JP2021008568A - Heat fusible film, laminate, manufacturing method of decorative compact, and decorative compact - Google Patents

Abstract

To provide novel technology capable of combining excellent adhesiveness and irregularity suppression of a decorative mold surface, in decoration of fiber-reinforced plastic using a decorative film.SOLUTION: With a heat-fusible film in which both of a surface on one-side and a surface on the other side are formed of a heat fusible resin layer containing 80 wt.% or larger of acid-modified polyolefin, a first member constituted of a decorative film and a second member constituted of fiber-reinforced plastic are connected, thereby excellent adhesiveness in the obtained decorative compact, and excellent irregularity suppression effect of a surface of the decorative mold may be obtained.SELECTED DRAWING: None

Description

The present disclosure relates to a heat-welding film, a laminate, a method for producing a decorative molded product, and a decorative molded product.

Fiber reinforced plastics (CFRPs), which are resin-reinforced with reinforcing fibers composed of a large number of continuous fibers, are frequently used in structures that require light weight and mechanical properties. For example, fiber reinforced plastics are used for transportation equipment such as aircraft, automobiles, motorcycles, and bicycles, tennis equipment, golf equipment, sports equipment such as fishing rods, construction structures such as seismic retrofitting materials, electrical and electronic equipment, and industry. It is used for members such as robot arms.

In recent years, fiber reinforced plastics have been expanded in use not only in terms of their light weight and mechanical properties, but also in terms of design. Such expanded applications include members used in products such as consumer robots and toys. These products using fiber reinforced plastics are offered as having further enhanced commercial value by having excellent designability in addition to excellent lightness and mechanical properties.

As a means for imparting design to the fiber reinforced plastic, a method of directly coating the fiber reinforced plastic molded product can be generally mentioned. However, this method has problems in terms of coating efficiency and quality control when coating is applied to a non-smooth surface reflecting the unevenness of the reinforcing fibers. On the other hand, a pretreatment in which the uneven surface of the fiber reinforced plastic is smoothed in advance by a polishing treatment is also generally performed, but in this case, a new problem of increasing man-hours arises. Further, in any case, the method of directly coating the fiber-reinforced plastic molded product has an essential problem in terms of environmental load.

Therefore, a decorative film has been proposed as a means for more easily imparting design to fiber reinforced plastics while considering the environmental load.

As an example of a decorative film, Patent Document 1 discloses a decorative sheet for carbon fiber reinforced plastic in which a colored layer containing a binder resin having a high softening point and a heat-adhesive layer are laminated on a base material. In this decorative sheet for carbon fiber reinforced plastic, by using a resin having a softening point of 90 ° C. or higher as the binder resin contained in the colored layer, the unevenness of the carbon fiber texture is reflected on the surface of the decorative composite material. The non-smoothness is improved. Further, Patent Document 1 demonstrates that the effect of improving the surface non-smoothness is exhibited regardless of the presence or absence of the heat-adhesive layer. The heat-adhesive layer laminated on the colored layer includes an acrylic resin, an acrylic-modified polyolefin resin, a chlorinated polyolefin resin, a vinyl chloride-vinyl acetate copolymer, a thermoplastic urethane resin, a thermoplastic polyester resin, and a polyamide resin. , And a thermoplastic resin such as a rubber resin, and a thermosetting resin such as a urethane resin and an epoxy resin are disclosed.

Further, as another example of the decorative film, in Patent Document 2, the highest temperature among the glass transition temperatures of the film is Tg [° C.], and the elongation at break at a temperature T [° C.] of Tg to Tg + 50 [° C.] or less. Films having a degree of 50% or more and having a specific spatial frequency characteristic under specific conditions are disclosed. By adhering this film to an adherend having irregularities such as scratches on the surface, the irregularities can be sufficiently reduced and the surface can be flattened, so that the decorative molded body has a good appearance quality. Can be obtained. Specifically, in Patent Document 2, the film has a multilayer structure of a base material layer and an adhesive layer, and the composition of the resin constituting the adhesive layer is a thermoplastic elastomer 100 containing an aromatic vinyl compound unit or the like. The obtained film has good adhesiveness as long as it is in the range of 1 to 30 parts by mass of the polypropylene resin with respect to the mass part, and the formability at the time of decorative molding and the appearance quality of the surface after decorative molding are improved. It is described as excellent.

Japanese Unexamined Patent Publication No. 2013-202922 International Publication No. 2018/021460

In the techniques disclosed in Patent Document 1 and Patent Document 2, the decorative film itself is configured to solve the problem of non-smoothness due to the surface unevenness of the decorative object being reflected on the surface of the decorative molded body. ing. Therefore, there are many restrictions on the materials that make up these decorative films. Considering that the decorative film is based on the integrated structure of the decorative layer and the adhesive layer, the required design of the decorative film in which the constituent materials are restricted in this way is becoming more and more diverse these days. The number of cases where the market demand cannot be met will increase.

Further, in the decorative film disclosed in Patent Document 1, a solution for obtaining the smoothness of the surface of the decorative molded body is being studied. However, in Patent Document 1, no study has been made on the adhesiveness to the object to be decorated. On the other hand, in the decorative film disclosed in Patent Document 2, the resin composition of the adhesive layer for providing the smoothness of the surface of the decorative molded body and the adhesiveness to the object to be decorated is disclosed. However, in the adhesive layer described in Patent Document 2, it is important to blend a dominant amount of thermoplastic elastomer for providing smoothness, so that the obtained adhesiveness cannot be said to be sufficient.

Therefore, an object of the present invention is to provide a new technique capable of achieving both excellent adhesiveness and suppression of unevenness on the surface of a decorative molded body in the decoration of fiber reinforced plastics using a decorative film.

The present inventors decorate the fiber reinforced plastic by using a physically independent heat-weldable film and heat-welding the decorative film between the fiber reinforced resin plastic or its prepreg. I came up with a novel idea. Then, when an attempt was made to decorate the fiber reinforced plastic using a heat-weldable film, surprisingly, the unevenness of the surface of the decorative molded body was suppressed as compared with the case of using the decorative film provided with the adhesive layer in advance. We found that the effect was further improved. Furthermore, when the adhesiveness between the decorative film and the fiber reinforced plastic was examined, both the surface on one side and the surface on the other side were composed of a specific heat-welding resin layer containing 80% by weight or more of acid-modified polyolefin. It has been found that by using the heat-weldable film obtained, a dramatically improved adhesive strength can be obtained and the above-mentioned unevenness suppressing effect is further improved. The present invention has been completed by further studies based on these findings.

That is, the present invention provides the inventions of the following aspects.
Item 1. A heat-weldable film for joining a first member made of a decorative film and a second member made of fiber reinforced plastic.
A thermosetting film in which both the surface on one side and the surface on the other side are composed of a thermosetting resin layer containing 80% by weight or more of an acid-modified polyolefin.
Item 2. Item 2. The heat-weldable film according to Item 1, wherein the acid-modified polyolefin has an acid modification degree of 0.05% by weight or more.
Item 3. Item 2. The heat-weldable film according to Item 1 or 2, wherein the acid-modification degree of the acid-modified polyolefin is 0.05 to 0.2% by weight.
Item 4. Item 2. The heat-weldable film according to any one of Items 1 to 3, wherein the modified polyolefin of the acid-modified polyolefin is selected from the group consisting of polyethylene and polypropylene.
Item 5. Item 2. The thermosetting film according to any one of Items 1 to 4, wherein the thermosetting resin layer has a thickness of 20 μm or more.
Item 6. Item 2. The heat-weldable film according to any one of Items 1 to 5, wherein the surface roughness of the surface of the fiber-reinforced plastic to be bonded to the heat-weldable film is 25 μm or more.
Item 7. Item 2. The heat-weldable film according to any one of Items 1 to 6, wherein the fiber in the fiber reinforced plastic is a plain weave cloth, a twill weave cloth, a satin weave cloth, or a one-way cloth.
Item 8. The decorative film includes a base material layer and a decorative layer, the decorative layer is provided on the side to be bonded to the heat-welding film, and a vinyl chloride / vinyl acetate copolymer resin and a chlorinated polypropylene resin are provided. Item 2. The item 1 to 7, which comprises a binder resin selected from the group consisting of polyester resin, polyamide resin, polybutylal resin, polystyrene resin, nitricellulose resin, urethane resin, acrylic resin, and acrylic urethane resin. Heat-weldable film.
Item 9. Item 8. The heat-sealing film according to Item 8, wherein the base material layer is selected from the group consisting of acrylic resin, polyester, polyolefin, vinyl resin, acrylonitrile butadiene styrene copolymer, polyurethane and polycarbonate.
Item 10. Item 2. The thermosetting film according to any one of Items 1 to 9, wherein the thermosetting resin layer is a single-layer film.
Item 11. At least, a first heat-welding resin layer, a support layer, and a second heat-welding resin layer are provided in this order, and the surface of the first heat-welding resin layer is the surface on one side, and the second. Item 2. The heat-weldable film according to any one of Items 1 to 9, wherein the surface of the heat-weldable resin layer is the surface on the other side.
Item 12. Item 2. The heat-weldable film according to any one of Items 1 to 11, wherein the matrix resin of the fiber reinforced plastic is a thermosetting resin.
Item 13. Item 2. The heat-weldable film according to any one of Items 1 to 11, wherein the matrix resin of the fiber-reinforced plastic is a thermoplastic resin.
Item 14. Item 2. The heat according to any one of Items 1 to 13, wherein the first member made of the decorative film and the second member made of the fiber reinforced plastic or the second member precursor made of the prepreg of the fiber reinforced plastic are used. Laminated body laminated through a weldable film.
Item 15. A laminate in which a first member made of a decorative film and a second member precursor made of a fiber reinforced plastic prepreg are laminated via the thermosetting film according to any one of claims 1 to 12. A method for producing a decorative molded product, wherein heat welding, thermosetting and molding of the prepreg are performed at the same time to obtain a decorative molded product in which the first member and the second member are joined.
Item 16. A laminate obtained by laminating a first member made of a decorative film and a second member made of a fiber reinforced plastic via a thermoforming film according to any one of Items 1 to 11 and 13 is heated. A method for manufacturing a decorative molded product, wherein heat welding and thermoforming are performed at the same time to obtain a decorative molded product in which the first member and the second member are joined.
Item 17. Decorative molding in which a first member made of a decorative film and a second member made of a fiber reinforced plastic are joined via a heat-welding film according to any one of Items 1 to 13. body.

