JPH1142738A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To eliminate occurrence of mold dirt with excellent productivity of molding by laminating so that a specific resin film becomes at least one surface layer, and laminating so that the film laminated on the surface layer is brought into contact with specific sheet-like mold compound. SOLUTION: The laminate for manufacturing a molding by heating and molding is obtained by laminating one sheet-like mold compound(SMC) 1 and two resin films 2 so that the films 2 become both surface layers and laminating so that the films 2 laminated on the surface layers are brought into contact with the SMC1. The SMC1 is obtained by mixing glass fiber having a fiber length of 10 to 50 mm with thermosetting resin composition and forming the resultant mixture in a sheet-like material having METSUKE amount of 50 to 1000 g/cm<2> . Incidentally, the film 2 is a resin film non-melted at temperature in the case of molding and having adhesive properties with thermosetting resin composition in the SMC1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate used for manufacturing molded articles such as interior parts for automobiles and building materials.

[0002]

2. Description of the Related Art Conventionally, a sheet-like molding compound (hereinafter, referred to as SMC) in which a glass fiber is blended with a thermosetting resin composition such as a phenol resin has been used.
Molding products manufactured by molding by heating and pressing,
It is used for interior parts such as ceiling materials of automobiles. Further, in order to satisfy the weight reduction and rigidity of this molded product, a molding laminate in which corrugated paper or a foam such as urethane is sandwiched between SMCs as described in JP-A-8-230085. Are also being considered.

[0003] Since the SMC is formed into a sheet using an uncured thermosetting resin composition, if the SMC and the above-mentioned laminate are directly stacked and stored, the SM
There was a case where a problem occurred that C and the laminates stuck together. Therefore, a molded article is manufactured by a method in which a resin sheet such as a polyphenylene ether resin (also called a polyphenylene oxide resin) or the like that is releasable from the SMC is sandwiched therebetween, and the sheet is peeled off and used before molding. Have been.

[0004] However, in the case of this method in which the sheet is used while peeling off the sheet before molding, a man-hour for peeling is required, and the productivity of molding is low. There is a problem that the remaining sheet may adhere to a mold for molding a molded article and cause stain on the mold. Therefore, there is a demand for a molding material which is excellent in molding productivity and hardly causes mold contamination.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide an SMC for manufacturing a molded article by heating and molding. It is an object of the present invention to provide a laminate obtained by laminating the above, which is excellent in molding productivity and hardly causes mold contamination.

[0006]

A laminate according to claim 1 of the present invention is a laminate for producing a molded article by heating and molding, wherein a fiber is added to a thermosetting resin composition. 5 to 50 mm long glass fiber blended, weight 5
An SMC (sheet-like molding compound) of 0 to 1000 g / m ² and a resin film that is non-melting at the temperature at the time of molding and that has adhesiveness to the thermosetting resin composition, The resin film is laminated so as to be at least one surface layer, and the resin film laminated on the surface layer is laminated so as to be in contact with the SMC.

A laminate according to a second aspect of the present invention is the laminate according to the first aspect, characterized in that the thermosetting resin composition contains a resol-type phenol resin which is liquid at normal temperature.

[0008] A laminate according to a third aspect of the present invention is the laminate according to the first or second aspect, wherein the thermosetting resin composition contains a foaming agent.

A laminate according to a fourth aspect of the present invention is the laminate according to any one of the first to third aspects, wherein the melting point of the resin film is 180 ° C. or higher.

A laminate according to a fifth aspect of the present invention is the laminate according to any one of the first to fourth aspects, wherein the resin film is selected from the group consisting of polyvinyl alcohol, polyethylene terephthalate and cellophane. Characterized in that it is at least one kind of resin film.

A laminate according to a sixth aspect of the present invention is the laminate according to any one of the first to fifth aspects, wherein the corrugated paper in which the corrugated paper and the flat paper are bonded is also laminated. Features.

A laminate according to a seventh aspect of the present invention is characterized in that, in the laminate according to any one of the first to sixth aspects, a foam is also laminated.

