JPS6228239A - 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] [Field of Industrial Application] The composite molded product of the present invention can be used as a lining insulation material for the main body or door of a refrigerator, or as a door for a show window case or a unit bath that requires heat insulation. It is useful for automotive interior materials such as automobile bumpers and door trims that require cushioning properties, surfing boards, etc.

[Prior art]

The main body and door of the Chii I1.1& are made of baked-on stainless steel or a styrene-based resin (acrylonitrile-butadiene-styrene copolymer) that also serves as rust prevention for the steel plate structural base (outer frame) and for forming shelves. The combined (commonly known as rABsJ) sheet is formed into a true cylindrical shape, pressure molded, or molded using a combination of vacuum and pressure (
Hereinafter, these molding methods are collectively referred to as thermoforming). In addition, it has been proposed to use a polypropylene cracked lining material that has excellent surface gloss and low water absorption compared to ABS internally made lining material.

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

Currently, door materials for unit baths are 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 instead of using a polyvinyl chloride sheet, and the aluminum sash frame is surrounded by the sheet. Consideration has been given to filling the space with foamed polyurethane to provide rigidity as a door.

Furthermore, filling polyurethane foam by injection method for the purpose of cushioning or heat insulation is being considered for the interior materials of automobile door inlets and the like due to the conversion from metal to resin.

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 a sheet or a sheet molded by thermoforming or injection molding, and when polyolefin resin in such a shape is used,
Due to insufficient adhesion to foamed polyurethane, voids are formed, which has the disadvantage that the purpose of rigidity and heat insulation cannot be fully achieved.

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 strength to urethane foam by eliminating such a treatment step and blending ABS or the like into an olefin resin that adheres to urethane foam.

(Structure 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 65-95% by weight B), ethylene/acrylic acid copolymer 35-5% by weight.

(Olefin Resin Molding) Olefin resins for forming olefin resin moldings include polyethylene, polypropylene, ethylene/propylene co-ffi combination, ethylene/propylene/butene copolymer, polyethylene, styrene/butadiene/styrene block. Non-polar olefin resins such as copolymers, ethylene/acrylic acid random copolymers, ethylene/methacrylic acid random copolymers, acrylic acid kraft polyethylene, methacrylic acid grafted polyethylene, maleic anhydride grafted polyethylene, maleic anhydride grafted Carbokylene group-containing olefin resins such as 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.

Polyamide and ABS are added 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 window cases or refrigerator interior materials, the surface layer is made of homogeneous polypropylene alone with good gloss, and the base material layer is made of fill 1. A sheet of the following composition is used.

(a) Polypropylene 20-80% double pickling, preferably 40-80% 70 heavy clearing% (b) Polyethylene 1-80% by weight, preferably 10-55% by weight (e) Styrenic resin 0-35% by weight, preferably 5-25 Heavy barge% (d) Inorganic fine powder 0-65 2% by weight, preferably 5-55 Heavy clearing%.

The polypropylene component (a) contributes to the adhesion of the glossy surface layer to the homopolypropylene. Component (b) polyethylene improves the deep drawability of the laminated sheet during vacuum forming. The styrene resin as component (e) 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) not only increases the rigidity of the olefin resin molded article, but also contributes to improving the cooling cycle when vacuum forming the laminated sheet.

The polypropylene component (a) is a homopolymer of propylene, containing propylene as the main component, and ethylene,
Random copolymers or block copolymers with olefins such as phthene-1, hexene, and 4-methylpentene-1, maleic anhydride grafted polypropylene, etc. can be used.

Component (b) polyethylene includes high-density polyethylene, low-density polyethylene, linear polyethylene, ethylene/vinyl acetate copolymer, ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, Surlyn ■ (DuPont Co., Ltd.) product name) etc. can be used.

As the styrene resin of component (C), polystyrene,
Styrene/furidiene/styrene block copolymer (S
BS), styrene-acrylonitrile copolymer B (SA)
, ABS, No-Iinno (Ctopolystyrene () IIP
S) etc. can be used.

As the inorganic fine powder of component (d), talc, carbonic acid, diatomaceous earth, calcined clay, titanium oxide, etc. can be used.

(Adhesive layer) The adhesive resin composition of the urethane foam and the olefin resin molded article is (4) 65 to 95% by weight of olefin resin.
and (8) an ethylene/acrylic acid copolymer of 35 to 5 weight and 70 weight. This mixture may contain a styrene resin, ethylene/propylene copolymer rubber, styrene butadiene rubber, etc., which will be described later.

■The component olefin resins include polypropylene,
The olefin resin mentioned in the section of the base material layer, such as polyethylene, can be used. Preferably, the same type of olefin type 1 sealant as that of the base material layer is used. For example, if the olefin resin of the base material layer is a 4-polymer of homogeneous polypropylene and high-density polyethylene, the adhesive 7:4 olefin type (sealing) 1 is a propylene/ethylene random copolymer or a propylene/ethylene random copolymer. A non-block copolymer alone or a mixture of homogeneous polypropylene and high-density polyethylene is used.