According to the present invention, there is provided a new technique capable of achieving both excellent adhesiveness and suppression of unevenness on the surface of a decorative molded body in the decoration of fiber reinforced plastics using a decorative film.

It is a schematic sectional view of an example of the heat-weldable film of this disclosure. It is a schematic sectional view of an example of the heat-weldable film of this disclosure. It is a schematic sectional view of an example of the heat-weldable film of this disclosure. It is a schematic sectional view of an example of the heat-weldable film of this disclosure. It is a schematic sectional view of an example of the heat-weldable film of this disclosure. It is a schematic sectional view of an example of the decorative molded article of this disclosure. It is a schematic diagram for demonstrating the measuring method of a seal strength. It is a schematic diagram for demonstrating an example of the manufacturing method of the decorative molded article of this disclosure. It is a schematic diagram for demonstrating an example of the manufacturing method of the decorative molded article of this disclosure. It is a schematic sectional view of an example of the decorative molded article manufactured by the manufacturing method of the decorative molded article of this disclosure.

The heat-weldable film of the present disclosure is a heat-weldable film for joining a first member made of a decorative film and a second member made of a fiber-reinforced plastic, and the heat-weldable film is a heat-weldable film. Both the surface on one side and the surface on the other side are characterized by being composed of a heat-welding resin layer containing 80% by weight or more of acid-modified polyolefin. Hereinafter, the heat-weldable film of the present disclosure, a method for producing a decorative molded product using the heat-weldable film, and a decorative molded product will be described in detail.

In this specification, the numerical range indicated by "-" means "greater than or equal to" and "less than or equal to". For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less.

1. 1. Heat-weldable film The heat-weldable film of the present disclosure is a heat-weldable film for joining a first member made of a decorative film and a second member made of a fiber-reinforced plastic. As an adhesive means used for joining the first member and the second member by heat welding, a heat-weldable film physically independent of the first member and the second member is used to form the first member or the second member. Compared with using a heat-weldable layer provided in advance, the effect of suppressing unevenness on the surface of the obtained decorative molded body can be improved. Although the mechanism for obtaining such an effect of improving unevenness suppression is not clear, the heat-weldable film of the present disclosure, which is physically independent of the first member and the second member, is previously applied to the first member or the second member. Compared with the provided heat-welding layer, the structure such as crystallinity of the resin is different due to the difference in manufacturing method, etc., and this difference causes a difference in the molten state at the time of hot pressing, and eventually a difference in the effect of suppressing unevenness. It is thought that it is.

More specifically, in the heat-weldable film of the present disclosure, the heat-weldable film is arranged between a first member made of a decorative film and a second member made of a fiber reinforced plastic, and heat is generated. It is used for joining the first member and the second member by heat-welding the first member and the second member through a weldable film. In addition to the first member and the second member, further other members may be joined using the heat-weldable film of the present disclosure. That is, the heat-weldable film of the present disclosure is a heat-weldable film for joining at least a first member made of a decorative film and a second member made of a fiber reinforced plastic by heat welding.

For example, as shown in the schematic diagram of FIG. 1, the heat-weldable film 10 of the present disclosure is configured to include at least a heat-weldable resin layer 1 containing a specific amount of acid-modified polyolefin. The heat-weldable film 10 shown in FIG. 1 is configured as a single-layer film of the heat-weldable resin layer 1. That is, the heat-weldable resin layer 1 containing a specific amount of acid-modified polyolefin constitutes both one side surface and the other side surface of the heat-weldable film 10.

In the heat-weldable film 10 of the present disclosure, as long as the heat-weldable resin layer 1 containing a specific amount of acid-modified polyolefin constitutes both one side surface and the other side surface of the heat-weldable film 10. It may have a multi-layer structure in which other layers are embedded. When the heat-weldable film 10 of the present disclosure has a multi-layer structure, the heat-weldable resin layer 1 containing a specific amount of the acid-modified polyolefin of the heat-weldable film 10 of the present disclosure is shown in FIGS. 2 to 5. As shown in the schematic diagram of, the first heat-weldable resin layer 1a constituting the surface on one side of the heat-weldable film 10 and the surface on the other side of the heat-weldable film 10 via at least the support layer 3. It may be divided into a second heat-weldable resin layer 1b constituting the above. That is, the heat-weldable film 10 of the present disclosure contains at least a first heat-weldable resin layer 1a containing a specific amount of acid-modified polyolefin, a support layer 3, and a second heat containing a specific amount of acid-modified polyolefin. It may be configured as a heat-weldable film provided with the weldable resin layer 1b in this order.

As a specific example of the laminated structure when the heat-weldable film 10 of the present disclosure has a multi-layer structure, the first heat-weldable resin layer 1a / support layer 3 / second heat-weldable resin as shown in FIG. Laminated structure including layers 1b in this order; Laminated structure including first heat-weldable resin layer 1a / support layer 3 / thermoplastic resin layer 4 / second heat-weldable resin layer 1b as shown in FIG. 3; A laminated structure including a first heat-welding resin layer 1a / a thermoplastic resin layer 4 / a support layer 3 / a second heat-welding resin layer 1b as shown in FIG. 4 in this order; a first as shown in FIG. Examples thereof include a laminated structure in which the heat-welding resin layer 1a / the thermoplastic resin layer 4 / the support layer 3 / the thermoplastic resin layer 4 / the second heat-welding resin layer 1b are provided in this order. As will be described later, the first thermosetting resin layer 1a and the second thermosetting resin layer 1b may each contain an adhesive component and have adhesiveness. Further, the thermoplastic resin layer 4 may have a heat-welding property as well as the first thermosetting resin layer 1a and the second thermosetting resin layer 1b. The heat-weldable film of the present disclosure may be further laminated with other layers different from these layers. For example, although not shown, an adhesion promoter layer described later may be provided on one side or both sides of the support layer 3.

From the viewpoint of low cost and simplification of the manufacturing process, the heat-weldable film of the present disclosure preferably has a single-layer structure composed of a single resin as shown in FIG. The single-layer structure makes it easier to provide a thermosetting resin layer containing a specific amount of acid-modified polyolefin relatively thicker than in the case of a multi-layer structure, thereby providing adhesiveness and decoration. It is also preferable in that the effect of suppressing unevenness on the surface of the molded body is further improved. On the other hand, in the case of a multi-layer structure, it is preferable to make the heat-weldable film thin from the viewpoint of low cost and simplification of the manufacturing process, and the heat-weldable film of the present disclosure is the first as shown in FIG. It is preferable to have a three-layer laminated structure including one heat-weldable resin layer 1a / support layer 3 / second heat-weldable resin layer 1b in this order. Further, from the viewpoint of improving the effect of suppressing unevenness, it is preferable to make the heat-weldable film thicker, and the heat-weldable film of the present disclosure has the first heat-weldable resin layer 1a, the support layer 3, and the second heat-weldability. It is preferable to provide a thermoplastic resin layer between each layer of the resin layer 1b. Specifically, a laminated structure of four layers including a first heat-weldable resin layer 1a / support layer 3 / thermoplastic resin layer 4 / second heat-weldable resin layer 1b as shown in FIG. 3; A four-layer laminated structure including a first heat-welding resin layer 1a / a thermoplastic resin layer 4 / a support layer 3 / a second heat-welding resin layer 1b as shown in FIG. 4 in this order; as shown in FIG. It is preferable to have a five-layer laminated structure including the first heat-welding resin layer 1a / the thermoplastic resin layer 4 / the support layer 3 / the thermoplastic resin layer 4 / the second heat-welding resin layer 1b in this order. Further, in the decorative molded body after joining, when the first thermoplastic resin layer 1a contains an adhesive component, the heat-weldable film of the present disclosure has five layers containing the adhesive component on both sides. Laminated structure (specifically, a first heat-welding resin layer 1a containing an adhesive component / a thermoplastic resin layer 4 / a support layer 3 / a thermoplastic resin layer 4 / a second heat-welding resin layer 1b containing an adhesive component. A laminated structure provided in this order) or a four-layer laminated structure containing an adhesive component on one side (specifically, a first heat-welding resin layer 1a containing an adhesive component / a thermoplastic resin layer 4 / a support layer 3). / A laminated structure in which the thermoplastic resin layer 4 / the second heat-welding resin layer 1b containing no adhesive component is provided in this order) may be provided.

From the viewpoint of low cost and suppressing the possibility of delamination, the number of layers of the heat-weldable film of the present disclosure is preferably small, and a preferable lower limit is 1 or more, and a preferable upper limit is 5 or less.

Further, the surface area of the heat-weldable film of the present disclosure can be appropriately set according to the size of the member to be heat-welded.

<Seal strength>
The adhesiveness between the first member and the second part by the heat-weldable film 10 of the present disclosure is evaluated by the sealing strength between the heat-weldable film 10 and each of the first member and the second member. Specifically, the heat-weldable film 10 of the present disclosure has a seal strength between the heat-weldable film and the member of about 10 N / 15 mm or more when heat-welded to each of the first member and the second member. It is more preferably about 15 N / 15 mm or more, further preferably about 17 N / 15 mm or more, further preferably about 18 N / 15 mm or more, and about 20 N / 15 mm or more. Is particularly preferable. Further, the sealing strength between the heat-weldable film and the first member is preferably about 15 N / 15 mm or more, more preferably about 17 N / 15 mm or more between the first member and the second member. It is more preferably about 18 N / 15 mm or more, and even more preferably about 20 N / 15 mm or more. Although there is no particular preferable upper limit of the seal strength, it is usually about 100 N / 15 mm or less. That is, the range of the seal strength is preferably about 10 to 100 N / 15 mm, more preferably about 15 to 100 N / 15 mm, further preferably about 17 to 100 N / 15 mm, still more preferably 18 to 100 N / 15 mm, and particularly preferably. Is about 20 to 100 N / 15 mm.