According to an eighth aspect of the present invention, in the laminate according to any one of the first to seventh aspects, a second film made of polyvinyl chloride and / or polyethylene is also laminated. It is characterized by the following.

According to a ninth aspect of the present invention, in the laminate according to any one of the first to eighth aspects, the method of laminating the resin film and the SMC is such that the resin film is formed on one surface of the SMC. Resin film and S to cover the whole
It is a method of laminating MC.

When the laminate according to the present invention is molded by heating, a resin film which is non-melting at the molding temperature and which has an adhesive property with the thermosetting resin composition adheres to the SMC portion. Therefore, when the molded product is taken out of the mold, the entire resin film is removed from the mold together, and the resin film hardly remains in the mold. Therefore, when the laminate of the present invention is used, molding can be performed without peeling off a film or the like, and molding productivity is excellent, and molding in which mold contamination is less likely to occur can be achieved.

[0016]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A laminate according to the present invention will be described with reference to the drawings. 1A and 1B are cross-sectional views illustrating a laminate according to the present invention. FIG. 1A is a first embodiment, and FIG. 1B is a second embodiment. FIGS. 2A and 2B are cross-sectional views illustrating a laminate according to the present invention. FIG. 2A is a third embodiment, FIG. 2B is a fourth embodiment, and FIG. 2C is a fifth embodiment. It is a form of.

As shown in FIG. 1 (a), a first embodiment of a laminate according to the present invention comprises one SMC (sheet-shaped molding compound) 1, two resin films 2, 2. Are laminated so that the resin films 2 and 2 are both surface layers, and the resin films 2 and 2 laminated on the surface layer are laminated so as to be in contact with the SMC 1 and are molded by heating and molding. It is a laminate for manufacturing a product.

SMC1 is obtained by mixing a thermosetting resin composition with glass fibers having a fiber length of 10 to 50 mm into a sheet having a basis weight of 50 to 1000 g / m ² .

The thermosetting resin composition used for the SMC 1 is not particularly limited as long as it contains a thermosetting resin such as a phenol resin, an epoxy resin, and an unsaturated polyester resin. And a liquid resol-type phenol resin is preferable because of excellent impregnation into glass fibers. The viscosity of the thermosetting resin composition is preferably about 1000 to 8000 cps at 25 ° C. In addition, the thermosetting resin composition, if necessary,
It may contain a curing agent, a release agent, a surfactant and the like.

It is preferable that the thermosetting resin composition contains a foaming agent which foams by heating during molding, since the resulting molded article can be reduced in weight. Examples of the foaming agent include nitrosotetramines such as dinitrosopentamethylenetetramine.

The glass fiber used for the SMC 1 is not particularly limited as long as it has a fiber length of 10 to 50 mm. In general, glass fibers such as alkali glass and E glass are used. The fiber length is 10
If it is less than 50 mm, the rigidity of the obtained molded product may be reduced. If it exceeds 50 mm, the thermosetting resin composition and the glass fiber are easily separated, and it is difficult to mold the laminate into a curved shape. Becomes

The mixing ratio of the thermosetting resin composition to the glass fibers is such that when 10 to 80 parts by weight of the glass fiber is mixed with 20 to 90 parts by weight of the thermosetting resin composition, the resulting molded article is obtained. Is excellent in the balance between rigidity and moldability.

The basis weight of the SMC 1 is 50 to 50%.
It is important that it is 1000 g / m ² . When the basis weight is less than 50 g / m ² , the SM should be in contact with a surface having irregularities, such as corrugated paper or foam, which will be described later.
In the case where C1 is laminated, the ability to follow the irregularities during molding becomes insufficient and the adhesion becomes insufficient, and the resulting molded product may peel at that portion. On the other hand, if it exceeds 1000 g / m ² , the obtained molded article becomes heavy, which is not practical.

