off. There were no scratches.

  As a result, when the thickness of the adhesive layer 2 containing the thermosetting resin is 10 μm to 50 μm, the thickness of the adhesive layer 2 is optimized from the viewpoint of adhesion to the substrate 1. 2 shows that the adhesiveness of 2 is specifically improved. Thereby, since the decoration layer 3 is firmly bonded to the base body 1 via the adhesive layer 2, the decoration layer 3 becomes extremely difficult to peel from the base body 1. Thus, despite the use of a common material (thermosetting resin) as the material for forming the adhesive layer 2, there is a significant difference in the peeling state of the decorative layer 3 depending on the thickness of the adhesive layer 2. Is apparent from the results shown in Table 1.

  In particular, when the thickness of the adhesive layer 2 is within an appropriate range (= 10 μm to 50 μm) (Experimental Examples 1-13 to 1-19), the decorative layer 2 is decorated depending on the material (type of resin) of the substrate 1. There was a slight difference in the peeling state and wear state of the layer 3.

  Specifically, when the material of the substrate 1 is a copolymer of acrylonitrile, butadiene and styrene, acrylic resin, nylon, polyethylene, polystyrene, and polycarbonate (Experimental Examples 1-31 to 1-18), Compared with the case where the material is polyvinyl chloride (Experimental Example 1-19), the decorative layer 3 is less likely to be peeled off from the base 1, and the surface of the decorative layer 3 is less likely to be scratched.

  More specifically, focusing on the test result of the pencil hardness test, when the material of the substrate 1 is polyvinyl chloride, the surface of the decorative layer 3 is not damaged when a 2H pencil is used. However, when a 6H pencil was used, the surface of the decorative layer 3 was scratched. On the other hand, when the material of the substrate 1 is a copolymer of acrylonitrile, butadiene and styrene, etc., the decoration layer 3 is obtained both when the 2H pencil is used and when the 6H pencil is used. There was no scratch on the surface.

  When the material of the substrate 1 is a copolymer of acrylonitrile, butadiene and styrene, polyethylene, polystyrene and polycarbonate (Experimental Examples 1-13, 1-16 to 1-18), the material of the substrate 1 is acrylic. Compared to the case of resin and nylon (Experimental Examples 1-14 and 1-15), the decorative layer 3 is more difficult to peel from the substrate 1 while suppressing the generation of scratches on the surface of the decorative layer 3. became.

<2. Fabrication and Evaluation of Laminate 2>
Next, in order to investigate the relationship between the manufacturing method of the adhesive layer 2 and the peel resistance and wear resistance of the laminate, the laminate shown in FIG. 1 was prepared by the following procedure.

<2-1. Production>
(Experimental example 2)
As shown in Table 3, a laminate was prepared in the same manner as in Experimental Example 1-3, except that the solvent ratio A and the solvent ratio B were changed. When changing the solvent ratio A and the solvent ratio B, the mixing amount of the organic solvent (ethylene glycol monobutyl ether) was changed.

<2-2. Evaluation>
When the peel resistance and wear resistance of the laminate were examined, the results shown in Table 3 were obtained. The procedure for examining the peel resistance and the wear resistance is as described above. For reference, Table 3 also shows the results regarding Experimental Examples 1-3, 1-7, 1-13, 1-15, and 1-16 shown in Tables 1 and 2.

  When the adhesive layer 2 is formed using a thermosetting resin solution (Experimental Examples 1-3, 1-13, 1-15, 1-16, 2), the state of the decorative layer 3 according to the solvent ratio A A big difference occurred.

  Specifically, when the solvent ratio A is less than 4 (Experimental Example 2), the adhesive layer 2 could not be formed so as to have an appropriate thickness, and thus the adhesive layer 2 was not provided (Experimental Example 1). The same result as in 7) was obtained. That is, the decorative layer 3 was peeled off from the base body 1 and the surface of the decorative layer 3 was scratched.