In the heat-weldable film 10 of the present disclosure for heat-welding the first member and the second member, when the seal strength at the time of heat-welding to these members has the above value, the decorative molded body obtained. In the present invention, it can be said that the heat-weldable film 10 of the present disclosure exhibits better adhesiveness between the first member and the second member to bring about a suitable bonding state. When the second member, which is a fiber reinforced plastic, is joined by heat welding in a fiber reinforced plastic prepreg (second member precursor) containing an uncured resin, the seal strength is the uncured. It means the sealing strength between the resin and the fiber reinforced plastic (second member) after being thermoset. The specific method for measuring the seal strength is as follows. The sealing strength when the heat-weldable film 10 of the present disclosure and the first member and the second member are heat-welded is not limited to this range.

In measuring the seal strength, first, the heat-weldable film is cut into a size of 50 mm in the length direction (y direction) × 25 mm in the width direction (x direction). Next, the heat-weldable film 10 and each member 50 are heat-sealed (heat-sealing conditions: temperature 190 ° C., surface pressure 1 MPa, pressurization time 5 seconds) at a depth of 7 mm (y direction) to prepare a test sample. obtain. In the schematic diagram of FIG. 7, the region S surrounded by the broken line indicates the heat-sealed region. In preparing the test sample, first, a release sheet is sandwiched between the heat-weldable film 10 and the member 50 (first member or second member) in a portion other than the region having a depth of 7 mm to be heat-sealed. , Heat seal only in the area with a depth of 7 mm. Next, the test sample is cut into a width of 15 mm as shown in FIG. 7A so that the seal strength (N / 15 mm) in the width direction (x direction) of 15 mm can be measured. Subsequently, as shown in FIG. 7B, the heat-weldable film 10 is peeled from the fixed member 50 in the length direction (y direction) using a tensile tester. At this time, the peeling speed is 300 mm / min, and the maximum load until peeling is the seal strength (N / 15 mm). As the member 50 in the preparation of the test sample, a member having a thickness of 4 mm in the case of fiber reinforced plastic and a thickness of 130 μm in the case of a decorative film is used. Each seal strength is an average value (n = 3) measured by preparing three test samples in the same manner.

<Surface roughness>
The unevenness-suppressing property of the surface of the decorative molded product is evaluated by the surface roughness of the decorated surface of the decorative molded product. The surface roughness of the surface of the decorative molded body is the arithmetic average roughness Ra measured with a cutoff value of 1.6 mm and a measurement length of 10 mm using a contact type roughness meter in accordance with JIS B0601: 2013. Is. As the contact type roughness meter, Surfcom NEX manufactured by Tokyo Seimitsu Co., Ltd. can be used.

(Thermosetting resin layer 1)
In the present disclosure, the thermosetting resin layer 1 is a layer constituting both one side surface and the other side surface of the heat welding film 10 of the present disclosure. That is, when the heat-weldable film 10 of the present disclosure has a single-layer structure of the heat-weldable resin layer 1, one surface and the other side of the heat-weldable resin layer 1 which are single layers are heat-welded, respectively. It corresponds to the surface on one side and the surface on the other side of the sex film 10.

The thermosetting resin layer 1 contains 80% by weight or more of acid-modified polyolefin. As a result, excellent sealing strength is exhibited for both the first member and the second member, which are different members from each other, and excellent adhesiveness between the first member and the second member can be obtained. In addition to this, the effect of suppressing unevenness on the surface of the decorative molded body obtained by joining the first member and the second member by heat welding can be satisfactorily obtained. The fact that the resin constituting the heat-sealing resin layer 1 contains 80% by weight or more of acid-modified polyolefin can be analyzed by, for example, infrared spectroscopy, gas chromatography-mass spectrometry, etc., and the analysis method is particularly It doesn't matter. For example, when measuring the infrared spectroscopy at a maleic anhydride-modified polyolefin, a peak derived from maleic acid is detected in the vicinity of the wave number of 1760 cm ^-1 and near the wave number 1780 cm ^-1. Furthermore, quantitative analysis can be performed based on the integral value of the peak.

Specific examples of the acid-modified polyolefin include polyolefins modified with unsaturated carboxylic acids or their anhydrides. Examples of the unsaturated carboxylic acid or its anhydride used for acid modification include maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, and maleic anhydride is preferable. Be done.

The polyolefin to be modified is not particularly limited, but is preferably low-density polyethylene, medium-density polyethylene, or high-density polyethylene from the viewpoint of further improving the adhesiveness in the decorative molded body and / or the effect of suppressing unevenness on the surface of the decorative molded body. Polyethylenes such as high density polyethylene, linear low density polyethylene; crystalline or non-crystalline such as homopolypropylene, polypropylene block copolymers (eg propylene and ethylene block copolymers), polypropylene random copolymers (eg propylene and ethylene random copolymers). Crystalline polypropylene; ethylene-butene-propylene tarpolymers can be mentioned. Among these, polyethylene and polypropylene are preferable as the modified polyolefin.

Among the thermosetting resins contained in the thermosetting resin layer 1, from the viewpoint of further improving the adhesiveness in the decorative molded product and / or the effect of suppressing unevenness on the surface of the decorative molded product, maleic anhydride-modified polypropylene, in particular, Maleic anhydride-modified polyethylene is preferable.

The acid-modified polyolefin contained in the thermosetting resin layer 1 may be used alone or in combination of two or more.

The ratio of the acid-modified polyolefin contained in the thermosetting resin layer 1 is not particularly limited as long as it is 80% by weight or more. From the viewpoint of further improving the adhesiveness in the decorative molded product, the lower limit of the proportion of the acid-modified polyolefin is preferably about 90% by mass or more, more preferably about 95% by mass or more, and the upper limit is preferably about 95% by mass or more. About 100% by mass or less can be mentioned. That is, the specific range of the ratio of the acid-modified polyolefin is about 80 to 100% by mass, preferably about 90 to 100% by mass, and about 95 to 100% by mass.

The lower limit of the acid modification degree of the acid-modified polyolefin is, for example, about 0.05% by weight or more. From the viewpoint of obtaining better adhesiveness in the decorative molded product, the lower limit is preferably about 0.07% by weight or more, more preferably about 0.09% by weight or more, and about 0.15% by weight. It is more preferably% or more. Although there is no particular preferable upper limit of the acid denaturation degree, it is usually about 0.5% by weight or less. That is, the specific range of the acid denaturation degree is, for example, about 0.05 to 0.5% by weight, preferably about 0.07 to 0.5% by weight, and more preferably 0.09 to 0.5% by weight. The degree is more preferably about 0.15 to 0.5% by weight.

Since the heat-weldable film 10 of the present disclosure exhibits excellent adhesiveness in a decorative molded product, even if the upper limit of the acid modification degree of the acid-modified polyolefin is lower than the above, excellent adhesiveness in the decorative molded product can be obtained. Can be obtained effectively. From this point of view, a preferable example of the upper limit of the acid modification degree of the acid-modified polyolefin is about 0.2% by weight or less. Thereby, the moldability at the time of manufacturing the decorative molded body can be improved. From the viewpoint of suppressing gel generation during molding and / or improving moldability by making the thickness uniform, the content may be 0.18% by weight or less. That is, the specific range of the acid modification degree is, for example, about 0.05 to 0.2% by weight, about 0.07 to 0.2% by weight, about 0.09 to 0.2% by weight, 0.15. ~ 0.2% by weight, 0.05 to 0.18% by weight, 0.07 to 0.18% by weight, 0.09 to 0.18% by weight, 0.15 to 0.18% by weight The degree can also be mentioned.

The degree of acid modification is the weight ratio of the acid-modified group in the acid-modified polyolefin. For example, in the case of maleic acid-modified polyolefin, it is the weight ratio of maleic acid-modified groups in the acid-modified polyolefin. The degree of acid denaturation is determined from the value quantified from the acid-derived peak area of ¹ H-NMR. Specifically, first, to measure a ¹ H-NMR of the _{ODCB-d4 / C 6 D 6} ( volume ratio 4/1) ¹ H-NMR and methyl esters of the acid-modified polyolefin of the acid-modified polyolefin in a solvent .. A comparison of both ^{1 1} H-NMR identifies the peak of the acid derivatized methyl esterified product. Furthermore, from ¹ H-NMR of the acid-modified polyolefin (before methyl esterification), the area of the impurity-derived peak that overlaps at the peak position of the methyl esterified product in ¹ H-NMR of the methyl esterified product is specified. By subtracting the peak area derived from impurities from the peak area at the peak position of the methyl esterified product, the peak area of the methyl esterified product is obtained, and the mass of the acid-modifying group derived based on this and the acid-modified polyolefin before methyl esterification The degree of acid modification is calculated from the ratio with the mass.

Further, in the heat-welding resin layer 1, assuming that the acid modification degree of the acid-modified polyolefin is a and the content ratio of the acid-modified polyolefin is b% by weight, the product (a × b / 100) thereof is, for example, about 0. 04 or more can be mentioned. From the viewpoint of obtaining better adhesiveness in the decorative molded product, as a preferable example of the above lower limit of the product, preferably about 0.08 or more, more preferably about 0.09 or more, still more preferably about 0.15. The above can be mentioned. Examples of the upper limit of the above product include, for example, about 0.5 or less, and preferably about 0.2 or less, more preferably about 0.18 or less from the viewpoint of obtaining more preferable workability. That is, the specific range of the above products is about 0.04 to 0.5, about 0.08 to 0.5, about 0.09 to 0.5, about 0.15 to 0.5, and 0. About .04 to 0.2, about 0.08 to 0.2, about 0.09 to 0.2, about 0.15 to 0.2, about 0.04 to 0.18, 0.08 to 0. Examples thereof include about 18, about 0.09 to 0.18, and about 0.15 to 0.18.

