JP2933643B2 - Laminated molded article for automotive interior parts and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a laminated molded article obtained by laminating a skin layer composed of another synthetic resin on an aggregate molded article composed of a synthetic resin mainly composed of a polyolefin-based resin, and the laminated molded article. It relates to a manufacturing method.

[Conventional technology]

Conventionally, in order to protect the surface of a three-dimensional molded product with a skin layer of a synthetic resin, or to decorate and print, a skin layer made of the same or another synthetic resin is laminated on the surface of an aggregate formed body made of a synthetic resin Laminated molded articles are known.

This laminated molded article is obtained by vacuum-forming a synthetic resin sheet on the inner surface of the cavity of the injection molding die by vacuum molding, pre-molding, and then injecting the synthetic resin in a fluidized state into the cavity by injection filling. Mainly automotive interior and exterior parts,
Widely used as building materials.

Then, as the aggregate formed body, one having affinity with the material of the skin layer and having good wearability is selected, and when, for example, polyvinyl chloride or the like is used as the skin layer, the aggregate formed body is also made of poly. It is customary to use vinyl chloride or similar polar resins.

[Problems to be solved by the invention]

Incidentally, it is desirable that the laminated molded article is produced and sold at a more economical price. From this viewpoint, when examining a conventional laminated molded body, since the aggregate molded body is not exposed on the surface, it is desirable to form the aggregate using the cheapest material unless the strength and other physical properties are extremely poor.

In this regard, it is preferable to use an inexpensive polyolefin-based resin. On the other hand, as the skin layer, considering the ease of vacuum forming, good touch, visual aesthetics, etc.
It is preferable to use ABS resin, polyamide, polyurethane, polyvinyl chloride, or the like.

However, these are polar resins and have no affinity with polyolefin resins that are non-polar resins, resulting in poor adhesive strength between the skin layer and the aggregate molding, resulting in poor durability as a product. I can't get it.

An object of the present invention is to solve such a problem, and it is an object of the present invention to provide an inexpensive laminated molded body and to provide a manufacturing method thereof.

[Means to solve the problem]

The laminated molded article for automotive interior parts of the present invention is a laminated molded article obtained by firstly laminating a skin layer via a primer layer on the surface of an aggregate molded article made of a synthetic resin mainly composed of a polyolefin resin, The primer layer is composed of a propylene-ethylene copolymer having a propylene content of 50 to 75 mol% and a crystallinity of 2 to 20% by X-ray diffraction and maleic acid or anhydride thereof in an amount of 0.5 to 15% by weight. A modified polymer obtained by dissolving 10 to 100 kg of a modified polymer having a [η] of 0.3 or more in 1 m ³ of an organic solvent, which is formed by graft copolymerization, wherein the surface layer is formed. Is a synthetic resin skin film made of polyurethane.

The aggregate formed body is made of polyolefin resin and ethylene.
a thermoplastic elastomer and / or polypropylene sheet made of a blend with a partially crosslinked α-olefin polymer rubber; and This is a concept that includes a composite sheet formed by laminating films.

Another laminated molded article of the present invention is obtained by laminating the composite sheet as a skin layer on the surface of an aggregate molded article made of a synthetic resin mainly composed of a polyolefin-based resin. That is, a skin layer is a thermoplastic elastomer comprising a blend of a polyolefin-based resin and a partially cross-linked ethylene / α-olefin-based polymer rubber, with the skin film as an outer layer and a primer layer on the outer layer, and / or It is obtained by laminating an inner layer of polypropylene.

If necessary, a synthetic resin paint layer having a picture pattern may be interposed between the skin layer and the aggregate formed body, or in the case above, between the skin layer and the primer layer. In the case of (1), a synthetic resin paint layer having a picture pattern may be interposed between the exterior and the primer layer.

 Next, the manufacturing method of the present invention is as follows.

(A) A primer solution is applied to one surface of a synthetic resin skin film made of polyurethane, and after preheating the skin film, the surface on which the primer solution is not applied is set to the cavity inner wall surface side, and a mold is formed. This skin film is suction-contacted to the inner wall surface of the cavity, then clamped, and then the injection molding is performed by injection-filling the cavity with a synthetic resin mainly composed of a polyolefin resin in a fluidized plasticized state. A method for producing a molded article.

(B) A primer liquid is applied to one surface of a synthetic resin skin film made of polyurethane, and after preheating the skin film, the polyolefin resin and ethylene are extruded onto the surface to which the primer liquid is applied.・
A method for producing a laminated molded article for an automotive interior part, in which a thermoplastic elastomer and / or polypropylene molten sheet made of a blend with a partially crosslinked product of an α-olefin polymer rubber is extruded and laminated to obtain a composite sheet. .

