JPS6228238A - Composite molded shape - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The composite molded product of the present invention can be used as a lining insulation material for the main body or door of a cold storage room, or as a door for a show window case or unit bath that requires heat insulation. It is useful for automotive interior materials such as rims (bumpers and doors of automobiles that require cushioning properties), surfing boards, etc.

[Prior art]

The main body and doors of the refrigerator are made of baked-on stainless steel or steel plates, and are made of acrylonitrile-butadiene-styrene composite (commonly known as "AB8J"), which is a styrene resin, to prevent rust from the structural base material (outer frame) and to form shelves. A lining material obtained by vacuum forming, pressure forming, or a combination of vacuum and pressure forming (all these forming methods are collectively referred to as thermoforming hereinafter) is provided.In addition, an ABS lining material is provided. Instead, it has been proposed to use polypropylene/outer lining material, which has excellent surface gloss and low water absorption.

In order to improve the heat insulation properties of these lining materials, it has been proposed to interpose foamed polyurethane between the structural base and the lining material (Japanese Patent Laid-Open No. 60-97841).

In addition, door materials for unit baths are currently made of polyvinyl chloride sheets, but when used at high temperatures,
There is a problem that the aluminum sash frame is corroded by the chlorine gas generated by decomposition, so in order to improve this problem, two polypropylene sheets are attached to the aluminum sash frame without using a polyvinyl chloride sheet, and the aluminum sash/frame and/or - It is being considered that the space surrounded by the door can be filled with foamed polyurethane to provide rigidity as a door.

Furthermore, with the switch from metal to resin for interior materials such as automobile door trims, filling polyurethane foam by injection method is being considered for the purpose of providing cushioning or heat insulation.

As described above, there is a demand for composites of resin materials and foamed polyurethane in resin products with various complex shapes.

[Problem that the invention seeks to solve]

However, the resin material is usually 1''' of the sheet.

Or, it is made into a molded product by fully matured sheet type or injection molding. When polyolefin resin in such a shape is used, voids are formed due to insufficient adhesive strength with foamed polyurethane, resulting in poor rigidity and heat insulation. It has the disadvantage that it cannot fully achieve its purpose.

In order to improve the adhesive strength between this resin material and foamed polyurethane, it is possible to apply a liquid adhesive or adhesive liquid or to treat the surface with chemicals (Japanese Patent Application Laid-Open No. 60-97841), but this increases the number of coating and surface treatment steps. The addition of complicated steps is not desirable.

The present invention improves the adhesive force with 7-ohm urethane by eliminating such a treatment step and blending ABS or the like into the olefin resin that adheres to the urethane foam.

(Components of the Invention) The present invention provides a composite molded product having a structure in which an olefin resin molded product and a urethane foam are integrally laminated via the following adhesive layer.

Adhesive composition A), olefin resin 40-85% by weight B), M
60-15% by weight of ethylene-acrylic acid copolymer with FR less than 3 Of/10 minutes.

(Olefin resin molded article) Olefin resins for forming olefin resin molded articles include polyethylene, polypropylene, ethylene/propylene copolymer, ethyleneΦpropylene/butene copolymer, polystyrene, styrene/butadiene/styrene block copolymer, etc. Non-polar olefin resins such as polymers, ethylene/acrylic acid random copolymer, ethylene/methacrylic acid "77dumb copolymer, acrylic acid graft polyethylene, methacrylic acid kraft polyethylene, maleic anhydride kraft polyethylene, maleic anhydride" Carboxyl group-containing olefin resins such as acid-grafted polypropylene, maleic anhydride-grafted ethylene/vinyl acetate copolymer, and itaconic acid kraft polyethylene can be used, and these can be used alone or as a mixture.

1 polyamide and ABS to this olefin resin.

Resins such as ethylene/vinyl acetate copolymers, stabilizers, rubbers, pigments, and inorganic fillers may also be blended.

Alternatively, the olefin resin may be formed into a layered structure, with each layer having a specific function. For example, when the olefin molded product is a skin material for a shop window case or refrigerator interior material, the surface layer is a homogeneous polypropylene film with good gloss, and the base layer is a film of gold with good vacuum formability as shown below. Use the sheet.

(a) Polypropylene 20-80M, preferably 40-70% by weight (b) Polyethylene, 51-80M, fit%, preferably 10-551
(C) Styrenic resin 0 to 35 weight ratio, preferably 5 to 25 weight ratio (d) Inorganic fine powder O to 65 weight ratio, preferably 5 to 55 1 (Amount to above component (a) The polypropylene contributes to the immersion properties with the homopolypropylene of the surface gloss layer.The polyethylene component (B) improves the deep drawability during vacuum forming of the laminated sheet.The styrene resin component (C) It contributes to reducing the sag of the laminated sheet softened or melted by heating due to its own weight.The inorganic fine powder of component (d) increases the rigidity of the olefin resin molding and also improves the laminated/melted sheet.
- Contributes to improving the cooling cycle when vacuum forming sheets.