The thermosetting resin layer 1 may further contain an adhesive component. More specifically, the thermosetting resin layer 1 may be composed of a thermosetting resin composition containing an adhesive component. Since the thermosetting resin layer 1 contains an adhesive component, the thermosetting resin layer 1 of the heat-welding film 10 can be suitably temporarily adhered to the surfaces of the first member and the second member, and at the time of heat welding. It is possible to suppress misalignment and more preferably perform decorative molding. In the present disclosure, temporary adhesion means that the material is temporarily adhered, and is in a state where it can be temporarily adhered and then peeled off.

The thickness of the thermosetting resin layer 1 is not particularly limited, but the lower limit is preferably about 20 μm from the viewpoint of further improving the adhesiveness in the decorative molded product and / or the effect of suppressing unevenness on the surface of the decorative molded product. As described above, more preferably about 40 μm or more, further preferably about 50 μm or more, still more preferably about 90 μm or more, and particularly preferably about 100 μm or more. The upper limit of the thickness of the thermosetting resin layer 1 is not particularly limited, and examples thereof include about 700 μm or less. Since the heat-weldable film 10 of the present disclosure is excellent in the effect of suppressing unevenness on the surface of the decorative molded body, even if the thermosetting resin layer 1 is relatively thin, the unevenness on the surface of the decorative molded body is effectively suppressed. be able to. From such a viewpoint, a preferable example of the upper limit of the thickness of the thermosetting resin layer 1 is preferably about 500 μm or less, more preferably 300 μm or less. That is, the specific range of the thickness of the thermosetting resin layer 1 is preferably about 20 to 700 μm, about 40 to 700 μm, about 50 to 700 μm, about 90 to 700 μm, about 100 to 700 μm, and about 20 to 500 μm. About 40 to 500 μm, about 50 to 500 μm, about 90 to 500 μm, about 100 to 500 μm, about 20 to 300 μm, about 40 to 300 μm, about 50 to 300 μm, about 90 to 300 μm, about 100 to 300 μm.

(1st thermosetting resin layer 1a and 2nd thermosetting resin 1b)
When the heat-weldable film 10 of the present disclosure has a multi-layer structure, the heat-weldable resin layer is divided into a first heat-weldable resin layer 1a and a second heat-weldable resin layer 1b via a support layer 3. There is. The first heat-weldable resin layer 1a is a layer constituting one surface of the heat-weldable film 10, and the second heat-weldable resin layer 1b constitutes the other surface of the heat-weldable film 10. It is a layer that is. That is, in this case, the first heat-weldable resin layer 1a constitutes the outermost layer on one side of the heat-weldable film 10 of the present disclosure, and the second heat-weldable resin layer 1b is the other of the heat-weldable film 10 of the present disclosure. It constitutes the outermost layer on the side.

The first thermosetting resin layer 1a and the second thermosetting resin layer 1b are the same as the above-mentioned thermosetting resin layer 1 except that they are interposed in the support layer 3. Further, the content of the acid-modified polyolefin, the type and thickness of the acid-modified polyolefin in the first heat-welding resin layer 1a and the second heat-welding resin layer 1b may be the same or different from each other. May be

The thickness of each of the first thermosetting resin layer 1a and the second thermosetting resin layer 1b is not particularly limited, but the adhesiveness in the decorative molded product and / or the effect of suppressing unevenness on the surface of the decorative molded product is further improved. From the viewpoint of this, the lower limit is preferably about 10 μm or more, more preferably about 15 μm or more. The upper limit of the thickness of the thermosetting resin layer 1 is not particularly limited, and examples thereof include about 300 μm or less. Since the heat-weldable film 10 of the present disclosure is excellent in the effect of suppressing unevenness on the surface of the decorative molded body, even if the thermosetting resin layer 1 is relatively thin, the unevenness on the surface of the decorative molded body is effectively suppressed. be able to. From such a viewpoint, a preferable example of the upper limit of the thickness of the thermosetting resin layer 1 is preferably about 150 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less. That is, the specific range of the thickness of the thermosetting resin layer 1 is preferably about 10 to 300 μm, about 10 to 150 μm, about 10 to 100 μm, about 10 to 50 μm, about 15 to 300 μm, and about 15 to 150 μm. The degree is about 15 to 100 μm, and about 15 to 50 μm.

(Support layer 3)
When the heat-weldable film 10 of the present disclosure has a support layer 3, the support layer 3 is located between the first heat-weldable resin layer 1a and the second heat-weldable resin layer 1b, and is heat-weldable. The film 10 can be provided with an excellent high tensile elasticity.

The material constituting the support layer 3 is not particularly limited as long as it has a high tensile elasticity, for example, polyester, polyimide, polyamide, epoxy resin, polyvinyl alcohol, polyphenylene sulfide, polyarylate, polycarbonate, acrylic resin, fluororesin. , Silicone resin, phenol resin, polyetherimide, and mixtures and copolymers thereof.

Specific examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene isophthalate, and ethylene terephthalate as the main constituents of the copolymerized polyester and butylene terephthalate as the main constituent of the repeating unit. Examples thereof include the copolymerized polyester. Further, as the copolymerized polyester having ethylene terephthalate as the main body of the repeating unit, specifically, a copolymer polyester having ethylene terephthalate as the main body of the repeating unit and polymerizing with ethylene isophthalate (hereinafter, polyethylene (terephthalate / isophthalate)). (Abbreviated after), polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sodium sulfoisophthalate), polyethylene (terephthalate / sodium isophthalate), polyethylene (terephthalate / phenyl-dicarboxylate) , Polyethylene (terephthalate / decandicarboxylate) and the like. Further, as the copolymerized polyester having butylene terephthalate as the main body of the repeating unit, specifically, a copolymer polyester which polymerizes with butylene isophthalate using butylene terephthalate as the main body of the repeating unit (hereinafter, polybutylene (terephthalate / isophthalate)). (Abbreviated after), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sevacate), polybutylene (terephthalate / decandicarboxylate), polybutylene naphthalate and the like.

In addition to the above, the polyester also includes an aromatic polyester which is a polycondensate containing a monomer selected from the group consisting of an aromatic diol, an aromatic dicarboxylic acid, and an aromatic hydroxycarboxylic acid in an arbitrary composition ratio. Among the aromatic polyesters, a total aromatic polyester having no aliphatic hydrocarbon in the main chain is preferable. Specific examples of the total aromatic polyester include a copolymer of p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, a copolymer of p-hydroxybenzoic acid, terephthalic acid and 4,4'-dihydroxybisphenyl, and the like. Polyaromatic rate can be mentioned.

These polyesters may be used alone or in combination of two or more.

From the viewpoint of reducing the heat shrinkage rate in a high temperature environment during heat welding and making the heat welding film 10 have a higher tensile elasticity, the material of the support layer 3 is preferably polyethylene terephthalate or polyethylene na. Examples include phthalate, total aromatic polyester, polyimide, polyphenylene sulfide, aramid, and vinylon (polyvinyl alcohol). These resins may be used alone or in combination of two or more.

The shape of the support layer 3 is not particularly limited, and examples thereof include a film and a fibrous sheet. Specific shapes of the fibrous sheet include woven fabric and non-woven fabric, and preferably non-woven fabric. From the viewpoint of obtaining a higher tensile elastic modulus of the heat-weldable film 10, the shape of the support layer 3 is preferably a film.

When the shape of the support layer 3 is a film, the support layer 3 is preferably composed of a polyethylene terephthalate film, a polyethylene naphthalate film, and a polyimide film, and more preferably a polyethylene naphthalate film.

When the shape of the support layer 3 is a fibrous sheet, examples of the constituent fibers of the fibrous sheet include polyphenylene sulfide fibers, aramid fibers, vinylon (polyvinyl alcohol) fibers, and total aromatic polyester fibers. These fibers may be used alone or in combination of two or more.

Among these fibers, the total aromatic polyester fiber is a fiber obtained by spinning a total aromatic polyester having a molecular orientation (melt anisotropy) in a molten state (melt anisotropic total aromatic polyester fiber). However, since the molecular orientation further progresses, the fibers are easily entangled with each other, and not only the fibers have strong mechanical strength and low moisture absorption, but also the resin easily penetrates into the gaps formed by division and subdivision, and the non-woven fabric has excellent resin impregnation property. Therefore, it is preferable that the heat-sealing film 10 has extremely high interlayer strength.

The thickness of the support layer 3 is not particularly limited, but the heat shrinkage rate in a high temperature environment at the time of heat welding is reduced, and the decorative molded body after joining has excellent strength against shear stress parallel to the joining surface. From the viewpoint of obtaining, the lower limit is preferably about 5 μm or more, more preferably about 10 μm or more. The upper limit of the thickness of the support layer is not particularly limited, and examples thereof include about 500 μm or less. From the viewpoint of securing the relative thicknesses of the first thermosetting resin layer 1a and the second thermosetting resin layer 1b and further improving the adhesiveness in the decorative molded product, it is preferable as a preferable example of the upper limit. It is about 200 μm or less, more preferably about 100 μm or less, still more preferably about 50 μm or less, still more preferably 40 μm or less, still more preferably 30 μm or less, and particularly preferably 20 μm or less. That is, the specific range of the thickness of the support layer 3 is about 5 to 200 μm, about 10 to 200 μm, about 5 to 100 μm, about 10 to 100 μm, about 5 to 50 μm, about 10 to 50 μm, and about 5 to 40 μm. , About 10 to 40 μm, about 5 to 30 μm, about 10 to 30 μm, about 5 to 20 μm, and about 10 to 20 μm.

(Thermoplastic resin layer 4)
In the present disclosure, the thermoplastic resin layer 4 is a layer laminated on the heat-weldable film 10 as needed. The thermoplastic resin layer 4 is preferably laminated between the first thermosetting resin layer 1a and the support layer 3 and between the support layer 3 and the second thermosetting resin layer 1b. One thermoplastic resin layer 4 may be laminated on the heat-welding film 10, or two or more layers may be laminated. The number of layers of the thermoplastic resin layer 4 in the heat-weldable film 10 is preferably about 0 to 2, more preferably about 0 to 1.