(C) The above-mentioned skin film is used as an outer layer, and the above-mentioned primer solution is applied to the inner side of the outer layer, and a thermoplastic resin comprising a blend of a polyolefin resin and a partially crosslinked ethylene / α-olefin polymer rubber is applied thereto. A composite sheet having an elastomer and / or polypropylene inner layer laminated is prepared, and after preheating this composite sheet, the outer layer side is set to the cavity inner wall surface side, and the mold is brought into close contact with the mold cavity inner wall surface. A method of manufacturing a laminated molded article in which a resin is tightened, and then the cavity is injection-filled with a synthetic resin mainly composed of a polyolefin resin in a fluidized and plasticized state, followed by molding. As a composite sheet used in this method,
What was manufactured by the method of (b) can be used conveniently.

(D) The primer solution is applied to one surface of the skin film, and the skin film is suction-adhered to the inner wall surface of the cavity where the primer solution is not applied. Pour a synthetic resin mainly composed of a polyolefin resin in a fluidized plasticized state into the cavity where the film adheres, and then
A method for manufacturing a laminated molded article that is molded by clamping.

(E) After preparing the composite sheet in (c) and preheating the composite sheet, the outer layer side is set to the cavity inner wall surface side, and the composite sheet is suction-contacted to the mold cavity inner wall surface. A method of manufacturing a laminated molded body in which a synthetic resin mainly composed of a polyolefin resin in a fluidized plasticized state is poured into a cavity in which a sheet is in close contact, and then molded by clamping.

[Action]

In the present invention, since a synthetic resin skin film made of polyurethane is used as the skin layer of the laminated molded body, vacuum forming is easy, and molding defects such as wrinkles and cracks do not occur. As the skin film used as the surface layer in the present invention, a film stretched biaxially in terms of strength is preferably used. Further, the thickness may be about 50 to 1500 μ.

The presence of the primer layer improves the adhesive strength between the skin film, which originally has poor affinity, and the polyolefin-based synthetic resin aggregate molding.

The primer liquid applied to form the primer layer includes a propylene-ethylene copolymer having a propylene content of 50 to 75 mol% and a crystallinity of 2 to 20% by X-ray diffraction. primer solution with maleic acid or modified polymer the anhydride formed by polymerizing from 0.5 to 15 wt% graft that [eta] is formed by 10~100kg dissolved in the organic solvent 1 m ³ to 0.3 or more modified polymer Can be suitably used.

In this primer solution, the propylene-ethylene copolymer as a raw material of the modified polymer is preferably a random copolymer of propylene and ethylene, and the propylene content is 50 to
75 mol%, particularly preferably in the range of 60 to 70 mol%,
Its molecular weight is [η] (in decalin at 135 ° C.), and the preferred range is 0.3 to 20, especially about 0.3 to 10. The crystallinity of the copolymer in this range is about 2 to 20%, particularly preferably about 5 to 18%, as measured by X-ray.

If the propylene content is less than 50 mol%, the resulting treatment liquid will have poor volatile oil resistance. On the other hand, if it exceeds 75 mol%, the solubility of the modified polymer in an organic solvent decreases, and the adhesion of the resulting treatment liquid also decreases.

The primer layer is provided to improve the adhesiveness between the aggregate molded product and the skin layer, or the adhesiveness between the outer layer and the inner layer in the composite sheet, and includes a synthetic resin material for forming the skin layer and an aggregate molding. The condition of choice is to have an affinity for any of the constituent resin materials mainly composed of a polyolefin resin forming the body, or for both the outer layer and the inner layer. In this regard, the primer liquid has a good affinity for the skin film forming the skin layer or the outer layer and the thermoplastic elastomer.

Next, as a synthetic resin mainly composed of a polyolefin-based resin used to mold an aggregate molded body, crystalline,
Regardless of amorphousness, α-olefins such as low-density polyethylene, high-density polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene or ethylene, propylene 1-butene, and 4-methyl-pentene A random or block copolymer can be exemplified, and these can be used alone or as a mixture. The thermoplastic elastomer is also a blend of a polyolefin-based resin and a partially cross-linked product of ethylene / α-olefin-based polymer rubber, and is included in the concept of the polyolefin-based resin for an aggregate formed article according to the present invention. You.

These polyolefin resins may be foamed with a blowing agent, if necessary, or within a range that does not impair the required physical properties, or for the purpose of further improving the physical properties, other synthetic resins, wood flour, fibers Pieces, fillers and the like may be mixed.

Next, in the present invention, a synthetic resin paint layer for drawing characters and pictures may be provided inside the skin film forming the skin layer. In this case, the skin film is required to be transparent or translucent. . As the synthetic resin paint, acrylic, polyethylene terephthalate, polyvinyl chloride, polyurethane, and the like can be presented.

In addition, the above-described composite sheet itself corresponds to the laminated molded article according to the present invention. By using this composite sheet, an aggregate molded article is formed so as to be in contact with the inner layer side, and another laminated molded article is formed. It can also be molded. At this time, since the inner layer is made of a thermoplastic elastomer and / or polypropylene made of a blend of a polyolefin-based resin and a partially cross-linked product of an ethylene / α-olefin-based polymer rubber, the inner layer is made of an aggregate formed article made of a polyolefin-based synthetic resin. Good affinity and sufficient adhesive strength can be obtained.