The polypropylene component (a) is a homopolymer of propylene, with propylene as a product component, and ethylene,
Random copolymers or block copolymers with olefins such as butene-1, hexene, and 4-methpentene-1, maleic anhydride grafted polypropylene, and the like can be used.

(g)) Component polyethylene includes high-density polyethylene, low-density polyethylene, linear polyethylene, ethylene/vinyl acetate copolymer, ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, Surlyn ciD
(Product name manufactured by DuPont) etc. can be used.

As the styrene resin of component (C), polystyrene,
Styrene-butadiene-styrene block copolymer (S
BS), styrene-acrylonitrile copolymer (SA)
, ABC, No impact polystyrene (HIPS)
etc. can be used.

As the inorganic fine powder of component (d), Merck, calcium carbonate, kieselguhr, calcined clay, titanium oxide, etc. can be used.

(Adhesive layer) The adhesive resin composition of the urethane 7 ohm and the olefin resin molded article is (4) Olefin resin 40-85]! :
J1% and ■ethylene-acrylic acid copolymer 60-15
It is a mixture of weight i-%. This mixture may contain a styrene resin, ethylene/propylene copolymer rubber, styrene/butadiene rubber, etc., which will be described later.

As the olefin resin of the captive component, polypropylene,
The olefin resins mentioned in the section of the base material layer, such as polyethylene, can be used. Preferably, the same type of olefin resin as the base material layer is used. For example, if the olefin resin in the base material layer is a mixture of homogeneous polypropylene and high-density polyethylene, the olefin resin in the adhesive layer may be propylene/ethylene random copolymer, propylene Φ ethylene block copolymer alone, or homogeneous olefin resin. When using a mixture of polypropylene and high-density polyethylene, preferably a propylene-ethylene block copolymer, the surface of the adhesive layer extruded into a film from an extruder will be
Since the surface is rougher than that of the film adhesive layer obtained from homopolypropylene or propylene/ethylene random copolymer, it has the advantage of improving adhesion to the urethane foam and the base material layer.

■The component ethylene/acrylic acid copolymer is JIS
The MFR measured at 190 °C according to the provisions of K-6758 is less than 3 o tyx o min, preferably 2 to 20 r7
10% resin, which contains 70 to 99% ethylene by weight.
It is a relatively high molecular weight resin obtained by random copolymerization of acrylic acid and 30 to 1 weight percent of acrylic acid. Such products are manufactured by Mitsubishi Yuka (from the text "Yukalon EAA A221M").
Yucalon EAAA20 OK”, 1 Yucalon EAAA
It is sold under the name XA21O8' (all product names).

If the concentration of component (5) in the ethylene-acrylic acid copolymer in the adhesive resin composition is less than 15% by weight, the adhesion between the urethane foam and the adhesive layer will be low, making it impractical. On the other hand, if it exceeds 60% by weight, the mold release property will be poor when the laminate sheet is subjected to vacuum forming, press forming, pressure forming, or injection molding. However, in the case of blow molding, the surface of the adhesive layer becomes the inner surface of the hollow molded product, so such problems with mold releasability can be ignored.

In order to improve such mold releasability, styrene resins are blended as necessary, and even if the amount of ethylene/acrylic acid copolymer added is reduced, the styrenic resins have a lower cost.Polystyrene, ABS, and SBS.

5AXHIPS etc. can be used. Among these, ABS
, the adhesion between the urethane foam and the adhesive layer is higher.

However, the olefin resin component (4) in the adhesive alone does not have adhesive properties with the urethane foam.

The adhesive layer can be formed together with the olefin resin molded article. For example, the resin compositions forming the gloss layer, base material layer, and adhesive layer are each melt-kneaded using separate extruders, then fed to a single coextrusion die, and the layers are laminated within the die. Then, it is extruded into a sheet or parinon shape, and then vacuum formed, compression molded, or blow molded, and used as a laminate for refrigerator lining materials and surfboards.

In the case of a molded object such as a bumper, an adhesive resin composition is first injected into a mold, then this adhesive injection molded product is transferred into another mold, and then the polypropylene/epoxy resin composition for the skin material is injected.
is injection molded to form a laminate.

The thickness of the olefin resin molded body is 0 in the thickness No. 1 of the laminate.
．． 5 to 15 JI, preferably 2 to 511 JI, and the thickness of the adhesive layer is 5 to 100 micron (extrusion molded product) or 0.5 to 2 micron (injection molded product).