The thermoplastic resin constituting the thermoplastic resin layer 4 is particularly limited as long as it is different from the constituent resins of the adjacent heat-welding resin layers 1a and 1b in the type and / or resin composition of the resin and has thermoplasticity. Not done. Examples of the thermoplastic resin include polyolefin, polyester, polyamide, acrylic resin, fluororesin, silicone resin and the like. The polyolefin may be either an acid-modified polyolefin or an acid-modified polyolefin. These thermoplastic resins may be used alone or in combination of two or more.

Since the heat-weldable film 10 of the present disclosure is excellent in the effect of suppressing unevenness on the surface of the decorative molded body, the unevenness on the surface of the decorative molded body is effectively suppressed even if the thermoplastic resin layer 4 is not included. be able to. From this point of view, a preferred example of the heat-weldable film 10 of the present disclosure is one having a structure that does not include the thermoplastic resin layer 4.

(Other layers)
When the thermosetting film 10 of the present disclosure has a multi-layer structure, a layer different from the first thermosetting resin layer 1a, the second thermosetting resin layer 1b, the support layer 3, and the thermoplastic resin layer 4 May be further laminated.

(Additive)
The heat-weldable film 10 of the present disclosure may contain various additives such as a lubricant, an antioxidant, an ultraviolet absorber, and a light stabilizer, if necessary. As the additive, a type and content at which the heat-weldable film 10 does not discolor are appropriately selected by those skilled in the art.

(Manufacturing method of heat-weldable film)
The thermosetting film 10 of the present disclosure can be produced by using at least a thermosetting resin layer 1 by a melt extrusion method and, if necessary, a stretching method. When the thermosetting film 10 of the present disclosure has a multi-layer structure, at least the first thermosetting resin layer 1a, the support layer 3, and the second thermosetting resin layer 1b are provided, if necessary. It can be manufactured by laminating the thermoplastic resin layer 4. The laminating method of these layers is not particularly limited, and for example, a thermal laminating method, a sandwich laminating method, an extruded laminating method, or the like can be used.

Further, when the heat-weldable film 10 of the present disclosure has a multi-layer structure and the support layer 3 is composed of a resin film, an adhesion accelerator is applied to both surfaces of the support layer 3 (that is, an adhesion accelerator). By providing the layer), the adhesion strength with the adjacent layer (for example, the first heat-welding resin layer 1a, the second heat-welding resin layer 1b, the thermoplastic resin layer 4, etc.) is improved and the laminated structure is stabilized. be able to. Further, if necessary, well-known easy-adhesion means such as corona discharge treatment, ozone treatment, and plasma treatment can be applied to the surface of the support layer 3.

As the adhesion accelerator for forming the adhesion accelerator layer, a well-known adhesion accelerator such as isocyanate-based, polyethyleneimine-based, polyester-based, polyurethane-based, or polybutadiene-based can be used. Further, the adhesion accelerator layer can also be formed by using a known adhesive such as a two-component curable adhesive or a one-component curable adhesive.

The adhesion accelerator layer can be provided on one side or both sides of the support layer 3. The adhesion accelerator layer can be formed by applying and drying by a known coating method such as a bar coating method, a roll coating method, or a gravure coating method.

(Element)
The first member joined by the heat-weldable film 10 is made of a decorative film, and the second member is made of fiber reinforced plastic.

[Decorative film]
The decorative film constituting the first member is a film used to impart designability to an article. The decorative film constituting the first member is not particularly limited as long as it includes the base material layer and the decorative layer. As shown in FIG. 6, which will be described later, a decorative molded body 20 in which the first member 30 and the second member 40 are joined by heat welding of the heat-weldable film 10, the decorative film, which is the first member 30, is a base material. The decorative layer 32 includes the layer 31 and the decorative layer 32, and the decorative layer 32 is provided on the side to be joined to the heat-weldable film 10 in the decorative film. That is, the decorative film, which is the first member 30, is joined to the second member 40 on the decorative layer 32 side via the heat-weldable film 10. Further, the decorative film may be provided with a release layer between the base material layer and the decorative layer. Further, the decorative film may be provided with an adhesive layer on the decorative layer. That is, as an example of a specific laminated structure of the decorative film, the base material layer / decoration layer, the base material layer / decoration layer / adhesive layer, the base material layer / release layer / decoration layer, the base material layer / Examples include a release layer / a decorative layer / an adhesive layer. Further, any layer other than the above may be further laminated on the decorative film.

The base material layer is not particularly limited as long as it can support the decorative layer and has moldability, heat resistance, and the like, but a resin is preferable.

The type of resin used for the base material layer is not particularly limited, and can be appropriately selected in consideration of moldability, heat resistance, and the like. Specifically, as the resin used for the base material layer, acrylic resins such as methyl poly (meth) acrylate and ethyl poly (meth) acrylate; polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyethylene. , Polyethylene and other polyolefins; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene / vinyl acetate copolymers, ethylene / vinyl alcohol copolymers and other vinyl resins; acrylonitrile / butadiene / styrene copolymers; polyurethane; polycarbonate And so on. These resins may be used alone or in combination of two or more. Among these resins, acrylic resin is preferable. Further, it is preferable to use a film of these resins as the base material layer.

The base material layer may be a single layer or may be composed of two or more layers. When the base material layer is composed of two or more layers, the base material layer may be a laminate in which a resin film is laminated with an adhesive or the like, or a resin obtained by co-extruding the resin into two or more layers. It may be a laminate of films. Further, the laminated body of the resin film obtained by co-extruding the resin into two or more layers may be used as the base material layer without being stretched, or may be uniaxially stretched or biaxially stretched as the base material layer.

The base material layer may be subjected to physical or chemical surface treatment such as oxidation treatment or unevenness treatment on one or both sides, if necessary, as long as the effects of the present invention are not impaired. Examples of the oxidation treatment include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method and the like. Further, as the unevenness treatment, for example, a sandblasting method, a solvent treatment method and the like can be mentioned.

The thickness of the base material layer is not particularly limited, but from the viewpoint of operability, workability, cost, etc., for example, about 10 to 500 μm, preferably about 30 to 300 μm, more preferably about 50 to 200 μm, still more preferably 70. About 150 μm, more preferably about 90 to 130 μm.

The decorative layer imparts design to the decorative sheet. The decorative layer is composed of a pattern layer and / or a concealing layer. Here, the pattern layer is a layer provided for expressing a pattern such as a pattern or characters and a pattern pattern, and the concealing layer is usually a solid layer on the entire surface and is provided for concealing coloring or the like of a molding resin or the like. It is a layer. The concealing layer may be provided inside the pattern layer in order to enhance the pattern of the pattern layer, or the concealing layer alone may form a decorative layer. The pattern of the pattern layer is not particularly limited, but for example, a stone pattern imitating the surface of a rock such as a wood grain pattern or a marble pattern (for example, a travertin marble pattern), a cloth pattern imitating a cloth grain or a cloth-like pattern, or a tile. Examples include pasted patterns, brick-layed patterns, patterns such as parquet or patchwork in which these are combined, symbols, letters, and combinations thereof.

The decorative layer is a layer composed of an ink composition and contains a colorant and a binder resin.

The colorant is not particularly limited, but is, for example, a metallic composed of scaly foil powder of a metal such as aluminum, chromium, nickel, tin, titanium, iron phosphate, copper, gold, silver, brass, an alloy, or a metal compound. Pigments: Pearl luster consisting of mica-like iron oxide, titanium dioxide-coated mica, titanium dioxide-coated bismuth oxychloride, bismuth oxychloride, titanium dioxide-coated talc, fish scale foil, colored titanium dioxide-coated mica, basic lead carbonate, etc. Pearl) Pigments; Fluorescent pigments such as strontium aluminate, calcium aluminate, barium aluminate, zinc sulfide, calcium sulfide; white inorganic pigments such as titanium dioxide, zinc oxide, antimony trioxide; zinc oxide, petals, vermilion, ultramarine , Cobalt blue, titanium yellow, yellow lead, carbon black and other colored inorganic pigments; Isoindolinon yellow, Hansa yellow A, quinacridone red, permanent red 4R, phthalocyanine blue, induslen blue RS, aniline black and other organic pigments (dye) Including) and the like. These colorants may be used alone or in combination of two or more.

The binder resin is not particularly limited, and examples thereof include a resin having a softening point of less than about 90 ° C. When the decorative layer of the decorative film, which is the first member, is joined to the second member so as to be in direct contact with the heat-weldable film 10, the binder resin is used from the viewpoint of further improving the adhesiveness in the decorative molded body. A preferable example of the above is a resin having a softening point of about 87 ° C. or lower. The lower limit of the softening point of the binder resin is not particularly limited, but from the viewpoint of coating stability of the decorative layer during the production of the decorative film, for example, about 50 ° C. or higher, preferably about 60 ° C. or higher can be mentioned. That is, specific ranges of the softening point of the binder resin include about 50 ° C. or higher and lower than about 90 ° C., about 50 ° C. to 87 ° C., about 60 ° C. or higher and lower than about 90 ° C., and about 60 to 87 ° C. Here, the softening point is measured using the JIS K5601-2-2 paint component test method-the ring-ball method, which is the softening point test method for the paint component of Part 2.

The resin used as the binder resin is not particularly limited, but for example, vinyl chloride / vinyl acetate copolymer resin, chlorinated polypropylene resin, polyester resin, polyamide resin, polybutylal resin, polystyrene resin, nitricellulose resin, urethane. Examples thereof include resins, acrylic resins, and acrylic urethane resins. These binder resins may be used alone or in combination of two or more. Among these binder resins, acrylic is used from the viewpoint of obtaining better adhesiveness in the decorative molded product and coating stability of the decorative layer during the production of the decorative film by selecting a resin having a preferable softening point. Urethane resin is preferable. In the present disclosure, the acrylic urethane resin refers to a urethane resin obtained by polymerizing isocyanate using an acrylic polyol as a main component. In the present disclosure, the urethane resin and the acrylic resin exemplified as the resin used for the binder resin do not include the acrylic urethane resin.