Preferably, when a propylene/ethylene block copolymer is used, the surface of the adhesive layer extruded into a film from an extruder may be a film adhesive obtained from homogeneous polypropylene or a propylene/ethylene random copolymer. Since the surface is rougher than the surface of the layer, it has the advantage of improving adhesion to the urethane foam and the base material layer.

B) Component ethylene/acrylic acid copolymer is JISK
MFR measured at 190℃ according to the regulations of -6758 is 3
0 to 400 y/1 o of resin, which contains 70 to 99 weight percent ethylene and 30 to 1 weight percent acrylic acid.
It is a relatively low molecular weight resin made by random copolymerization of 1%. Such products are manufactured by Mitsubishi Yuka ■ “Yukalon E”
It is sold under the name AA A300W' (product name).

If the concentration of component (1) in the ethylene/acrylic acid copolymer in the adhesive resin composition is less than 5% by weight or less than 1% by weight, the adhesion between the urethane foam and the adhesive layer is low and is not practical. On the other hand, if it exceeds 35% by weight, the mold releasability 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, a styrene resin may be added if necessary to reduce the amount of ethylene/acrylic acid copolymer addition. Such styrene resins include polystyrene, ABS, and SBS.

SA, HIPS, etc. can be used. Among these, ABS
O has higher adhesion between the urethane foam and the adhesive layer.

However, the olefinic resin of component (e) 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, the base material portion, and the adhesive layer are each melt-kneaded using separate extruders, then fed to a single coextrusion die, and each layer is laminated within the die. Then, it is extruded into a sheet or parison shape, and then subjected to X-air molding, compression molding, and blow molding, and is 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 polypropylene for the skin material is injected. It is molded into a laminate.

The wall thickness of the laminate is such that the wall thickness of the olefin resin molded body is 0.
5 to 15 layers, preferably 2 to 5 layers, and the thickness of the adhesive layer is 5 to 100 microns (extrusion) or 0.5 microns.
~2 m (injection molded product).

If necessary, the surface of each of these products may be subjected to corona discharge treatment or plasma treatment.

FIG. 2 is a cross-sectional view of the laminate 2, where 2a is a surface gloss layer;
2b is a base material layer, and 2c is an adhesive layer.

(Composite molded product) The composite molded product is a composite molded product in which the olefin resin molded product and urethane foam are bonded together via an adhesive layer.

In the case of a surfing board, a foaming urethane liquid is injected into the hollow portion of the blow-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 multilayer structure is manufactured in which the urethane foam (4') and the lining material (2) are integrated into one.

Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that the part 70 in the column is based on weight.

Note production example 1 (i) Resin provided for glossy surface layer: MF R2, Oy/
A crystalline propylene homopolymer with a residual amount of 991% after being extracted with boiling butane for 1° was used.

(11) Resin used for deep drawing layer: Ethylene content 5%
, MF RO, 5f/10 min, boiling hebutane extraction residue 198% by weight of crystalline propylene-ethylene block copolymer 30% by weight, density 0.950? /ad.

A mixture consisting of 451% MFRo, 69/10 min polyethylene and 20% talc having a particle size of 1.5μ was kneaded in an extruder, extruded into strands, and cut into pellets.

(Adhesive resin on the side to be bonded to 11D urethane foam: ethylene impregnated 5-layer is %, MFRo, sr/1° min, crystal ratio of % propylene to boiling Heflin extraction residue 898 weight)
Ethylene block copolymer 90ffi4A% and ethylene/acrylic acid (20wt%) copolymer manufactured by Mitsubishi Yuka ■
A mixture of "s o ow" (trade name, MFR300y/lo min.) io weight, 1% was kneaded with an extruder, extruded into a strand shape, and cut into pellets.

The deep drawing layer side resin pellets (10) were supplied to a 3-layer multi-manifold die with a width of 700 m at 230°C using an extruder with a diameter of 90 m, and the resin for the glossy layer (i)
The iD adhesive resin compositions were each fed into the same die at 220° C. using a separate caliber 40 extruder. The die temperature was 220°C. The molten sheet extruded from the die is sequentially cooled and solidified using three rolls with a width of 700 mm.
Then, a corona discharge treatment was performed to obtain a vacuum-formed laminated, 1.1 sheet. The temperature of the rolls is 40°C starting from the roll closest to the die.
℃, 95℃, 50℃, and the rotation speed of the roll is 1
．． The speed was 5 m/min. The total sorting thickness is 1.6 m.
The glossy surface layer is 0.15%, and the deep drawing layer (intermediate layer)
The fi was 1.35 was, and the adhesive resin layer side with the urethane foam was 0.1 was.