The entire surface of these laminates may be subjected to corona discharge treatment or plasma treatment, if necessary.

FIG. 2 is a cross-sectional view of the 18-piece body 2, in which 2a represents a surface gloss layer, 2b represents a base material layer, and 2C represents an adhesive layer.

(Composite molded product) The composite molded product is obtained by bonding the olefin resin molded product and urethane foam together via an adhesive layer.

In the case of a surfing board, a foaming urethane liquid is injected into the hollow portion of the hollow-molded laminate and foamed.

When used as interior material for a refrigerator, as shown in Fig. 1, a formwork (1) made of decorative steel plate and the vacuum-formed laminate (2) are used.
A foamable urethane solution (4) is injected into the cavity (3) formed by the mold, which is then foamed and hardened to form the mold (
A multi-layered structure in which 1), the urethane foam (4'), and the lining material (2) are integrated is manufactured.

Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that the divisions and divisions in the column are based on weight.

Sheet production example 1 (1) Resin for glossy surface layer: MFR2,05'/1
A crystalline propylene homopolymer having a residual amount of 99 weight ff 1% after extraction with boiling tit heptane for 0 minutes was used.

(11) Resin for deep drawing layer: Ethylene content 5% by weight, MF RO, 5f/10 min, boiling heptane extraction residue ff
98 quintillion i% crystalline propylene number ethylene block copolymer 30% by weight, density 0.9 s o y /ctd
, 8iF RO, 6f / 10min polyethylene 45
A mixture of F4, talc having a particle size of 1.5, and 20 ffi of talc was kneaded using an extruder, extruded into a strand, and cut into pellets.

(Kawa) Adhesive on the side that is bonded to the urethane foam: Ethylene content 5M Dosuke, MF R O. 5y/1
0 minutes, boiling hebutane extraction residual amount 98% by weight of crystalline propylene-ethylene block copolymer 90% by weight and Mitsubishi Yuka 61-side ethylene-acrylic acid (8.5Wt) copolymer "E A A A 2 2 1 M'' (product name,
The mixture with MFRIy/1o min) 20M was kneaded using an extruder, extruded into a strand, and cut into a pellet.

The deep drawing/J hI fat pellets of (11) above were prepared with a diameter of 9
The gloss 7'd resin of (1) and the adhesive resin composition of (1i1) were each separately fed to a +6700 m three-layer multi-manifold die at 230°C using a zero-force extruder. The mixture was supplied to a press at 220° C. using an extruder with a diameter of 401 mm. The die temperature was 220°C. The molten sheet extruded from Da.1 was sequentially cooled and solidified using three rolls with a width of 700 mm, and then subjected to corona discharge treatment to obtain a laminate sheet for vacuum forming. The temperature of the rolls was 40°C, 95°C, and 50°C starting from the roll closest to the die, and the rotational speed of the rolls was 1.5 m/min. The total sheet thickness is 1.61, and the glossy surface layer is Q. 15w
The deep drawing layer (intermediate layer) was 1.35 mm, and the adhesive resin layer 1111 with the urethane foam was 0.1 mm.

Example 2 An fR layered sheet was obtained in the same manner as in Example 1, except that the composition of the adhesive resin layer was changed as shown in Table 1.

The abbreviations in the table are as follows.

PP diglobylene ethylene block copolymer E-AA: Ethylene/acrylic acid copolymer A200: Ethylene/acrylic acid copolymer manufactured by Mitsubishi Yuka@ (acrylic acid content 7% by weight, MFR sr, io minutes) 3t 8.5% by weight, MF' R7y / 10 minutes) PS: Polystyrene "Dialex HT516" manufactured by Mitsubishi Monsanto Kasei ■ (product name) SBS: Asahi Kasei (5LIS - Toughprene A'' manufactured by Chikara)
(Product name) Example 1 The three-layer laminate obtained in Example 1 was introduced into a heating furnace set at about 230°C using a vacuum/pressure forming machine, and
Plug assist molding was carried out using a combination of pressure reduction (-600 .mu.Hg) (drawing ratio H/D=1/1). The release properties of the sheet were good, and the plug was easily separated from the sheet.

After drilling an injection port in a part of this shaped sheet, this sheet is inserted into the stainless steel frame that is the frame of the refrigerator body, and then the space (cavity) formed by the frame and the shaped sheet is inserted. Inject polyurethane Kagaku Kasei dM2 moldable foaming urethane solution "HM-151" into the inlet.
When 0'' (trade name) was injected, foaming started after 10 seconds, and the space was completely filled with urethane foam after 1 minute.The density of this urethane foam was 0.05.
It was 2/-. The same operation was repeated 20 times) to obtain 20 composite molded body samples.