The thickness of the decorative layer is not particularly limited, and examples thereof include about 1 to 40 μm, preferably about 3 to 30 μm, and more preferably about 3 to 20 μm.

When the adhesive layer is laminated on the decorative film, the resin constituting the adhesive layer is not particularly limited, but for example, acrylic resin, acrylic modified polyolefin resin, chlorinated polyolefin resin, polyvinyl chloride, vinyl chloride / vinyl acetate. Examples thereof include copolymers, thermoplastic urethane resins, thermoplastic polyester resins, polyamide resins, rubber-based resins, curable urethane resins, and epoxy resins. These resins may be used alone or in combination of two or more.

Since the heat-weldable film 10 of the present disclosure is excellent in the effect of suppressing unevenness on the surface of the decorative molded body, when an adhesive layer is laminated on the decorative film, the adhesive layer is a large amount of elastomer that improves the effect of reducing unevenness. Even if it does not contain the above, the unevenness on the surface of the decorative molded product can be effectively suppressed. From such a viewpoint, as a preferable example of the decorative film when the adhesive layer is laminated, the adhesive layer has an elastomer content of less than about 50% by weight, preferably less than about 30% by weight, more preferably. Those containing less than about 10% by weight are mentioned, and more preferably those containing no elastomer.

The thickness of the adhesive layer is not particularly limited, and examples thereof include about 1 to 100 μm, preferably about 5 to 50 μm.

Since the heat-weldable film 10 of the present disclosure is excellent in adhesiveness in the decorative molded body and an effect of suppressing unevenness on the surface of the decorative molded body, the decorative film is decorated even if the adhesive layer is not laminated on the decorative molded body. Excellent adhesiveness in the molded product can be effectively obtained, and unevenness on the surface of the decorative molded product can be effectively suppressed. From this point of view, a suitable example of the decorative film is one that does not contain an adhesive layer.

When the decorative film has a release layer, the release layer is integrally molded with the second member by a heat-welding film, and then the interface with the decorative layer is peeled off to form a base from the decorative molded body. The material layer (and the release layer) is provided for the purpose of peeling and removing.

[Fiber reinforced plastic]
The fiber reinforced plastic constituting the second member may be a composite material whose strength is improved by including the fibers in the matrix resin. Examples of the matrix resin of the fiber-reinforced plastic include a thermosetting resin (cured body of a thermosetting resin) and a thermoplastic resin, and preferably a thermosetting resin (cured body of a thermosetting resin).

Examples of the thermosetting resin used as the matrix resin of the fiber-reinforced plastic include epoxy resin, unsaturated polyester resin, phenol resin, silicone resin, urethane resin, and polyimide resin, and preferably epoxy resin. These thermosetting resins can be used alone or in combination of two or more. Examples of the thermoplastic resin used as the matrix resin of the fiber-reinforced plastic include polysulfone, polyethersulfone, polyetherimide, polyimide, and various thermoplastic elastomers. These thermoplastic resins can be used alone or in combination of two or more.

The shape of the fiber of the fiber reinforced plastic is not particularly limited, and a fibrous sheet is preferable. Specific shapes of the fibrous sheet include chopped strands, non-woven fabrics and woven fabrics. Examples of the fiber include inorganic fiber such as carbon fiber and glass fiber, and organic fiber such as aramid fiber. Among these, carbon fibers and glass fibers are preferably mentioned, and carbon fibers are more preferable, from the viewpoint of obtaining the decorative molded body after joining as having superior strength against shear stress parallel to the joining surface. The carbon fiber is not particularly limited, and any of polyacrylonitrile (PAN) type, pitch type and the like may be used, and those in which they are mixed may be used.

Since the heat-weldable film 10 of the present disclosure is excellent in the effect of suppressing unevenness on the surface of the decorative molded body, even if the surface of the fiber reinforced plastic which is the second member is relatively rough, the unevenness on the surface of the decorative molded body can be prevented. It can be effectively suppressed. From this point of view, examples of suitable forms of the fiber include a cloth having a rough surface, such as a plain weave cloth, a twill weave cloth, a satin weave cloth, and a unidirectional cloth. Among these fiber forms, plain weave cloth is preferable.

Examples of the surface roughness Ra of the fiber reinforced plastic include about 25 μm or more. Since the heat-weldable film 10 of the present disclosure is excellent in the effect of suppressing unevenness on the surface of the decorative molded body, even if the surface roughness Ra of the fiber reinforced plastic as the second member is relatively large, the surface of the decorative molded body The unevenness of the surface can be effectively suppressed. From this point of view, preferable examples of the surface roughness Ra of the fiber reinforced plastic include preferably about 28 μm or more, more preferably about 30 μm or more, still more preferably about 33 μm or more, still more preferably about 35 μm or more. .. The upper limit of the surface roughness Ra is not particularly limited, but from the viewpoint of suppressing unevenness, for example, about 100 μm or less, preferably about 60 μm or less can be mentioned. That is, the specific range of the surface roughness Ra is about 25 to 100 μm, about 28 to 100 μm, about 30 to 100 μm, about 33 to 100 μm, about 35 to 100 μm, about 25 to 60 μm, about 28 to 60 μm, and so on. Examples thereof include about 30 to 60 μm, about 33 to 60 μm, and about 35 to 60 μm. The surface roughness Ra is an arithmetic mean roughness measured using a contact type roughness meter with a cutoff value of 1.6 mm and a measurement length of 10 mm in accordance with JIS B0601: 2013. As the contact type roughness meter, Surfcom NEX manufactured by Tokyo Seimitsu Co., Ltd. can be used.

The fiber-reinforced plastic as the second member may be in the form of a prepreg of the fiber-reinforced plastic at the time of welding with the heat-weldable film 10. The fiber-reinforced plastic and the fiber-reinforced plastic prepreg differ in whether or not the matrix resin is cured, but the surface roughness Ra is the same. Therefore, when the heat-weldable film is used for welding with a fiber-reinforced plastic having a predetermined surface roughness Ra, and when a fiber-reinforced plastic prepreg is used at the time of welding, the fiber-reinforced plastic prepreg is used. Those having the predetermined surface roughness Ra may be used.

The fibers may not be exposed or the fibers may be exposed on the surface of the fiber reinforced plastic. The treatment for exposing the fibers may be performed for the purpose of adjusting the surface roughness Ra of the fiber reinforced plastic. Specifically, the treatment for exposing the fibers is performed by removing the matrix resin on the surface of the fiber reinforced plastic in which the fibers are not exposed. Since the heat-weldable film 10 of the present disclosure is excellent in the effect of suppressing unevenness on the surface of the decorative molded body, even if the fiber exposure on the surface of the fiber reinforced plastic which is the second member is small, the surface of the decorative molded body Unevenness can be effectively suppressed. From this point of view, the ratio of the area occupied by the exposed fibers to the surface of the fiber reinforced plastic is preferably about 50% or less, more preferably about 30% or less. Further, from the viewpoint of obtaining better adhesiveness in the decorative molded product, the ratio of the area occupied by the exposed fibers to the surface of the fiber reinforced plastic is more preferably about 10% or less, still more preferably about 5%. The following are mentioned, and most preferably 0%, that is, the fibers are not exposed on the surface of the fiber reinforced plastic.

If necessary, the fiber reinforced plastic may contain various additives such as lubricants, antioxidants, ultraviolet absorbers, light stabilizers, and colorants (pigments, dyes, etc.).

The shape and size of the member are not particularly limited, and may be a shape and size corresponding to the decorative molded body to be manufactured by joining the members. In the present disclosure, the decorative molded body manufactured by joining the members can be suitably used for, for example, an interior member or an exterior member of an automobile. Therefore, as the shape and size of the member, those suitable for these uses can be selected.

2. 2. Laminated body, decorative molded body, and method for producing the decorative molded body In the laminated body of the present disclosure, the first member 30, the second member 40, or the precursor of the second member 40 is a heat-weldable film of the present disclosure. It is characterized in that it is laminated via 10. Details of the heat-weldable film 10, the first member 30, and the second member 40 of the present disclosure are as described above. Further, the precursor of the second member 40 refers to a fiber reinforced plastic prepreg which is in a state before the thermosetting resin of the second member 40 is cured, as described later as the second member precursor 40a in FIG. ..

The laminate of the present disclosure may be such that the first member 30 and the precursor of the second member 40 or the second member 40 are laminated via the heat-weldable film 10, for example, when there are two members to be laminated. If there is, it is an embodiment in which the first member / heat-weldable film / the precursor of the second member or the second member is laminated in order, and if there are three members to be laminated, the first member / heat-weldability The film / the precursor of the second member or the precursor of the second member / the heat-weldable film / the other member are laminated in this order, or the first member and the other member are arranged side by side on one surface of the heat-weldable film. By arranging the second member or the precursor of the second member on the other surface of the heat-weldable film, three members are laminated via one heat-weldable film. The other members are not particularly limited, and those skilled in the art can appropriately select necessary members, and examples thereof include urethane foam, polyvinyl chloride, and polyvinyl acetate for vibration damping and / or soundproofing. .. Further, the heat-weldable film may be laminated in such a manner that the heat-weldable film exists in the entire region between the first member and the second member or the precursor of the second member, or the heat-weldable film may be laminated. However, these members may be laminated in such a manner that they exist in a part of the region between the first member and the second member or the precursor of the second member.

In the decorative molded body 20 of the present disclosure, for example, as shown in the schematic view of FIG. 6, the first member 30 and the second member 40 are heat-welded and molded by the heat-weldable film 10 of the present disclosure. It is characterized by being a body. That is, in the decorative molded body 20 of the present disclosure, the first member 30 and the second member 40 are in a bonded state and a molded state via the heat-weldable film 10 of the present disclosure. Details of the heat-weldable film 10, the first member 30, and the second member 40 of the present disclosure are as described above.