The method of producing the SMC 1 is not particularly limited. For example, after applying a predetermined amount of the thermosetting resin composition on a release sheet, the glass fiber is sprayed while being cut with a chopper. After stacking the release sheet thereon, it is pressed with a press roll. Next, the resin composition is aged by storing it in a state of being sandwiched between release sheets, and the thermosetting resin composition is B-staged, and then cut into a predetermined size to produce SMC1. Then, at the time of manufacturing the laminate, the release sheet is peeled off and laminated with the resin film 2 or the like.

Examples of the release sheet used for manufacturing the SMC 1 include films of polypropylene, polyvinyl chloride, polyethylene and the like. In addition, when using a resin sheet that can be melted at the time of molding, such as polyvinyl chloride or polyethylene, the release sheet is melted at the time of molding and adheres to other laminated materials.
As shown in FIGS. 2A to 2C, the release sheet (second film 5) may be laminated in the laminate by peeling off only one of the release sheets and laminating. In this case, the number of steps for peeling the release sheet is reduced, so that the productivity when manufacturing the laminate is improved, which is preferable.

It is important that the resin film 2 used in the present invention is a film that is not melted at the molding temperature. In the case of a film that melts, if the laminate is formed in a state where the film is laminated on the surface layer without being peeled off, the film may be melted and adhere to a mold, and mold stains are likely to occur. In addition, in the film to be melted,
It also includes a film in which some components in the film are melted and leached to the surface, and the `` non-melting '' of the present invention refers to excluding a film in which such components are melted. Represent.

When laminated with an SMC 1 using a thermosetting resin composition containing a resol type phenol resin which is liquid at normal temperature, a resin film 2 having a melting point of 180 ° C. or more, such as polyvinyl alcohol, polyethylene terephthalate, cellophane, etc. Is preferred because it is easy to form the laminate at a temperature at which the resin film 2 is not melted.

It is important that the resin film 2 is a resin film having an adhesive property with the thermosetting resin composition in the SMC 1. When a resin film having an adhesive property with the thermosetting resin composition in the SMC1 is molded in a state of being laminated so as to be in contact with the SMC1, the resin film 2 is adhered and integrated with the SMC1 portion. When the product is taken out of the mold, the entire resin film 2 is removed from the mold together, so that the resin film 2 hardly remains in the mold, and the stain on the mold hardly occurs.

When a film such as a polyphenylene ether resin having low adhesion to the thermosetting resin composition in the SMC1 is laminated so as to be in contact with the SMC1, a resin having an adhesive property to the thermosetting resin composition is used. When the film 2 and the SMC1 are laminated so that they do not come into contact with each other by sandwiching another material having low adhesiveness between the resin film 2 and the SMC1 made of resin, and molded without peeling anything, a polyphenylene ether resin or the like is obtained. The film or the material sandwiched between the films may adhere to the mold and remain, resulting in mold contamination. In addition, as a countermeasure, when a film or the like of a polyphenylene ether resin is peeled and molded before molding, a man-hour for peeling is required, and the productivity of molding is low, and even if the film is peeled, it does not peel partially. However, there is a problem that the remaining sheet may adhere to a mold when molded and the remaining sheet may be formed on the surface of the SMC 1, thereby causing mold contamination.

When the resin film 2 and the SMC 1 are laminated, the resin film 2 is laminated so as to cover one entire surface of the SMC 1 so that the entire SMC 1 does not contact the mold. This prevents the thermosetting resin composition from adhering to the mold and generating mold stains, and is particularly preferred because mold stains are less likely to occur.

As the resin film 2 as described above, S
Selection is necessary according to the thermosetting resin composition in MC1, and examples thereof include resin films such as polyvinyl alcohol, polyethylene terephthalate, cellophane, and nylon. The thickness of the resin film 2 is not particularly limited, but is generally about 5 to 100 μm.