Here, the following are shown as thermoplastic elastomers comprising a blend of a polyolefin-based resin and a partially crosslinked product of an ethylene / α-olefin-based polymer rubber.

(I) Various polyolefin-based resins represented by homopolymers of ethylene or propylene or copolymers with a small amount of other polymerizable monomers, and ethylene and carbon atoms of 3 to
Blend of partially crosslinked ethylene / α-olefin-based copolymer rubber, which is a binary copolymer rubber with α-olefin (14) or a terpolymer rubber obtained by further copolymerizing various polyethylene compounds with the same. (See, for example, Japanese Patent Publication No. 53-21021 and Japanese Patent Application Laid-Open No. 55-71738).

(II) A thermoplastic composition obtained by dynamically heat-treating a blend of a polyolefin-based resin and an ethylene / α-olefin-based copolymer rubber (for example, JP-B-53-34210)
, JP-A-53-149240 and JP-A-53-149241).

(III) A thermoplastic composition obtained by dynamically heat-treating a blend of a polyolefin-based resin and an ethylene / α-olefin-based copolymer rubber, and further blending a polyolefin-based resin (For example, see
-145857 and JP-A-54-16554).

(IV) a peroxide-crosslinked polyolefin resin represented by a homopolymer of ethylene or a copolymer with a small amount of another polymerizable monomer, a homopolymer of propylene or a small amount of another polymerizable monomer, Thermoplastic composition obtained by dynamically heat-treating a blend of a peroxide non-crosslinked polyolefin resin represented by a copolymer of and an ethylene / α-olefin copolymer rubber (for example,
JP-A-55-71739).

In these various thermoplastic elastomers, a polyolefin resin and a partially crosslinked product of an ethylene / α-olefin polymer rubber are 90/10 to 10/90, preferably 80/20.
It is used by blending so as to have a weight ratio of 2020/80.

As the polyolefin-based resin, polyethylene, especially low-density polyethylene and polypropylene are used in terms of ease of molding during sheet molding and scratch resistance of the sheet.
It is preferable to use a mixture in a weight ratio of / 90 to 70/30.

Further, as the ethylene / α-olefin-based polymer rubber to be partially crosslinked, ethylene and α-olefin are preferably 50/50 to 90/10, preferably for reasons of strength.
70 / 30-85 / 15 molar ratio, Mooney viscosity ML1 + 4
(121 ° C.) of about 20 or more, preferably about 40 to 80 is used. And these ethylene
The partial cross-linking of the α-olefin polymer rubber is generally carried out by dynamically heat-treating the organic elastomer using about 0.1 to 2 parts by weight of organic peroxide per 100 parts by weight of the thermoplastic elastomer.

And, in these thermoplastic compositions, if necessary, peroxide non-crosslinked hydrocarbon-based rubbery substances represented by polyisobutylene, butyl rubber and the like, and / or
Alternatively, a mineral oil-based softener can be mixed.

As described above, since the thermoplastic elastomer has flexibility, it is backed by the outer layer of PET as an inner layer, thereby giving flexibility to the formed composite sheet.

As the inner layer forming the composite sheet, polypropylene may be used instead of the thermoplastic elastomer or by mixing with the thermoplastic elastomer.

The above-mentioned methods (a) and (c) will be described in more detail with reference to an apparatus for performing the method. As shown in FIGS. 1 (a) to 1 (d), this apparatus comprises at least a pair of male and female. Equipped with injection molds (1, 2). The female piece 1 is provided with an air suction path 7 connected to a vacuum pump 6 for reducing the pressure in the cavity 3.

First, a primer solution is applied to one surface of the skin film, or the skin film is used as an outer layer, and a primer solution is applied inside the outer layer, and a polyolefin-based resin and an ethylene / α-olefin-based polymer are applied thereto. A composite sheet is prepared in which an inner layer of a thermoplastic elastomer and / or a polypropylene, which is a blend with a partially crosslinked product of a united rubber, is laminated.

The application of the primer solution is performed by a doctor knife method, a roll coater method, a gravure coating method, a spray method, or the like.

Then, with the pair of male and female molds (1, 2) open, the surface side of the skin film where no primer is applied, and the outer layer side of the composite sheet is the female cavity inner wall surface side. Then, the skin film or the composite sheet 4 is stretched so as to cover the cavity opening of the male mold 1, and the heater section 5 of the preheating device is brought close to the skin film or the composite sheet 4 in the opening portion to perform the preliminary heating. I do. The preheating temperature is 150-250 ° C. As means for preheating, not only the approach of the heater section 5 but also various means such as blowing of warm air and contact of a heating roll can be used.

Thereafter, the interior of the cavity 1 of the female mold 1 is made negative pressure by suction by the vacuum pump 6, and the skin film or the composite sheet 4 is brought into close contact with the inner wall surface of the cavity (FIG. 1 (b)).

Thereafter, the heater section 5 is retracted, and the pair of male and female molds (1, 2) are clamped as shown in FIG.
Is injected with a synthetic resin mainly composed of a polyolefin resin in a fluidized and plasticized state, and solidified by cooling or the like, and then taken out as a product.

