JPS60155443A - Expanded polyurethane laminate - 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 The present invention is suitable for complex-shaped heat insulating structures made by laminating α-olefin resin and foamed polyurethane via a specific modified resin, and rigidity-imparting bodies filled with foam. The present invention relates to a laminate.

Examples of resin products with complex shapes include refrigerator bodies, door lining materials, unit bath door materials, and automobile interior materials.

The lining material for refrigerators is made of acrylonitrile-butadiene-styrene copolymer (A
The sheet obtained by vacuum forming a sheet of BS) is used. Recently, attempts have also been made to use polypropylene lining materials with excellent surface gloss and low water absorption in place of ABS lining materials. These lining materials are
In order to improve the heat insulation properties, it is proposed to interpose foamed polyurethane between the structural base and the lining material.

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 on a polyvinyl chloride sheet lapois, and the frame is surrounded by the aluminum sash frame and the sheet. Consideration is being given to filling the space with foamed polyurethane to give it the ability to function as a door.

Furthermore, with the shift from metal to resin for automobile interior materials, filling polyurethane foam by injection method is being considered for the purpose of rigidity or heat insulation.

There is a demand for composites of resin materials and foamed polyurethane for resin products with various complex shapes, such as 1. However, resin materials are usually used as sheets or by thermoforming or injection molding to form molded products. When using a polyolefin resin with such a shape,
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 an adhesive or an adhesive liquid or to treat the surface. is not a good place to be.

The present invention (1) has strong lamination adhesion with a-olefin resin, (2) has good stretching processability during ripening, (3) has excellent lamination adhesion with foamed polyurethane, (4) It does not necessarily require surface treatment such as corona discharge treatment or fire treatment, and (5) It does not require adhesives or surface treatment agents. The inventors have discovered that these requirements can be met by using a modified resin in a laminated manner with an a-olefin resin.

That is, the present invention provides that "the layer of α-olefin resin and the layer of foamed polyurethane contain 0.1 to 20 hydroxyl group-containing monomers.
Melt flow rate (MFR) containing 0.1% by weight
"A foamed polyurethane laminate" characterized in that the polyurethane foam is bonded via a layer of an α-olefin modified resin having a content of 50 tlxo.

Since the laminate of the present invention is an excellent product that achieves the above object, it can be expected to find useful applications in a wide range of fields.

The α-olefin resin used in the present invention is preferably one that exhibits good stretching processability during thermoforming, such as low, medium or high density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-butene, etc. In addition to homopolymers and mutual copolymers of olefins such as polymers, ethylene-butene copolymers, propylene-butene copolymers, and propylene-hexene copolymers, these polyolefins can be used with styrene, vinyl esters, vinyl acetate, etc. Graft-modified resins are suitable.

Among these, propylene-based resins such as polypropylene and propylene-ethylene copolymer are preferred from the viewpoint of heat resistance against heat generation during injection foaming of urethane.

These resins can also be used in combination with other thermoplastic resins such as polystyrene, ABS, styrene-butadiene-styrene copolymer (SBS), polyacrylonitrile, high impact polystyrene (HIP83 etc., rubber,
For example, ethylene-propylene rubber, styrene-butadiene rubber, etc. Appropriate amounts of various stabilizers, pigments, and inorganic fillers such as talc and calcium carbonate can also be blended. In particular, 10 to 85 parts by weight of high-density polyethylene and 90 to 15 parts by weight of propylene resin are used in combination, and 100 parts by weight of this combination is further combined with 1 to 30 parts by weight of polystyrene and 1 to 20 parts by weight of 5BS.
Those used in combination with parts by weight have particularly excellent outward stretching processability.

Furthermore, the modified resin used in the present invention contains 0.1 to 20 parts by weight of a hydroxyl group-containing monomer and has an MFR of 0.1 to 50 t.
/ 10 minutes a-olefin modified resin. Preferably the monomer is present in an amount of 0.3 to 10% by weight, especially 0.3% to 10% by weight.
5 to 5 weight and has an MFR of 0.5 to 109/
10 minutes, especially 1 to S t/10 minutes. If the amount of the hydroxyl group-containing monomer is less than the lower limit, the adhesion to polyurethane foam will be insufficient, and if it exceeds the upper limit, the modified resin will lack mechanical strength and poor stretchability, which is not preferable. On the other hand, if the MFR is less than the lower limit, the load will be large during extrusion molding, and if it exceeds the upper limit, it will tend to sag during sheet molding, which is undesirable.

This modified resin is obtained by introducing a predetermined amount of a hydroxyl group-containing monomer into the above-mentioned a-olefin resin in the form of random, block or graft copolymerization. Graft copolymerization is preferred because the adhesion to foamed polyurethane is improved by introducing a small amount of the monomer and the physical properties of the resin used for modification are not significantly impaired.

Note that during graft copolymerization, the homopolymer of the hydroxyl group-containing monomer, which is competitively produced, does not contribute to adhesion with foamed polyurethane, so it is necessary to select conditions that allow copolymerization to occur efficiently.