After 24 hours, the sheet with the urethane foam adhered to it was cut out, and the adhesion between the urethane foam and the sheet was measured by the following method.

After separating the urethane foam from the sample piece by hand, use a knife to remove the urethane foam from the remaining urethane foam.
Suppose that the first sieve cell is cut into pieces, then additional adhesive tape is pasted on this cell, and the adhesive tape is vigorously peeled off from the entire sheet. /-t111. i], the remaining 44 stitches of the urethane foam were examined.

The results are shown in Table 1.

The evaluation criteria for adhesion are as follows.

○: Cohesive failure of Nirarethane foam ×: Adhesion between the urethane foam and the adhesive layer is weak, and the notebook is easily peeled off from the interface with the urethane foam.

Examples 2 to 8, Comparative Examples 1 to 4 Composite molded bodies were obtained in the same manner except that the laminate sheets of Example 1 were replaced with those of Examples 2 to 9.

The adhesion of these composite molded bodies to the urethane foam notebook is shown in Table 1.

(Left below) Example 7 Propylene/ethylene block copolymer 8Qffit% used in Example 1 and ethylene/acrylic acid copolymer "A"
A mixture of 20% by weight of 221M″ was used as an adhesive, and homopolypropylene was used as a skin layer, and each was magnetically kneaded at about 220°C using separate extruders, supplied to one die, and laminated within the die. Thereafter, it was extruded into a parison shape and then hollow-molded to obtain a molded article for a surfing board.

A two-component urethane solution was injected into the hollow part of this molded body and foamed to obtain a surf inno board.

The adhesion between the urethane foam and adhesive layer of this product is as follows:
It was stronger than that of Example 2.

Example 8 (1) Resin provided for gloss layer: MFR2, oy/lo minute,
A crystalline propylene homopolymer weighing 99 ft of boiling hebutane extraction residue was used.

(It) Resin for deep drawing layer (intermediate layer): Ethylene content 5 Hs, MF RO, 5? / 10 minutes, boiling to butane extraction residual amount: 98% market weight, crystalline propylene-ethylene block copolymer: 40% by weight, density: 0.950 f/
L: fA, MF R0,6r/l 0 minute polyethylene 40X'Jk%, talc 20 weight ff1 with particle size 1.5μ
The composition was kneaded in a total extruder, extruded into strands, and cut into berets.

(iii) Adhesive resin: The same one as in Example 1 was used (PP80m, E-EA″A 22 i M″20
weight%).

The above (II) deep drawing/& resistant resin pellet all diameters 90
Using an extruder with a diameter of 40 m, the resin for the glossy layer was fed into a three-way multi-manifold die with a width of 700 mm at 230°C, and the resin for the glossy layer (1) was fed into a multi-manifold die with a diameter of 40 m at 230°C.
of adhesive resin was fed into the same die at 220° C. using a separate extruder. The die temperature was 230°C. If'c melting value is extruded from the die, it is sequentially cooled and solidified using three rolls with a width of 700 mm, and then corona discharge treatment is performed.
A sheet for layered vacuum forming was obtained. The temperature of the rolls ζ was 40°C, 95°C, and 50°C from the roll closest to the die, and the rotational speed of the rolls was 1.5 m/min. The total sheet thickness is 1.6 m, and the gloss layer is 0.20 rui.
, the deep drawing layer was 1.25 m, and the adhesive layer was 0.15 m.

This was vacuum-formed as in Examples 1 and 1'i'8], and further mounted in a frame and urethane foam-molded to obtain a composite molded body.

The results are shown in Table 1.

[Brief explanation of drawings]

FIG. 1 is a sectional view showing one embodiment of the present invention, and FIG. 2 is a sectional view of a notebook. In the figure, 1 is a stainless steel frame, 2 is a laminated notebook for differential pressure molding (lining material), 2a is a glossy surface layer, and 2b is a chestnut squeeze J-1
2CVi adhesive layer, 3 a cavity, 4' a urethane foam, and 5 an injection port.

Claims (1)

[Claims] 1) A composite molded article adhesive composition having a structure in which an olefin resin molded article and a urethane foam are integrally laminated via the following adhesive layer A) Olefin resin 40 to 85 Weight% B) 60-15% by weight of an ethylene/acrylic acid copolymer with an MFR of less than 30 g/10 minutes 2) An olefin resin molded body made of homogeneous polypropylene as a surface layer and the following composition as a base material Composite molded body base material layer composition according to claim 1, characterized in that it is a laminate in the form of a layer (a) 20 to 80% by weight of polypropylene (b) 10 to 80% by weight of polyethylene (c) Styrenic resin 0-35% by weight (d) Inorganic fine powder 0-65% by weight. 3) The composite molded article according to claim 1, wherein the olefin resin of the adhesive composition is polypropylene.