The trimming for taking out the product can be performed in the mold (1, 2) at the same time as the mold clamping, so that trimming in a subsequent step is unnecessary.

Next, an example of an apparatus used in the above-mentioned manufacturing method (b) will be described. This apparatus is, as shown in FIG. 2, a T-die extruder for extruding the thermoplastic elastomer and / or polypropylene into a sheet. 31, a supply device 32 for supplying the skin film 34 coated with the primer liquid to the extrusion port side of the T-die extruder 31, and a preheating device 33 for preheating the skin film 34 at the time of supply. Furthermore, after the molten sheet-like resin extruded from the die of the T-die extruder 31 and the primer coating surface of the skin film 34 supplied from the supply device 32 are overlaid, these are paired with a pair of rolls 35, It is designed to be pinched and stuck at 35 and picked up by a pick-up machine 36.

Lastly, the production methods (d) and (e) will be described. Also in this case, a skin film coated with a primer solution or the composite sheet is prepared. Here, the composite sheet manufactured by the method (b) can be used as it is.

Then, as shown in FIG. 3, there is provided a pair of molding dies (1, 2) with the female mold 1 down and the male mold 2 up, and with the molds (1, 2) open. While preheating the composite sheet or film 4 with the heater 5 of the preheating apparatus, the composite sheet or film 4 is supplied between the molds (1, 2). In the case of using a composite sheet, the outer layer side is extended to cover the cavity opening of the female mold 1 such that the outer layer side is on the inner wall surface side of the female mold cavity. The skin film or the composite sheet 4 is brought into close contact with the inner wall surface of the cavity by suction.

Thereafter, a synthetic resin mainly composed of a polyolefin resin in a fluidized and plasticized state is poured into the cavity 3 from the extruder 10 and then clamped. By closing the mold, a synthetic resin mainly composed of a polyolefin resin in a fluidized plastic state is filled in the cavity 3 by the pressing force of the molds (1, 2). After solidification, it is taken out as a product. Also in this case, the trimming can be performed in the mold (1, 2) simultaneously with the mold clamping.

Here, a synthetic resin mainly composed of a polyolefin resin in a fluidized plasticized state is poured into the cavity 3 by:
An injection nozzle 11 movable in the X and Y directions is provided on the cavity 3 so that the injection nozzle 11 can be uniformly poured over the entire area of the cavity 3.
It is preferable to inject a synthetic resin mainly composed of a polyolefin resin in a fluidized plasticized state.

In the above description, the synthetic resin mainly composed of a polyolefin resin in a fluidized plasticized state is, for example, a molten resin obtained by heating, kneading, and dispersing with a screw type extruder, and a fluidized plasticized state with a solvent. And the like.

Further, in the manufacturing methods (a), (c), (e), and (d), a mold for vacuum-forming the sheet or film made of the thermoplastic elastomer by suction and intimate contact with the inner surface of the cavity; A mold for molding a body is prepared separately, and first, a preform made of a sheet or film made of the thermoplastic elastomer is vacuum-molded with a mold for vacuum molding. In the case of the methods (a) and (c), the mold is closed in the cavity of the mold, and a synthetic resin mainly composed of a polyolefin resin in a fluidized plasticized state is filled in the cavity. In the case of the methods (d) and (e), injection-filling is performed, and in the case of the methods (d) and (e), the preformed article formed by vacuum molding is mounted on a molding die, and then a polyolefin-based fluidized state is formed in the cavity. Resin-based Pouring synthetic resin, then, it may be molded by mold clamping.

〔Example〕

 Hereinafter, embodiments of the present invention will be described.

<Examples by Production Method (a)> First, a laminated molded product obtained by laminating a skin layer via a primer layer on the surface of an aggregate molded product made of a synthetic resin mainly composed of a polyolefin resin was produced as shown in (a). Examples and comparative examples manufactured by the method will be described.

Prior to the implementation, the following A, B, C, and D4 types of films were produced and a primer solution was applied to one surface, and the above film was heated in advance, and the primer was applied by the apparatus shown in FIG. The surface that is not covered is the female mold cavity inner wall surface side, and drawn into vacuum by vacuum contact with the female mold cavity inner surface, then the male mold is closed and the molten resin is injected from the injection molding machine into the cavity from this male mold side. Injection filling,
When solidified and integrated with the film, the mold was opened and taken out, and the adhesive strength between the film and the formed aggregate was evaluated.

(1) First, the film used here will be described.

<< Film A >> A propylene-ethylene copolymer having a propylene content of 600 mol% and a crystallinity of 10% by X-ray diffraction on one surface of a biaxially stretched ABS film having a thickness of 500 μm and a width of 500 mm. coalescence, maleic acid or primer liquid doctor knife and the anhydride thereof with 8 wt% graft copolymerization to become modified polymer [eta] is obtained by 30kg dissolved to toluene 1 m ³ to 0.5 or more modified polymer What was applied by the method. The thickness of the primer layer was 30μ.