Hydroxyl group-containing monomers are unsaturated organic compounds containing hydroxyl groups, such as esters of aliphatic polyhydric alcohols and unsaturated fatty acids and unsaturated alcohols, among them acrylic acid or methacrylic acid and aliphatic polyhydric alcohols. Esters with alcohols are convenient.

Preferred resins to be modified are propylene resins such as polypropylene and styrene-modified polypropylene in terms of heat resistance.

The modified resin is generally produced by a known method.

For example, graft copolymerization relies on a method in which an organic peroxide is added to a hydroxyl group-containing monomer and reacted in a solution state, melt state, or suspension state.

If the modified resin is a propylene-based resin, it is difficult to keep the MFR low because molecular chains are broken during modification, and the selection of the organic peroxide to be used is of utmost importance. , ketone peroxide, dialkyl peroxide, hydroperoxide, diacyl peroxide, peroxy ester, etc., and benzoyl peroxide is particularly preferred.

In addition, a modified resin into which the monomer has been introduced at a high concentration can be diluted with an unmodified resin. It is also possible to adjust the amount. moreover,
Stabilizers, inorganic fillers, pigments, rubbers, etc. can also be blended within the range that does not impede the effects of the invention.

Next, 1. The above a-olefin resin layer and modified resin layer are generally formed in advance by coextrusion, extrusion lamination of the modified resin onto an a-olefin resin sheet, or lamination by pressure bonding of both resin sheets or films. The layers are laminated by a known method such as a method.

The laminated sheet obtained by this pressing is molded in a matured form if necessary, and then a foamable urethane solution is introduced onto the surface of the modified resin layer, and then the foamable urethane solution is foamed and cured to form a resin laminated sheet. A laminate is formed in which the polyurethane foam is firmly bonded together.

Since the laminate of the present invention is characterized by being composed of the three layers described above, in cases where there are two or more layers of a-olefin resin, there may be an additional layer on the surface of the layer of a-olefin resin. It also includes those laminated with other resins, metal foils, etc.

Reference example 1 Polypropylene (VFRo
, 8 f/10 min, density 0.91 y/d) 5 odor,
After adding 90 tons of xylene and purging the system with nitrogen, the temperature was raised to 120° C. with stirring to dissolve polypropylene in xylene. Separately, benzoyl peroxide 400f
and 1 t of 2-hydroxypropyl methacrylate were dissolved in 10 t of xylene, and this was fed into the reactor above over 2 hours.

After the supply, the temperature was kept at 120° C. for 5 hours while stirring to complete the polymerization. After the reaction, the mixture was cooled to 60° C. and the product was precipitated with a large amount of acetone. After separating the product from F, it was thoroughly washed with acetone and dried in a vacuum drier to obtain 2-hydroxypropyl methacrylate-modified polypropylene. The content of 2-hydroxytalobil methacrylate in this product was determined by infrared spectroscopy and was found to be 1.
．． 4 weight.

After mixing 100 parts by weight of the obtained modified polypropylene, 0.1 part by weight of 2,6-di-t-butyl-p-cresol, and 0.05 part by weight of calcium stearate, 2 in extruder
It was extruded at 30°C, cooled with water, and then pelletized. The obtained pellets (MFH4, 2v/1° min) were compression molded at 210°C to form a 1 m sheet.

This sheet was placed in a 300 x 300 x 10 spacer, a two-component foaming urethane solution rHM-xsto (trade name) manufactured by Polyurethane Kagaku Kasei Co., Ltd. was injected, and part E was covered with a lid, and then left for 24 hours.

Thereafter, the modified polypropylene sheet adhered to the foamed polyurethane was taken out from the spacer and its adhesion to the foamed polyurethane was evaluated, and the entire surface of the foamed polyurethane base material was destroyed.

Reference Example 2 Polyethylene (MP'R20
9710 minutes, density 0.956 f/, J) 5 kg was dissolved in xylene 701 at 120° C. with stirring in a nitrogen atmosphere. Separately, benzoyl peroxide 500
t and 2-hydroxypropyl methacrylate) IKf was dissolved in 10 L of xylene, and this was supplied over 2 hours.

Further, the mixture was kept at 120°C for 5 hours while stirring to complete polymerization, and after cooling to 60°C, the product was precipitated with a large amount of acetone.

After separating the product from P, it was thoroughly washed with acetone and dried in a vacuum drier to obtain 2-hydroxypropyl methacrylate-modified polyethylene. The 2-hydroxypropyl methacrylate content of this product was 1.3% by weight.

50 parts by weight of the obtained modified polyethylene, polyethylene (
MFRl, 5 tlx o min, density 0.9529/, J
) 50 parts by weight and 0.1 parts by weight of 2,6-di-t-butyl-p-cresol were mixed in a Henschel mixer, and then
The mixture was extruded into pellets at 200°C using an extruder. The MFR of this pellet is 4.1t/l.

It's a minute.