The decorative molded body 20 of the present disclosure is molded into an arbitrary shape. For example, FIG. 6 shows an aspect in which the decorative molded body 20 of the present disclosure has a plate shape. Further, FIG. 10 shows an embodiment in which the decorative molded body 20 of the present disclosure is molded by a mold.

The decorative molded body 20 of the present disclosure is produced by heat-welding the first member 30, the second member 40, or the precursor of the second member 40 in the above-mentioned laminated body via a heat-weldable film 10. be able to. In this case, specifically, the heat-weldable film 10 is heated and pressurized in a state where the heat-weldable film 10 is arranged between the first member 30 and the second member 40 or the precursor of the second member 40. The surface portion or the whole of the second member 40 is heat-melted, or the precursor of the second member 40 is heat-cured. After that, by cooling and solidifying the heat-weldable film 10, a molded body 20 in which the first member 30 and the second member 40 are joined via the heat-weldable film 10 is obtained.

When the matrix resin of the fiber reinforced plastic constituting the second member 40 is a thermosetting resin, an example of the state of the member at the time of heat welding is a state in which the thermosetting resin is cured. In this case, the heat-weldable film 10 is between the first member of the decorative film molded into a predetermined shape and the fiber-reinforced plastic (the one in which the thermosetting resin is cured) molded into the predetermined shape. , And heat welding is performed by pressurization and heating to obtain a decorative molded body in which the first member and the second member are joined.

When the matrix resin of the fiber reinforced plastic constituting the second member 40 is a thermosetting resin, another example of the state of the member at the time of heat welding is the state before the thermosetting resin is cured, that is, the first. Two-member precursors can be mentioned. In this case, the first member composed of the decorative film and the second member precursor composed of the prepreg of the fiber reinforced plastic are heat-welded by heating the laminated body laminated via the thermosetting film 10. The thermosetting and molding of the prepreg can be performed at the same time, that is, in one step, whereby a decorative molded body in which the first member and the second member are joined can be obtained. More specifically, for example, as shown in a series of schematic views of FIGS. 8 to 10, heat welding is performed on a decorative film (first member 30) and a fiber reinforced plastic prepreg (second member precursor 40a). The laminate is laminated via the sex film 10 (FIG. 8), and the laminate is deformed by pressing or heat-pressing with a mold 60 or the like, and the laminate is heated to prepare a fiber reinforced plastic prepreg (second). Heat curing of the member precursor 40a) and heat welding by melting the heat-weldable film 10 are performed (FIG. 9). After cooling the mold 60, as shown in FIG. 10, the first member 30 and the second member 40 (the one in which the thermosetting resin is cured) are joined by the heat-weldable film 10. The molded body 20 is obtained.

When the matrix resin of the fiber-reinforced plastic constituting the second member 40 is a thermoplastic resin, the first member composed of the decorative film and the second member composed of the fiber-reinforced plastic are thermoformed film 10. By heating the laminated body laminated through the above, heat welding and thermoforming can be performed at the same time, that is, in one step, to obtain a decorative molded body in which the first member and the second member are joined. .. More specifically, it is shown in a series of schematic views of FIGS. 8 to 10, except that the fiber reinforced plastic prepreg (second member precursor 40a) is changed to the fiber reinforced plastic (second member 40). The same process as the process can be performed. That is, a laminate in which a decorative film (first member 30) and a fiber reinforced plastic (second member 40) are laminated via a heat-weldable film 10 is heat-pressed with a mold or the like to plasticize the laminate. The laminate is deformed and the laminate is heated to perform heat welding by melting the heat-weldable film 10. After cooling the mold, a decorative molded body 20 is obtained in which the first member 30 and the second member 40 are joined by a heat-weldable film 10.

The temperature at which the first member 30, the second member 40, or the second member precursor 40a is heat-welded through the heat-weldable film 10 is a temperature at which the surface portion or the whole of the heat-weldable film 10 is heat-melted. However, the temperature is not particularly limited, but is preferably about 130 to 280 ° C, more preferably about 130 to 250 ° C. Further, at the temperature, the curing temperature (in the case of thermosetting resin) or the softening point (in the case of thermoplastic resin) of the matrix resin in the fiber reinforced plastic is appropriately considered. The pressure (surface pressure) for heat welding is not particularly limited, but is preferably about 0.1 to 5 MPa, more preferably about 0.2 to 3 MPa. The heating / pressurizing time for heat welding is usually about 1 to 30 seconds.

When a decorative film having a release layer is used, it is integrally molded with the second member by a heat-welding film, and then the interface between the release layer and the decorative layer is peeled off for decorative molding. The base material layer (and mold release layer) can be peeled off from the body.

The present invention will be described in detail below with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

<Measurement of heat-weldable film materials, members to be joined, and their physical properties>
Tables 1 to 3 show the degree of acid modification of the acid-modified polyolefin (acid-modified PO) constituting the heat-weldable film, the softening point of the binder resin used for the decorative layer of the decorative film as the first member, and The surface roughness and the fiber exposure of the fiber-reinforced plastic, which is the second member, are values measured by the following methods.

(Measurement of acid denaturation)
First, in _{ODCB-d4 / C 6 D 6} ( volume ratio 4/1) solvent, was measured and ¹ H-NMR of ¹ H-NMR and methyl esters of the acid-modified polyolefin to be measured (acid-modified polyolefin) .. By comparing both ¹ H-NMR obtained, the peak of the methyl esterified product in which the acid was derivatized was identified. Furthermore, from ¹ H-NMR of the acid-modified polyolefin (before methyl esterification), the area of the impurity-derived peak overlapping at the peak position of the methyl esterified product was identified in ¹ H-NMR of the methyl esterified product. The peak area of the methyl esterified product was obtained by subtracting the peak area derived from impurities from the peak area at the peak position of the methyl esterified product, and the degree of acid denaturation was calculated from the peak area derived from the acid derived based on this. For polyolefins that have not been acid-modified, the degree of acid modification was set to 0% by weight.

(Measurement of softening point)
The softening point was measured using the ring-and-ball method specified in JIS K5601-2-2 Paint component test method-Part 2 Softening point test method for paint components.

(Measurement of surface roughness)
The surface roughness Ra is based on JIS B0601: 2013, using a contact type roughness meter, Surfcom NEX manufactured by Tokyo Seimitsu Co., Ltd., with a cutoff value of 1.6 mm and a measurement length of 10 mm, as an arithmetic mean roughness. It was measured.

(Measurement of fiber exposure)
The fiber exposure degree was measured by calculating the area ratio occupied by the exposed portion of the fiber by microscopic observation of the surface.

<Heat-weldable film>
(Examples 1 to 3 and 6 to 15)
It is composed of a heat-welding resin layer containing the maleic anhydride-modified polypropylene resin (PPa) or the maleic anhydride-modified polyethylene resin (PEa) shown in Tables 1 and 2 at the content in the table, and has the thickness in the table. A layer film was prepared as a heat-weldable film. The thermowelable resin layer in the thermowelable films of Examples 1 to 11 and 13 to 15 is composed of 100% by weight of maleic anhydride-modified polypropylene resin (PPa) or maleic anhydride-modified polyethylene resin (PEa). The thermowelable resin layer in the thermowelable film of Example 12 is composed of a resin composition containing 80% by weight of maleic anhydride-modified polypropylene resin (PPa) and 20% by weight of polypropylene resin (PP). ing. The layer thickness of each layer constituting the heat-weldable film shown in Tables 1 and 2 indicates the layer thickness of the heat-weldable film.

(Example 4)
The maleic anhydride-modified polypropylene resin (PPa) shown in Table 1 as a thermosetting resin was applied to one surface of a fully aromatic polyester (polyarylate (PAR)) non-woven fabric prepared as a support layer by a T-die extruder. The first thermosetting resin layer was formed by extrusion coating with the thickness shown in. Next, the same maleic anhydride-modified polypropylene resin (PPa) was extruded and applied to the other surface of the support layer with a T-die extruder to the thickness shown in Table 1 to form a second heat-welding resin layer. A laminated film in which a first heat-weldable resin layer (PPa, thickness 20 μm) / support layer (PAR, thickness 40 μm) / second heat-weldable resin layer (PPa, thickness 20 μm) is laminated in this order is heat-welded. Obtained as a sex film.

(Example 5)
First thermosetting resin layer (PPa, thickness 44 μm) / support layer (PEN, thickness 12 μm) in the same manner as in Example 4, except that a polyethylene naphthalate (PEN) film was used as the support layer. / A laminated film in which a second thermosetting resin layer (PPa, thickness 44 μm) was laminated in this order was obtained as a thermosetting film.

(Comparative Examples 1 and 2)
In Comparative Examples 1 and 2, the thermosetting resin was not used.

(Comparative Examples 3 and 4)
A single-layer film composed of a heat-weldable resin layer containing the acrylonitrile butadiene styrene resin (ABS) or unstretched polypropylene film (CPP) shown in Table 3 at the content in the table and having the thickness in the table is heat-weldable. Prepared as a film.

(Comparative Example 5)
A single-layer film composed of a heat-weldable resin layer containing the maleic anhydride-modified polypropylene resin (PPa) shown in Table 3 at a content in the table and having a thickness in the table was prepared as a heat-weldable film. Specifically, the heat-weldable resin layer in the heat-weldable film of Comparative Example 5 is a resin composition containing 20% by weight of maleic anhydride-modified polypropylene resin (PPa) and 80% by weight of polypropylene resin (PP). It is configured.

<Decorative film>
As the decorative film as the first member, an ink composition containing a binder resin having a softening point shown in Tables 1 to 3 is applied to one surface of a base material layer made of an acrylic resin film (thickness 125 μm). A decorative layer (picture, layer thickness 5 μm) was formed by work. Specifically, the binder resin in the decorative layer of the decorative film used in Examples and Comparative Examples other than Example 13 is an acrylic urethane resin having a softening point of 85 ° C., and the addition used in Example 13 The binder resin in the decorative layer of the decorative film is a vinyl chloride-vinyl acetate copolymer resin having a softening point of 65 ° C.