<< Film B >> A wood pattern is printed on a biaxially stretched polyurethane film having a thickness of 500 μm and a width of 550 mm with a urethane-based paint, and the propylene content is 60 mol% on the printed surface side. A modified polymer obtained by graft copolymerizing 8% by weight of maleic acid or its anhydride with a propylene-ethylene copolymer having a degree of polymerization of 10%, and a modified polymer having [η] of 0.5 or more in 1 m ³ of toluene. 30kg dissolved in primer solution applied by doctor knife method. The thickness of the primer layer was 30μ.

<< Film C >> A propylene-ethylene copolymer having a propylene content of 60 mol% and a crystallinity of 10% by X-ray diffraction on one surface of a biaxially stretched 500 μm thick, 550 mm wide polyamide film, maleic acid or modified polymer the anhydride formed by polymerizing 8 wt% graft that [eta] is applied to 0.5 or more modified polymer primer liquid formed by 30kg dissolved to toluene 1 m ³ with a doctor knife method What you did. The thickness of the primer layer was 30μ.

<< Film D >> A primer obtained by dissolving 60% by weight of chlorinated polypropylene in toluene on one surface of a biaxially stretched polyvinyl chloride film having a thickness of 500μ and a width of 550mm (solid content: 15%)
And dried at 70 ° C. The thickness of the chlorinated polypropylene was 10μ.

<< Film E >> A biaxially stretched ABS film having a thickness of 500 μm and a width of 550 mm, which is not treated with any primer.

<< Film F >> An untreated primer film in which a wood pattern is printed with a urethane-based paint on a polyurethane film with a thickness of 500μ and a width of 550mm.

<< Film G >> A biaxially stretched polyamide film having a thickness of 500 μ and a width of 550 mm which is not treated with a primer. << Film H >> A polyvinyl chloride film having a thickness of 500 μ and a width of 550 mm which is not treated with a primer.

(2) Next, the following was used as a molding material for the aggregate molded article. << Molding Material TPE (1) >> Ethylene content 70 mol%, iodine value 15, Mooney viscosity
ML1 + 4 (100 ° C) 120 ethylene / propylene-ethylidene norbornene copolymer rubber (hereinafter referred to as EPDM (1)) 70 parts by weight Melt index (ASTM D-1238-65)
T, 230 ° C) 13, 30 parts by weight of polypropylene (hereinafter referred to as PP) having a density of 0.91 g / cm ³ , butyl rubber (11R-0 manufactured by Esso)
65, 0.8 mol% of unsaturation, hereinafter abbreviated as 11R) 10 parts by weight,
And 30 parts by weight of paraffin-based process oil (hereinafter abbreviated as oil) were kneaded with a Banbury mixer in a nitrogen atmosphere at 190 ° C. for 5 minutes, and then passed through a roll to produce square pellets by a sheet cutter.

Next, 100 parts by weight of the square pellet and 1,3-bis (tert
0.3 parts by weight of -butylperoxyisopropyl) benzene (hereinafter abbreviated as peroside (A)) and 0.5 parts by weight of divinylbenzene (hereinafter abbreviated as DVB) were stirred and mixed with a Henschel mixer. Then, the pellets were extruded at 220 ° C. under a nitrogen atmosphere by an extruder to obtain a thermoplastic elastomer (TPE (1)) having an MFR of 3 g / 10 min.

<< Molding material TPE (2) >> Ethylene content 78mol%, Iodine value 10, Mooney viscosity
ML1 + 4 (100 ° C.) 160, oil-extended amount 40 parts by weight, ethylene-propylene-ethylidene norbornene copolymer rubber (hereinafter referred to as EPDM (2)) 60 parts by weight (accordingly, ED
43 parts by weight of PM, 17 parts by weight of oil), 40 parts by weight of PP, 2,5 dimethyl-2,5 di (t-butylperoxy) hexyne-
3 (hereinafter abbreviated as peroxide (B)) 0.5 parts by weight was stirred and mixed with a Henschel mixer. Then, the mixture was subjected to a Warner twin-screw extruder (L / D = 43, meshing type, isotropic rotation, triple-type screw) under a nitrogen atmosphere for 220 hours.
Extruded at ℃ to obtain a thermoplastic elastomer (TPE (2)) having an MFR of 15 g / 10 min.

<< Molding material PP (1) >> Melt index (ASTM D-1238-65T, 230 ℃)
13, polypropylene with a density of 0.91 g / cm ³ .

<< Molding material PP (2) >> MFR 8 polypropylene containing 20% fine talc.

<< Molding material PP (3) >> MFR 5 polypropylene containing 10% fine talc and 10% short fiber glass fiber.

(3) In this example, the vacuum forming conditions are as follows.

Heater temperature: 260 ° C. (both sides) Preheating time: 45 seconds Vacuum pressure: 700 mmHg (4) The injection molding conditions in this example are as follows.

Forming shape machine; Dainameruta (Akira machine Seisakusho) Molding temperature; 220 ° C. injection pressure; primary pressure 1000 kg / cm ² Secondary pressure 700 kg / cm ² Injection speed: Maximum molding cycle; 90 sec / 1 cycle Gate; Direct Gate (Land length: 10 mm, width: 10 mm, thickness: 3 mm) Molded product: length: 500 mm, width: 400 mm, thickness: 3 mm (5) Next, a method for evaluating the laminated molded article in this example will be described.