FIG. 1 (b) and FIG. 2 (b)
As shown in FIG. 2, a corrugated paperboard 3 formed by bonding corrugated paperboard and flat paper, and a foam 4 formed into a sheet while foaming hard urethane or polypropylene as shown in FIG. 2C are also laminated. This is preferable because the resulting molded article can be reduced in weight. As shown in FIG. 1 (b), the position where the corrugated paper 3 and the foam 4 are laminated is SM
By laminating at a position in contact with C1 or at a position in contact with the second film 5 as shown in FIG. 2B and FIG. It is laminated at a position where it is bonded and integrated. In addition, the corrugated paper 3 and the foam 4 may be laminated so as to be one surface layer of the laminate as shown in FIG.

The layers such as the SMC 1, the resin film 2, and the corrugated paper 3 to be laminated may be laminated in a state where they are separated from each other, or may be laminated in a state where they are partially or wholly bonded. .

When a molded article is manufactured using the laminate according to the present invention, the laminate is sandwiched between molds having a desired shape, and S
A temperature at which the thermosetting resin composition in MC1 is cured;
Further, the resin film 2 is molded by heating to a temperature at which the resin film 2 does not melt. Then, the laminated layers are integrated to obtain a molded product. The molding at this time is excellent in productivity and less likely to cause mold contamination.

[0035]

【Example】

(Example 1) 100 parts by weight of a resol type phenol resin liquid at room temperature and 20 parts of a solid novolak type phenol resin
Parts by weight, 5 parts by weight of dinitrosopentamethylenetetramine [manufactured by Eiwa Kasei Kogyo Co., Ltd., trade name: Cellular D], 3 parts by weight of hexamethylenetetramine as a curing agent, and polyether-modified silicone as a surfactant [Toshiba Silicone Company, trade name: TFA4205] in an amount of 3 parts by weight, and zinc stearate as a release agent in an amount of 2 parts by weight.
The mixture was mixed to obtain a thermosetting resin composition.

Next, the obtained thermosetting resin composition is
Release sheet made of polyvinyl chloride [Nihon Carbide Industry Co., Ltd.
400 g / m.
m ^TwoGlass fiber cut to a fiber length of 25 mm after coating
About 400 g / m^TwoAnd then release the release sheet on it
After stacking, they were pressed with a press roll. Next, release mold
Aged at 40 ° C for 2 days while sandwiched between
The fat composition was B-staged and the basis weight was 800 g / m.^Two
SMC sandwiched between release sheets was obtained.

Next, using the obtained SMC and a film made of polyvinyl alcohol (PVA) [Kuraray Co., Ltd., trade name # 2000, thickness 20 μm] as a resin film, as shown in FIG. The resin film 2 was laminated so as to be both surface layers, and the resin film 2 laminated on the surface layer was laminated so as to be in contact with the SMC 1 to obtain a laminate. The SMC was laminated by releasing the release sheets on both sides. In addition, resin film and SM
C was laminated such that the resin film covered one entire surface of the SMC.

Next, the obtained laminate is sandwiched between molds,
Molding was performed by heating and pressing at a maximum temperature of 170 ° C. and a pressure of 1 Pa for 2 minutes to obtain a molded article. Then, this molding was repeated 12 times, and the stain on the mold was evaluated. The result is
No melted resin or peeled film remained in the mold, and it was confirmed that the laminate was particularly resistant to mold contamination.

When the resin film used was brought into contact with a hot plate heated to 170 ° C. for 2 minutes to confirm the presence or absence of melting, the resin film was not melted and was not melted at the molding temperature. It was confirmed that. In addition, it was confirmed that the resin film on the surface of the obtained molded product was peeled off but did not peel off, and that the resin film used was a resin film having adhesiveness to the thermosetting resin composition in the SMC. Was.

Example 2 A laminate was obtained in the same manner as in Example 1 except that a polyethylene terephthalate (PET) film [Toyobo, 12 μm thick] was used as the resin film.

As a result of evaluating the stain on the mold in the same manner as in Example 1, no melted resin or peeled film remains on the mold, and the laminate is particularly resistant to mold stain. It was confirmed that. In addition, in the same manner as in Example 1, as a result of confirming whether or not the used resin film was melted and the adhesiveness between the used resin film and the thermosetting resin composition in the SMC, it was found that the resin film was not heated at the molding temperature. It was confirmed that the film was a molten film and a resin film having adhesiveness.