Further, in Examples 1 to 14 and Comparative Examples 3 to 5, a decorative film composed of only a base material layer and a decorative layer was used. In Example 15 and Comparative Examples 1 and 2, a decorative film having an adhesive layer having a layer thickness in the table was used on the decorative layer. Specifically, the adhesive layer in the decorative film used in Example 15 and Comparative Example 2 is composed of acrylonitrile butadiene styrene resin (ABS), and the adhesive layer in the decorative film used in Comparative Example 1 is , Ethylene-vinyl acetate copolymer resin (EVA). The adhesive layer in the decorative films used in Example 15 and Comparative Examples 1 and 2 does not contain an elastomer.

<Fiber reinforced plastic>
As the fiber reinforced plastic used as the second member, a fiber material (plain weave cloth) impregnated with the resin materials shown in Tables 1 to 3 was used. As the fiber reinforced plastics used in Examples and Comparative Examples other than Example 13, those in which the epoxy resin impregnated in the carbon fibers had already been completely cured were used.

<Measurement of each physical property of the decorative molded product>
A test sample and a decorative molded product were prepared under the conditions described below, and the seal strength and surface roughness were measured.

(Measurement of seal strength)
The sealing strength (N / 15 mm) between each surface of the heat-weldable films of Examples and Comparative Examples and the decorative films and fiber-reinforced plastics shown in Tables 1 to 3 was measured. More specifically, first, each heat-weldable film was cut into a size of 50 mm in the length direction (y direction) x 25 mm in the width direction (x direction). Next, when measuring the seal strength of the heat-weldable film of the example as a heat-weldable film, for example, as shown in FIG. 7, each heat-weldable film 10 of the example and each member 50 are 7 mm. A test sample was obtained by heat-sealing (heat-sealing conditions: temperature 190 ° C., surface pressure 1 MPa, pressurization time 5 seconds) at the depth (y direction). In the schematic diagram of FIG. 7, the region S surrounded by the broken line indicates the heat-sealed region. In preparing the test sample, first, a depth of 7 mm to be heat-sealed between the heat-weldable film 10 and the member 50 (decorative film which is the first member or fiber reinforced plastic which is the second member) is formed. A release sheet was sandwiched in a portion other than the region so that the heat seal was performed only in the region having a depth of 7 mm. Next, the test sample was cut to a width of 15 mm as shown in FIG. 7 (a) so that the seal strength (N / 15 mm) in the width direction (x direction) of 15 mm could be measured. Subsequently, using a tensile tester, the heat-weldable film 10 was peeled from the fixed member 50 in the length direction (y direction) as shown in FIG. 7 (b). At this time, the peeling speed was set to 300 mm / min, and the maximum load until peeling was set to the seal strength (N / 15 mm). As the member 50 in the preparation of the test sample, a member having a thickness of 4 mm in the case of a fiber reinforced plastic member and a member having a thickness of 130 μm in the case of a decorative film was used. Each seal strength is an average value (n = 3) measured by preparing three test samples in the same manner. The results are shown in Tables 1-3.

(Measurement of surface roughness)
The decorative film, heat-weldable film, and fiber-reinforced plastic shown in Tables 1 to 3 are all cut into a size of 70 mm × 140 mm, and the decorative film / heat-weldable film / fiber-reinforced plastic are laminated in this order. , The temperature was 130 ° C., the surface pressure was 0.25 MPa, and the pressurization time was 2 hours. The decorative molded body was prepared by hot pressing and then cooling to room temperature. For the decorated surface of the obtained laminate, a contact type roughness meter (Surfcom NEX manufactured by Tokyo Seimitsu Co., Ltd.) was used, and the cutoff value was 1.6 mm and the measurement length was 10 mm in accordance with JIS B0601: 2013. The arithmetic mean roughness Ra was measured. The results are shown in Tables 1-3.

Comparative Example 2 in which a 100 μm ABS adhesive layer was provided on the decorative film and bonded to a fiber reinforced plastic without using a heat-welding film, and the ABS adhesive layer of the decorative film were physically independent. From the comparison with Comparative Example 3 in which the decorative film and the fiber reinforced plastic were bonded using a 100 μm heat-weldable film made of ABS, the heat-weldable film physically independent of the decorative film and the fiber reinforced plastic. It was found that the use of the above improves the effect of suppressing unevenness on the surface of the decorative molded body.

Further, from the comparison between Comparative Example 3 in which ABS was used as the material of the heat-weldable film and Comparative Examples 4 and 5 and Examples 1 to 15 in which the polyolefin resin was used as the material of the heat-weldable film, the heat-weldability was obtained. It has been found that the use of a polyolefin-based resin as the material of the film further improves the effect of suppressing unevenness on the surface of the decorative molded body. Further, from the comparison between Comparative Example 4 in which a polyolefin-based resin containing no acid-modified polyolefin was used as the material of the heat-sealing film, and Comparative Examples 5 and Examples 1 to 15 in which a polyolefin-based resin containing an acid-modified polyolefin was used. , It was found that the use of a polyolefin-based resin containing an acid-modified polyolefin further improves the effect of suppressing unevenness on the surface of the decorative molded body.

Further, Comparative Example 5 using a polyolefin-based resin containing an acid-modified polyolefin in a content of less than 80% by weight, and Examples 1 to 15 using a polyolefin-based resin containing an acid-modified polyolefin in a content of 80% by weight or more. In comparison with the above, by using a polyolefin-based resin containing an acid-modified polyolefin in a content of 80% by weight or more, in addition to improving the effect of suppressing unevenness on the surface of the decorative molded product, the obtained decorative molded product is excellent. It was shown that adhesiveness was obtained.

That is, the heat-weldable film (Examples 1 to 15) in which both the surface on one side and the surface on the other side are composed of a heat-weldable resin layer containing 80% by weight or more of acid-modified polyolefin is decorated. It has been shown that by using it as a heat-weldable film for joining a film and a fiber-reinforced plastic, a decorative molded product having excellent adhesiveness and suppressing unevenness on the surface of the decorative molded product can be obtained.

1 Heat-welding resin layer 1a 1st heat-welding resin layer 1b 2nd heat-welding resin layer 3 Support layer 4 Thermoplastic resin layer 10 Heat-welding film 20 Decorative molded body 30 1st member (decorative film)
31 Base material layer 32 Decorative layer 40 Second member (fiber reinforced plastic)
40a Second member precursor (fiber reinforced plastic prepreg)
50 members (first member or second member)
60 Mold S Heat-sealed area

Claims (17)

A heat-weldable film for joining a first member made of a decorative film and a second member made of fiber reinforced plastic.
A thermosetting film in which both the surface on one side and the surface on the other side are composed of a thermosetting resin layer containing 80% by weight or more of an acid-modified polyolefin. The heat-weldable film according to claim 1, wherein the acid-modified polyolefin has an acid modification degree of 0.05% by weight or more. The heat-weldable film according to claim 1 or 2, wherein the acid-modified polyolefin has an acid modification degree of 0.05 to 0.2% by weight. The heat-weldable film according to any one of claims 1 to 3, wherein the modified polyolefin of the acid-modified polyolefin is selected from the group consisting of polyethylene and polypropylene. The heat-weldable film according to any one of claims 1 to 4, wherein the thermosetting resin layer has a thickness of 20 μm or more. The heat-weldable film according to any one of claims 1 to 5, wherein the surface roughness of the surface of the fiber-reinforced plastic to be bonded to the heat-weldable film is 25 μm or more. The heat-weldable film according to any one of claims 1 to 6, wherein the fiber in the fiber reinforced plastic is a plain weave cloth, a twill weave cloth, a satin weave cloth, or a one-way cloth. The decorative film includes a base material layer and a decorative layer, the decorative layer is provided on the side to be bonded to the heat-welding film, and a vinyl chloride / vinyl acetate copolymer resin and a chlorinated polypropylene resin are provided. The present invention according to any one of claims 1 to 7, further comprising a binder resin selected from the group consisting of polyester resin, polyamide resin, polybutylal resin, polystyrene resin, nitricellulose resin, urethane resin, acrylic resin, and acrylic urethane resin. Heat-weldable film. The heat-sealing film according to claim 8, wherein the base material layer is selected from the group consisting of acrylic resin, polyester, polyolefin, vinyl resin, acrylonitrile butadiene styrene copolymer, polyurethane and polycarbonate. The heat-weldable film according to any one of claims 1 to 9, wherein the thermosetting resin layer is a single-layer film. At least, a first heat-welding resin layer, a support layer, and a second heat-welding resin layer are provided in this order, and the surface of the first heat-welding resin layer is the surface on one side, and the second. The heat-weldable film according to any one of claims 1 to 9, wherein the surface of the heat-weldable resin layer is the surface on the other side. The heat-weldable film according to any one of claims 1 to 11, wherein the matrix resin of the fiber-reinforced plastic is a thermosetting resin. The heat-weldable film according to any one of claims 1 to 11, wherein the matrix resin of the fiber-reinforced plastic is a thermoplastic resin. The first member made of a decorative film and a second member made of a fiber reinforced plastic or a second member precursor made of a fiber reinforced plastic prepreg are according to any one of claims 1 to 13. A laminate laminated via a heat-weldable film. A laminate in which a first member made of a decorative film and a second member precursor made of a fiber reinforced plastic prepreg are laminated via the thermosetting film according to any one of claims 1 to 12. A method for producing a decorative molded product, wherein heat welding, thermosetting and molding of the prepreg are performed at the same time to obtain a decorative molded product in which the first member and the second member are joined. A laminate obtained by laminating a first member made of a decorative film and a second member made of a fiber reinforced plastic via a thermoforming film according to any one of claims 1 to 11 and 13 is heated. A method for manufacturing a decorative molded product, wherein heat welding and thermoforming are performed at the same time to obtain a decorative molded product in which the first member and the second member are joined. A decoration in which a first member made of a decorative film and a second member made of a fiber reinforced plastic are joined via the heat-weldable film according to any one of claims 1 to 13. Molded body.