<< Sample collection method >> As shown in FIG.
A peel test piece 20 having a width of 25 mm and a width of 25 mm, and a stripped test piece 21 having a length of 100 mm and a width of 100 mm were punched and collected.

<< Peeling Test >> Peeling off the skin layer film from the end of the peeling test piece, 18
The film was peeled off by pulling it at a pulling speed of 25 mm / min in the reverse direction at 0 °, and the adhesion speed at that time was evaluated. The adhesion strength was indicated by a value obtained by dividing the peeling load by the width of the test piece.

The results are shown in Table 1. However, when the film was damaged, it was described as “material breakage”.

<< Goban peeling test >> A film with a sharp razor is used to make 11 wounds of 1 mm in depth on the film surface in parallel at 2 mm intervals, and 11 similar wounds are made at right angles to it.

As a result, 100 squares cut into 2 mm squares are formed.
Cellotape made by Nichiban Co., Ltd. was stuck so as to cover all the 100 squares, and the stuck tape was vigorously peeled off to observe the peeling state. The evaluation of the peeled state was represented by the number of remaining 100 pieces / 100 out of 100 pieces. 100/100 indicates the state where no peeling occurred, 0/1
00 indicates a state in which all parts are removed. The results are shown in Table 1.

<< Comparative Example >> Without applying a primer liquid to the films A to D,
In the same manner as described above, the laminate was laminated with the aggregate formed body and subjected to a peeling test and the like. The results are shown in Table 1.

<Examples by Production Method (b)> Next, the thermoplastic elastomer and / or polypropylene sheets are laminated on the primer-coated surface side of the skin films A to D to obtain a composite sheet as a laminated molded article. Examples will be described.

2, the same films A to D as those in the previous embodiment are first supplied while being preheated to 180 ° C. by the preheating device 33, and the molten resin is extruded from the die of the T die extruder 31. Composite films A to D by laminating the surfaces of the films A to D on which the primer has been applied with a chill roll.
Was molded, and the peel strength and the like were measured. Table 2 shows the test results of the adhesive strength.

Here, as the resin extruded from the extruder, the TPE
(1), (2) and PP (1) to (3) were used.

 The T-die extrusion molding conditions are as follows.

Extruder; Toshiba 50mm screw; Full flight type L / D; 28 compression; 3.5 die; Coat hanger die Extrusion temperature; 230 ° C <Examples by the manufacturing method of (c)> Using the composite sheets A to D obtained in the above examples, the composite sheets A to D are preliminarily heated, and vacuum molded using a male mold to obtain molded articles. Obtained. Thereafter, the skin films A to D side are set to the female mold cavity inner wall surface side, inserted into the injection mold, the male mold is closed, and the molten resin is injected and filled from the injection molder into the cavity from the male mold side, The mold was opened and taken out when it was solidified and integrated with the film, and the adhesive strength between the composite sheet and the aggregate molded product was evaluated. Other conditions such as the material of the aggregate formed body were the same as those in the example of (a). As a test of the adhesive strength, the above-mentioned peeling test and gobang-peeling test were performed by making a cut deeper than the thickness of the composite sheet. The results were almost the same as those of Examples (1) to (9) of (a).

<Examples by Production Method (d)> A laminated molded product obtained by laminating a skin film via a primer layer on the surface of an aggregate molded product made of a synthetic resin mainly composed of a polyolefin resin is produced by the production method (d). An example in the case of manufacturing will be described.

The same skin films A to D as in the previous embodiment were heated in advance, and the surface on which the primer was not applied was turned to the inner wall surface side of the female mold by the apparatus shown in FIG. After drawing in close contact with the inner wall surface of the cavity, place the molten resin on the film with good distribution,
When the male mold was closed and the molten resin was solidified and integrated with the film, the mold was opened and taken out, and the adhesive strength between the film and the molding material was evaluated.

(1) The vacuum forming conditions are the same as in the previous embodiment.

(2) The molding material of the aggregate molding is as follows.

 TPE (1) and TPE (2) are the same as in the previous embodiment.

However, unlike PP (1), the melt index (ASTM D-1238-65T, 230 ° C) 3 and the density 0.91 g /
cm ³ of polypropylene was used.

In addition, MF containing 30% of fine powder talc as PP (2)
R2 polypropylene was used.

Further, as PP (3), polypropylene of MFR 0.7 containing 15% of fine powder talc and 15% of short fiber glass fiber was used.

(3) The molding conditions in this example are as follows.

Forming shape machine; Ikegai ISM-300 Screw type; 50 mm [phi] a resin temperature; 230 ° C. The pressing pressure; 200 kg / cm ² molding cycle; 50 (sec) formed molded article; length 500 mm, width 500 mm, thickness 3 mm (4) then Next, a method for evaluating a laminated molded product in this example will be described.