Example 3 A laminate was obtained in the same manner as in Example 1, except that a cellophane film [thickness: 30 μm, made of regenerated cellulose film] was used as the resin film.

As a result of evaluating the stain resistance of the mold in the same manner as in Example 1, no melted resin and no peeled film remain on the mold, and the laminate is particularly resistant to mold stain. It was confirmed that. In addition, in the same manner as in Example 1, as a result of confirming whether or not the used resin film was melted and the adhesiveness between the used resin film and the thermosetting resin composition in the SMC, it was found that the resin film was not heated at the molding temperature. It was confirmed that the film was a molten film and a resin film having adhesiveness.

Example 4 As shown in FIG. 1 (b), a corrugated paperboard 3 having a thickness of 5 mm formed by bonding flat paper to both sides of corrugated paperboard is sandwiched between SMCs, and the SMCs A laminate was obtained in the same manner as in Example 1 except that a resin film was laminated on the outside.

As a result of evaluating the stain resistance of the mold in the same manner as in Example 1, no melted resin or peeled film remains on the mold, and the laminate is particularly resistant to mold stain. It was confirmed that.

Example 5 As shown in FIG. 2B, a corrugated paperboard 3 having a thickness of 5 mm formed by bonding flat paper to one side of corrugated paperboard is sandwiched between the second films 5, and SMC1 is laminated on the outside of the second film 5, and
A laminate was obtained in the same manner as in Example 1 except that the resin film 2 was laminated outside the MC 1. The second film 5 was used as the second film 5 without peeling the release sheet.

As a result of evaluating the stain on the mold in the same manner as in Example 1, no melted resin or peeled film remains on the mold, and the laminate is particularly resistant to mold stain. It was confirmed that.

(Example 6) A resin film, an SMC, a second film, and a corrugated paperboard were formed by bonding flat paper to one side.
A laminated body was obtained in the same manner as in Example 1 except that corrugated paper having a thickness of 5 mm was laminated in this order. In addition, the second film 5 may be removed without peeling the release sheet.
Used as

Then, as a result of evaluating the stain resistance of the mold in the same manner as in Example 1, no laminate containing the melted resin or the peeled film remains on the mold, and the laminate is particularly resistant to mold stain. It was confirmed that.

(Example 7) Instead of a polyvinyl alcohol resin film, a nylon film [thickness 20
μm] was laminated on both surface layers in the same manner as in Example 1.

Then, in the same manner as in Example 1, the stain on the mold was evaluated. As a result, a small amount of the resin melted in the mold after molding 10 times remained in the mold. It was confirmed that there was. In addition, in the same manner as in Example 1, as a result of confirming whether or not the used resin film was melted and the adhesiveness between the used resin film and the thermosetting resin composition in the SMC, it was found that the resin film was not heated at the molding temperature. It was confirmed that the film was a molten film and a resin film having adhesiveness.

Comparative Example 1 A polyphenylene ether resin (P) was used instead of a polyvinyl alcohol resin film.
A laminate was obtained in the same manner as in Example 1, except that a film made of PE) was laminated on both surface layers.

Then, as a result of evaluating the stain resistance of the mold in the same manner as in Example 1, the polyphenylene ether resin film used had a low adhesiveness to the thermosetting resin composition in the SMC, so the first time It was confirmed that the laminate was left in the mold after molding and was liable to cause mold contamination. The presence or absence of melting of the used resin film was confirmed in the same manner as in Example 1, and as a result, it was confirmed that the resin film was a non-melted film at the temperature at the time of molding.

(Comparative Example 2) The laminate obtained in Comparative Example 1 was evaluated for mold stainability in the same manner as in Example 1, except that the surface layer of a polyphenylene ether resin film was peeled off and then molded. did. As a result, it was confirmed that the thermosetting resin composition in the SMC was slightly left in the mold when molded three times, and the laminate was liable to cause mold contamination. In addition, since the film of the surface layer was peeled off, the molding was lower in productivity than in each example.