  On the other hand, when the solvent ratio A was 4 or more (Experimental Examples 1-3, 1-13, 1-15, 1-16), the adhesive layer 2 could be formed to have an appropriate thickness. The decorative layer 3 did not peel from the substrate 1 and the surface of the decorative layer 3 was not damaged.

  As a result, when a large amount of organic solvent is contained in the thermosetting resin solution, the thickness of the adhesive layer 2 can be easily controlled, so that the adhesive layer 2 can be easily formed to have an appropriate thickness. Represents that. Thereby, it is considered that the adhesive layer 2 having an appropriate thickness can be easily and stably formed.

  From the results shown in Tables 1 to 3, an adhesive layer 2 (thermosetting resin) is provided between the substrate 1 and the decorative layer (ultraviolet curable resin) 3, and the thickness of the adhesive layer 2 is 10 μm to When it is 50 μm, the peel resistance and the wear resistance are improved.

  While the present invention has been described above with reference to the embodiments and examples, the present invention is not limited to the modes described in the embodiments and examples, and various modifications can be made. For example, the laminate of the present invention is not limited to the use described above, and may be applied to other uses.

  DESCRIPTION OF SYMBOLS 1 ... Base | substrate, 2 ... Adhesive layer, 3 ... Decoration layer, 4 ... Protective layer.

Claims (14)

A substrate;
A decorative layer containing an ultraviolet curable resin;
An adhesive layer provided between the base and the decorative layer, including a thermosetting resin and having a thickness of 10 μm or more and 50 μm or less ;
The adhesive layer is adjacent to the decorative layer and has a porous structure.
Laminated body. The substrate includes at least one of iron, aluminum, titanium, brass, stainless steel, copper, a copolymer of acrylonitrile, butadiene, and styrene, acrylic resin, nylon, polyethylene, polystyrene, polycarbonate, and polyvinyl chloride,
The ultraviolet curable resin includes a polyacrylate ester,
The thermosetting resin includes a thermosetting reaction product of at least one of urethane resin, phenol resin, unsaturated polyester, urea resin, melamine resin, and epoxy resin.
The laminate according to claim 1. The urethane resin includes a vinyl urethane resin,
The laminate according to claim 2. The adhesive layer is adjacent to the substrate ;
The laminate according to any one of claims 1 to 3 . The decorative layer is an ultraviolet (UV) printed layer;
The laminate according to any one of claims 1 to 4 . The decorative layer includes a coloring material,
The laminate according to any one of claims 1 to 5 . Furthermore, provided with a protective layer provided on the decorative layer and containing a cured resin,
The laminate according to any one of claims 1 to 6 . Preparing a first solution containing a thermosetting resin and an organic solvent and having a weight of the organic solvent of at least 4 times the weight of the thermosetting resin;
Supplying the first solution on the substrate ;
By heating the first solution supplied on the substrate, an adhesive layer containing a thermosetting resin and having a thickness of 10 μm or more and 50 μm or less is formed.
Supplying a second solution containing an ultraviolet curable resin on the adhesive layer ;
By irradiating the second solution supplied on the adhesive layer with ultraviolet rays , a decorative layer containing an ultraviolet curable resin is formed.
A manufacturing method of a layered product. The weight of the organic solvent is 12 times or less with respect to the weight of the thermosetting resin.
The manufacturing method of the laminated body of Claim 8 . The first solution includes a curing agent;
The weight of the organic solvent is 17.5 times or more with respect to the weight of the curing agent.
The manufacturing method of the laminated body of Claim 8 or Claim 9 . The weight of the organic solvent is not more than 26 times the weight of the curing agent.
The manufacturing method of the laminated body of Claim 10 . The organic solvent includes at least one of toluene, acetone, and ethylene glycol monobutyl ether.
The manufacturing method of the laminated body of any one of Claim 8 thru | or 11. Forming the adhesive layer using a spray method;
The manufacturing method of the laminated body of any one of Claims 8 thru | or 12 . Forming the decorative layer using an inkjet method;
The manufacturing method of the laminated body of any one of Claims 8 thru | or 13 .

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