From the molded product, a 100 mm long, 25 mm wide peel test piece and a 100 mm long, 100 mm wide gobang peel test specimen were punched and sampled, and a peel test and a goban peel test were performed in the same manner as in the previous example. went. The results are shown in Table 3.

<Example of the manufacturing method of (e)> The composite sheets A to D obtained in the example of (b) were heated in advance, and vacuum molded using a male mold to obtain a molded product. Then, the surface film side was inserted into the stamping mold with the female mold cavity inner wall surface side, the molten resin was placed on the composite sheet with good distribution, the male mold was closed and the molten resin was solidified and integrated with the composite sheet. The mold was opened and taken out, and the adhesive strength between the composite sheet and the molding material was evaluated.

The molding material to be filled in the mold and other conditions were the same as in the example of (d). As a test of the adhesive strength, the above-mentioned peeling test and the stripping test were performed by making a cut deeper than the thickness of the composite sheet. The results were almost the same as those of Examples (1) to (9) of (d).

〔The invention's effect〕

According to the present invention, since a polyolefin-based resin is used as an aggregate molded product, an inexpensive laminated molded product can be obtained. In addition, since the skin film of the ABS resin, polyamide, polyurethane, and polyvinyl chloride was laminated on the aggregate formed body of the polyolefin resin through the primer layer formed by the application of the primer solution, sufficient adhesive strength was obtained. Can be obtained.

Since ABS resin, polyamide, polyurethane, and polyvinyl chloride are used as the surface film, it is easy to perform vacuum forming, and it is possible to obtain a molded product with extremely few molding defects.

Moreover, when using a composite sheet obtained by laminating the thermoplastic elastomer on a skin film and laminating it on an aggregate molded article of a polyolefin resin, it is possible to impart appropriate flexibility in addition to the properties inherent in the skin film, It can be suitably used for a molded article in which the touch is important such as an automobile interior part.

[Brief description of the drawings]

1 (a) to 1 (d) are process drawings showing (a) and (c) of the manufacturing method, FIG. 2 is a schematic diagram of an apparatus used in the manufacturing method of (b), and FIG. d) Schematic diagram of an apparatus used in the manufacturing method of (e), and FIG. 4 is a plan view showing a sampling method. 1,2 ... mold (female mold 1, male mold 2), 3 ... cavity, 4
... skin film or composite sheet, 5 ... heater section, 6 ... vacuum pump, 7 ... air suction path, 8 ... injection molding machine, 10 ... extruder, 11 ... injection nozzle, 20 ... peeling Test piece, 21: Gobang peel test piece, 31: T-die extruder, 32: Feeding device, 33: Preheating device, 34: Skin film, 35: Roll, 36: Take-up machine.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI B29C 45/16 B29C 45/16 45/17 45/17 B32B 27/32 101 B32B 27/32 101 27/40 27/40 B60R 13 / 04 B60R 13/04 Z // B29K 23:00 75:00 B29L 31:58 (56) References JP-A-55-48260 (JP, A) JP-A-63-272547 (JP, A) JP 1-195044 (JP, A) JP-B 63-59383 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) B32B 1/00-35/00 B29C 45/00-45 / 84 B29C 39/00-39/44 B60R 13/04

Claims (10)