Comparative Example 3 In the same manner as in Example 1 except that a film made of polypropylene (PP) (thickness: 20 μm, melting point: 150 ° C.) was laminated on both surface layers instead of the polyvinyl alcohol resin film. A laminate was obtained.

Then, in the same manner as in Example 1, the stain on the mold was evaluated. As a result, the polypropylene film was melted and adhered to the mold, and the laminate was liable to cause mold stain. Was confirmed. In addition, as in Example 1, the presence or absence of melting of the used film was confirmed. As a result, it was confirmed that the film was molten when it was in contact with the hot plate and melted at the temperature at the time of molding. Was done.

(Summary of Results) As shown in Table 1, it was confirmed that mold contamination was less likely to occur in each example than in each comparative example. Further, in each of the examples, it was confirmed that compared with the comparative example 2 in which the film of the surface layer was peeled off, the sheet was not required to be peeled off as compared with the comparative example 2 which was molded, and the molding productivity was excellent. That is, it was confirmed that the laminate obtained in each of the examples was a laminate having excellent molding productivity and hardly causing mold contamination.

Further, in Examples 1 to 6 using a resin film made of polyvinyl alcohol, polyethylene terephthalate, or cellophane, it was confirmed that the laminates were less likely to cause mold contamination as compared with Example 7.

[0059]

[Table 1]

[0060]

According to the laminate of the present invention, the resin film is laminated so as to form at least one surface layer, and the resin film laminated on the surface layer is formed by the SMC.
Therefore, the laminate is excellent in molding productivity and hardly causes mold contamination.

The laminate according to the fifth aspect of the present invention is a laminate which is unlikely to cause mold contamination.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a laminate according to the present invention;
(A) is the first embodiment, and (b) is the second embodiment.

FIG. 2 is a cross-sectional view illustrating a laminate according to the present invention;
(A) is the third embodiment, (b) is the fourth embodiment, and (c) is the fifth embodiment.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 SMC (sheet-shaped molding compound) 2 Resin film 3 Corrugated paper 4 Foam 5 Second film

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI B32B 27/42 101 B32B 27/42 101 (72) Inventor Akira Ueno 1048, Ojimon, Kadoma, Osaka Pref. Matsushita Electric Works, Ltd.

Claims (9)

[Claims] Claims: 1. A laminate for producing a molded article by molding by heating, comprising:
A sheet-shaped molding compound (1) having a basis weight of 50 to 1000 g / m ² and a glass fiber having a fiber length of 10 to 50 mm, and the thermosetting resin composition which is non-melting at the temperature at the time of molding and And a resin film (2) having adhesiveness, such that the resin film (2) is at least one surface layer, and the resin film (2) laminated on the surface layer is formed by the sheet-like molding. A laminate characterized by being laminated so as to be in contact with the compound (1). 2. The laminate according to claim 1, wherein the thermosetting resin composition contains a resol-type phenol resin which is liquid at room temperature. 3. The laminate according to claim 1, wherein the thermosetting resin composition contains a foaming agent. 4. The melting point of the resin film (2) is 180 ° C.
The laminate according to any one of claims 1 to 3, wherein: 5. The resin film (2) is a film made of at least one resin selected from the group consisting of polyvinyl alcohol, polyethylene terephthalate and cellophane. The laminate according to any one of the above. 6. The laminate according to claim 1, wherein a corrugated paper (3) in which corrugated paperboard and flat paper are bonded is also laminated. 7. The laminate according to claim 1, wherein a foam (4) is also laminated. 8. The laminate according to claim 1, wherein a second film (5) made of polyvinyl chloride and / or polyethylene is also laminated. 9. A method of laminating a resin film (2) and a sheet-shaped molding compound (1) is performed such that the resin film (2) covers one entire surface of the sheet-shaped molding compound (1). The laminate according to any one of claims 1 to 8, wherein the laminate is a method of laminating the sheet-like molding compound (2) and the sheet-like molding compound (1).