Examples 2 to 9 A laminate 7-t 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 Nia'lopylene ethylene block copolymer E-AA: Ethylene/acrylic acid copolymer A300W
, Mitsubishi Yuka ■ ethylene/acrylic acid copolymer (acrylic acid content 20% by weight, MFR300y/10 minutes) A221M: Mitsubishi Yuka ■ ethylene/acrylic acid copolymer (acrylic acid content 8.5% by weight, MFR7F/10 minutes) PS: Polystyrene "Dialex HT516" manufactured by Mitsubishi Monsanto Kasei@ (Product name) sBs "Tuffrene A" manufactured by SBS Niasahi Kasei@ (Product name) Example 1 One or three layer laminate sheet in Example 1 above was introduced into a heating furnace set at approximately 230°C using a vacuum/pressure forming machine, and then heated with compressed air (
5,0 pharyngeal/layer) and reduced pressure (-600 pharyngeal Hg),
Plug assist molding was performed (diaphragm 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 notebook was inserted into a stainless steel frame that is a wooden frame of a refrigerator, and then the space formed by the frame and the shaped sheet ( Pour 2-component polyurethane foaming solution a-HM-1SLO from the injection port into the chamber.
When ``(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 0.05S.
'/cTd. The same operation was repeated <20 times, and the composite molded sample was 201ii! It's il shou.

After 24 hours, the sheet to which the urethane foam had been adhered 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.
After cutting into individual IW squares, adhesive tape was pasted onto the squares, and when the adhesive tape was vigorously peeled off from the notebook, the squares of urethane foam remaining on the sheet side were examined.

The results are shown in Table 1.

The evaluation criteria for adhesion are as follows.

◯: Nirarethane foam ui damaged 1 100 Adhesive portion on two sides of square ~Tτ Δ: Nirarethane foam cohesive failure and interfacial peeling between adhesive and urethane occur simultaneously.

Square size 2 - 100 stones - T surface ×: The adhesion between the urethane foam and the adhesive layer is weak, and the sheet is easily peeled off from the interface with the urethane 7 ohm.

Square Neal-R Stone Hyaku Examples 2 to 5, Comparative Examples 1 to 3 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 Row 7.

Table 1 shows the adhesion between the urethane foam and the sheet of the cholera composite molded product.

(Left below) Example 5 80% by weight of the propylene/ethylene block copolymer used in Example 1 and 500% of the ethylene/acrylic acid copolymer
A mixture of 20% by weight of W'' was used as the adhesive and homopolypropylene was used as the skin layer.
The mixture was melt-kneaded at 0° C., fed into one die, laminated in the die, extruded into a parison, and then blow-molded to obtain a surfboard side shell.

A two-component urethane solution was injected into the hollow part of this molded body and foamed to obtain a surfing 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 6 (1) Resin provided for gloss layer: MFR2, or/lo minute,
A crystalline propylene homopolymer with a residual amount of 99% by weight after extraction with boiling hebutane was used.

(ii)! Resin for the squeeze layer (intermediate layer): ethylene content 5% by weight, MFRo, 5 r/10 min, boiling hebutane extraction residue JJkg 8% by weight crystalline propylene-dethylene block copolymer 40% by weight A, density 0.950r/
i, MF RO, 6y/ A composition consisting of 40 weight percent of polyethylene of 1a and 10 weight percent of tal with a particle size of 1.5 μ was kneaded with an extruder, extruded into a strand, and cut into pellets.

G11) Adhesive resin: The same adhesive resin as in Example 1 was used (
PP90 supernatant, E-EA “500W” 10% by weight)
.

The resin pellet for the deep drawing layer of (ii) above has a diameter of 90+m.
Using an extruder with a diameter of 40 m, the resin for the glossy layer of (1) was fed to a three-layer multi-manifold die with a width of 700 mm at 230°C, and (iii)
) was fed into the same die at 220° C. using a separate extruder. The die temperature was 230°C. The molten sheet extruded from the die has three openings with a width of 700 mm.
The mixture was sequentially cooled and solidified in a vacuum molding chamber, and then subjected to corona discharge treatment to obtain a three-layer vacuum forming sheet. The roll temperature 1i is 40°C, 95°C, and 50°C from the roll closest to the die, and the roll rotation speed is 1. It was sm7 minutes. The sheet thickness is
Total 1.6 pus, gloss ffJtd O, 20rm
, the deep drawing test was in the 1.25 range, and the adhesive and d were in the 0.15 range.

This was vacuum formed in the same manner as in Example 1, and further mounted within the frame.
A composite molded article was obtained by urethane foam molding.

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 sheet. In the figure, 1 is a stainless steel frame, 2 is an A-layer sheet for differential pressure molding (lining material), 2a is a surface glossless layer, 2b is a deep drawing layer,
2c is an adhesive layer, 3 is a cavity, 4' is a urethane foam, and 5 is 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, Olefin resin 65-95 Weight % B) 35-5 weight % ethylene/acrylic acid copolymer with MFR of 30-400 g/10 min. 2) A composite molded body base according to claim 1, wherein the olefin resin molded body is a laminate having a surface layer of homopolypropylene and a base layer of the composition below. Material layer composition (a) Polypropylene 20-80% by weight (b) Polyethylene 10-80% by weight (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.