(57) [Claims] 1. A laminated molded article obtained by laminating a skin layer via a primer layer on the surface of an aggregate molded article composed of a synthetic resin mainly composed of a polyolefin resin, wherein the primer layer has a propylene content of 50 to 50. Propylene which is 75 mol% and has a crystallinity by X-ray diffraction of 2 to 20%.
Maleic acid or its anhydride is added to ethylene copolymer in 0.5
15 A% by weight graft copolymerization to become modified polymer thereof [eta] those formed by applying a liquid obtained by 10~100kg dissolving 0.3 or more modified polymer in an organic solvent 1 m ³ Wherein the skin layer is a synthetic resin skin film made of polyurethane. 2. The aggregate formed article is a thermoplastic elastomer and / or polypropylene sheet made of a blend of a polyolefin resin and a partially crosslinked ethylene / α-olefin polymer rubber. 2. The laminated molded article for automobile interior parts according to claim 1, wherein the skin film is laminated on the sheet-shaped aggregate molded article via the primer layer to form a composite sheet. 3. An automotive interior part according to claim 1, wherein a synthetic resin paint layer having a picture pattern is interposed between said skin layer and said primer layer. Laminated moldings. 4. The method according to claim 1, wherein the propylene content is 50 to 75 mol% and X
Maleic acid or its anhydride is added to a propylene-ethylene copolymer having a crystallinity of 2 to 20% by line diffraction in an amount of 0.5 to 1%.
5% by weight of a modified polymer obtained by graft copolymerization and having a [η] of 0.3 or more with respect to 1 m ³ of organic solvent
Apply 10 to 100 kg of a primer solution dissolved on one surface of a synthetic resin skin film made of polyurethane,
After pre-heating this skin film, the surface on which the primer solution is not applied is set to the cavity inner wall surface side, and the skin film is suction-contacted to the mold cavity inner wall surface, and then the mold is clamped. A method for producing a laminated molded article for an automobile interior part, which comprises injection-molding and molding a synthetic resin mainly composed of a polyolefin resin in a fluidized plasticized state. 5. The method according to claim 1, wherein the propylene content is 50-75 mol% and X
Maleic acid or its anhydride is added to a propylene-ethylene copolymer having a crystallinity of 2 to 20% by line diffraction in an amount of 0.5 to 1%.
5% by weight of a modified polymer obtained by graft copolymerization and having a [η] of 0.3 or more with respect to 1 m ³ of organic solvent
Apply 10 to 100 kg of a primer solution dissolved on one surface of a synthetic resin skin film made of polyurethane,
After preheating the skin film, on the surface on which the primer liquid has been applied, a thermoplastic elastomer comprising a blend of a polyolefin resin and a partially crosslinked ethylene / α-olefin polymer rubber by extrusion molding; and A method for producing a laminated molded article for an automobile interior part, in which a molten sheet material made of polypropylene is extruded and laminated to obtain a composite sheet. 6. A synthetic resin skin film made of polyurethane is used as an outer layer, and a propylene content is set inside the outer layer.
50 to 75 mol%, and the crystallinity by X-ray diffraction is 2 to 20
% Of a propylene-ethylene copolymer grafted with 0.5 to 21% by weight of maleic acid or an anhydride thereof, wherein the modified polymer having [η] of 0.3 or more is treated with 1 m ³ of organic solvent. A primer solution obtained by dissolving 10 to 100 kg of a thermoplastic elastomer comprising a blend of a polyolefin resin and a partially crosslinked product of an ethylene / α-olefin copolymer rubber and / or
Or, after preheating the composite sheet formed by laminating the inner layer made of polypropylene, the outer layer is set on the inner wall surface side of the cavity, this composite sheet is brought into close contact with the inner wall surface of the mold cavity, and then the mold is clamped. A method for producing a laminated molded article for an automobile interior part, which comprises injection-molding and molding a synthetic resin mainly composed of a polyolefin resin in a fluidized plasticized state. 7. A mold for vacuum-forming the synthetic resin skin film or the composite sheet made of polyurethane by suction and intimate contact with the inner surface of the cavity, and a preform obtained by vacuum forming are mounted in the cavity and clamped. What is a molding die?
These preformed products, which are separate from each other, are mounted in a molding die and then clamped, and the cavity is injection-filled with a synthetic resin mainly composed of a polyolefin resin in a fluidized plasticized state. The method for producing a laminated molded product for an automobile interior part according to claim 4 or 6, wherein the molded product is formed by molding. 8. A propylene content of 50 to 75 mol%, wherein X
Maleic acid or its anhydride is added to a propylene-ethylene copolymer having a crystallinity of 2 to 20% by line diffraction in an amount of 0.5 to 1%.
5 A wt% graft copolymerization to become modified polymer thereof [eta] is in organic solvent 1 m ³ to 0.3 or more modified polymer 10
Kg100 kg of primer solution is applied to one surface of a synthetic resin skin film made of polyurethane, and after preheating this skin film, the surface on which the primer solution is not applied is placed on the inner wall surface of the female cavity. To make the skin film adhere to the cavity inner wall surface by suction,
A method of manufacturing a laminated molded body for an automobile interior part, in which a synthetic resin mainly composed of a polyolefin resin in a fluidized plastic state is poured into the cavity in which the skin film is in close contact, and then the mold is clamped and molded. 9. A synthetic resin skin film made of polyurethane is used as an outer layer, and a propylene content is set inside the outer layer.
50-75 mol%, and the crystallinity by X-ray diffraction is 2-20.
Propylene is the percent - that the ethylene copolymer to maleic acid or its anhydride to a modified polymer obtained by polymerizing 0.5 to 15 wt% graft [eta] is an organic solvent 1 m ³ to 0.3 or more modified polymer A primer solution obtained by dissolving 10 to 100 kg is applied to a thermoplastic elastomer and / or polypropylene made of a blend of a polyolefin resin and a partially crosslinked product of an ethylene / α-olefin polymer rubber. After preheating the composite sheet formed by laminating the inner layers, the outer layer is placed on the inner wall surface of the cavity, the composite sheet is suction-contacted to the inner wall surface of the mold cavity, and then flows into the cavity where the composite sheet adheres. Manufacture of laminated molded products for automotive interior parts in which a synthetic resin mainly composed of a plasticized polyolefin resin is poured, and then molded and clamped. Law. 10. A mold for vacuum forming the synthetic resin skin film or the composite sheet made of the polyurethane on the inner surface of the cavity by suction, and a preformed product obtained by vacuum forming is mounted in the cavity to close the mold. The molding die to be formed is separate from each other, and is mainly composed of a polyolefin-based resin in a fluidized plasticized state in the cavity after the vacuum-formed preform is attached to the molding die. The method for producing a laminated molded article for an automobile interior part according to claim 8 or 9, wherein a synthetic resin is poured, and then molded by clamping.