Reference example 3 Polypropylene (PP) powder (MFRo, 8t/
l0 min, dense [o, c+ 1 f/cJ) 1 o o parts by weight, 2-hydroxypropyl methacrylate (I(P
MA) 4 parts by weight, benzoyl peroxide (BPO)
After mixing 3 parts by weight in a Henschel mixer, a diameter of 4 (
The mixture was extruded at 230° C. using an extruder of JWm, L/D28, cooled with water, and then pelletized. Using the obtained pellets, Reference Example 1
Adhesion to polyurethane foam was evaluated in the same manner as above.

The results are shown in Table 1.

Reference Examples 4 to 5 Modified polypropylene was obtained by pressing in the same manner as in Reference Example 3, except that the blending ratio of each component in Reference Example 3 was variously changed, and its adhesion to foamed polyurethane was evaluated. The results are shown in Table 1.

Reference example 6 Dicumyl peroxide (DCP) as peroxide
) 2 parts by weight was used and reference example 1 was used except that no antioxidant was used.
Modified polypropylene pellets were obtained in the same manner as above, and their adhesion to foamed polyurethane was evaluated. The results are shown in Table 1. Note that the modified polypropylene sheet obtained by compression molding was brittle.

Reference Examples 7 to 9 The modified polypropylene (modified PP) obtained in Reference Example 1 was diluted with unmodified polypropylene (PP) (Mitsubishi Noblen MH8 manufactured by Mitsubishi Yuka Co., Ltd.) at various ratios, and diluted in the same manner as in Reference Example 1. Adhesion to polyurethane foam was evaluated. The results are shown in Table 2.

(Left below) Table 1 Formula (parts by weight) MFR Reference example 3100 4 BPO30,94141# zl
4.8 3 15N IIO, 55, 12 *<Adhesion evaluation criteria for polyurethane foam and sheet> 1-
The foamed polyurethane on the entire surface and sheet interface peels off easily.

2-Most of the polyurethane foam can be peeled off at the sheet interface, but there is some resistance when peeling off.

3-Polyurethane foam peels off from the sheet interface in some areas.

4-The entire foamed polyurethane base material is destroyed.

Table 2 Composition (parts by weight) Reference Example 7 70 30 4 s 5o 50 4 9 30 70 3 Reference Example 10 The modified polypropylene obtained in Reference Example 3 was molded into a 2-sheet at 260°C using a 5-ounce injection molding machine. Molded. A two-component urethane paint (R263, manufactured by Nippon B Chemical Co., Ltd.) was applied to the obtained sheet using a spray gun, and baked in an oven at 90°C for 40 minutes to harden it to form a modified polypropylene sheet coated with a 30μ coating. Obtained. After leaving it for 1 day, make a 2sm wide slit in the paint film with a razor and apply 10011.
When I1 angle goblets were formed and cellophane tape was removed, all the goblets were peeled off.

Example 1 Filler-containing polypropylene (Mitsubishi Noprene E3542 manufactured by Mitsubishi Yuka Co., Ltd.) was prepared with a diameter of 90. 230 using an extruder
On the other hand, the modified polypropylene pelletized in Reference Example 1 was heated to a width of 700 m at 230°C using an extruder with a diameter of 40 m.
The temperature of the die supplied to the two-layer multi-manifold die was 230 to 240°C. The molten sheet extruded from the die was sequentially cooled and solidified using three rolls each having a width of 700 m. The temperature of the rolls is 80℃ starting from the roll closest to the die.
110℃, 100℃, and the rotational speed of the roll d
It was 1.5 m and 7 minutes. The total thickness of the sheet is 1
．． It was 0+a+, and the modified polypropylene layer had a weight of 0.1. When the adhesion between the obtained sheet and foamed polyurethane was evaluated in the same manner as in Reference Example 1, the entire surface of the foamed polyurethane base material was destroyed, which was sufficient for practical use.

Example 2 High-density polyethylene (Yukalon Hard EX manufactured by Mitsubishi Yuka Co., Ltd.
40') at 240°C using an extruder with a diameter of 90mm.
On the other hand, the modified polyethylene composition pelletized in Reference Example 2 was processed using an extruder with a diameter of 40. Boiled width 70 (1
m+ two-layer multi-manifold die. The die temperature was 230-250°C. The molten sheet extruded from the die was sequentially cooled and solidified using three rolls each having a width of 700+wm.

The total thickness of the sheet was 1.0-m, and the modified polyethylene layer was 0.1 m. The adhesion between the obtained sheet and the foamed polyurethane was evaluated using the same buttons as in Reference Example 1, and the entire surface of the foamed polyurethane base material was destroyed (2), which was sufficient for practical use.

Patent applicant Mitsubishi Yuka Co., Ltd. Agent: Patent Attorney Hidetoshi Furukawa Agent: Patent Attorney Masahisa Nagatani

Claims (1)

[Claims] The layer of α-olefin resin and the layer of foamed polyurethane contain a layer of α-olefin modified resin containing 0.1 to 20% by weight of a hydroxyl group-containing monomer and having a melt flow rate of 0.1 to sop/1o. A foamed polyurethane laminate characterized in that it is bonded through a polyurethane foam.