JPH06344520A - Laminate - Google Patents

Abstract

PURPOSE:To provide a laminate wherein a polyolefinic resin layer and an acrylic resin layer are strongly bonded. CONSTITUTION:In a laminate wherein a polyolefinic resin layer and an acrylic resin layer are laminated through an adhesive layer, the adhesive layer is composed of at least one rubbery resin selected from a group consisting of a styrene/ethylene.diene/styrene block copolymer (a) obtained by the addition polymerization of an unsaturated carboxylic acid derivative or an alkoxysilane derivative, a polyolefinic elastomer (b) obtained by the addition polymerization of an unsaturated carboxylic acid derivative or an alkoxysilane derivative, a mixture (c) of a chlorinated polyolefinic resin and a polyolefinic elastomer and a chlorinated polyolefinic elastomer (d).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate in which a polyolefin resin layer and an acrylic resin layer are laminated via a strong adhesive layer. INDUSTRIAL APPLICABILITY The laminate of the present invention takes advantage of the advantages of polyolefin resin and acrylic resin, and is used for various outdoor applications such as rain gutters, window frames, corrugated boards, deck boards, automobile molding materials, bumpers, etc. To be done.

[0002]

2. Description of the Related Art Polyolefin resins have a wide range of uses because of their excellent molding processability, mechanical properties, chemical resistance, ozone resistance, heat resistance, water resistance and the like. But,
Molded products of polyolefin resin have drawbacks such as loss of gloss and easy scratches on the surface, poor colorability, and poor weather resistance.

On the other hand, acrylic resins have established their own fields of application due to their excellent transparency, decorativeness, surface hardness, weather resistance and oil resistance. However, this resin
It was inferior in impact resistance, moisture resistance and organic solvent resistance.

Therefore, it is expected that an extremely excellent material can be obtained by laminating the polyolefin resin layer and the acrylic resin layer. However, when these two resin layers are laminated, the adhesiveness between the two is remarkably poor, and no adhesive has been found that firmly adheres the two.

In order to solve such a problem, a layer of the general formula (AB) n (where A is substantially a monovinyl-substituted aromatic fragrance) is used as a layer for adhering the laminated polyolefin resin layer and the acrylic resin layer. A polymer block composed of a group compound,
B means a polymer block consisting essentially of a conjugated diolefin) and the like have been proposed (JP-B-60-4202).
No. 9).

[0006]

However, even with the above method, sufficient adhesion between the polyolefin resin layer and the acrylic resin layer cannot be obtained.

In view of the above points, an object of the present invention is to provide a laminate in which a polyolefin resin layer and an acrylic resin layer are firmly adhered to each other.

[0008]

The laminate according to the present invention comprises:
It is devised to achieve the above-mentioned object, and in a laminated body in which a polyolefin resin layer and an acrylic resin layer are laminated via an adhesive layer, by using a specific one as the adhesive layer, It was completed with the knowledge that a layered product in which the layers are firmly bonded can be obtained.

That is, the laminate according to the present invention is a laminate obtained by laminating a polyolefin resin layer and an acrylic resin layer via an adhesive layer, wherein the adhesive layer comprises (a) an unsaturated carboxylic acid derivative or A styrene-ethylene / diene-styrene block copolymer obtained by addition-polymerizing an alkoxysilane derivative, (b) a polyolefin elastomer obtained by addition-polymerizing an unsaturated carboxylic acid derivative or an alkoxysilane derivative, (c) a chlorinated polyolefin Mixture of resin and polyolefin elastomer, and
(d) At least one rubber-like resin selected from the group consisting of chlorinated polyolefin elastomers.

The styrene / ethylene / diene / styrene block copolymer is a block copolymer of styrene and an ethylene / diene copolymer, and the diene component is, for example, 1,3-butadiene, Examples include isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene and the like. These may be hydrogenated at the time of copolymerization, or the double bond may remain.

When the amount of the ethylene / diene component is too small, the obtained rubber-like resin layer becomes too hard, and when it is too large, the strength becomes low. In either case, the adhesive strength of the finally obtained laminate is low, which is preferable. Absent. The preferred amount of the ethylene / diene component is 30 to 90% by weight based on the total components of the block copolymer.

When the rubber-like resin layer is formed by, for example, extrusion molding, the above-mentioned styrene-ethylene-diene-
If the weight average molecular weight of the styrene block copolymer is small, resin leakage from a mold or the like tends to occur, and if the weight average molecular weight is large, moldability is deteriorated, so 40,000 to 150,000.
Is preferred.

Such styrene-ethylene diene-
Examples of the styrene-based block copolymer include those manufactured by Asahi Kasei, trade name: H1041 (styrene-ethylene / butadiene-styrene-based block copolymer), manufactured by Kuraray Co., Ltd.,
Trade name: Septon 2043 (styrene-ethylene / isoprene-styrene block copolymer) and the like.

The above-mentioned polyolefin elastomer is an α-olefin resin having rubber-like elasticity at around room temperature, such as ethylene-propylene rubber and ethylene-1.
-Butene rubber, propylene-1-1 butene rubber, ethylene-propylene-diene rubber, polyisobutylene and the like. Examples of the above ethylene-propylene rubber include P-0280 manufactured by Mitsui Petrochemical Co., Ltd., and Thermoran 2940 manufactured by Mitsubishi Petrochemical Co., Ltd.

In the present invention, the unsaturated carboxylic acid derivative addition-polymerized to the styrene-ethylene / diene-styrene block copolymer or the polyolefin-based elastomer means an ethylenically unsaturated bond or an acetylenic unsaturated bond in the hydrocarbon group. A carboxylic acid having a saturated bond and its derivatives. Examples of the unsaturated carboxylic acid include (meth) acrylic acid, maleic acid, fumaric acid and itaconic acid, and examples of the unsaturated carboxylic acid derivative include unsaturated carboxylic acid anhydrides such as maleic acid anhydride and (meth ) Methyl acrylate, unsaturated carboxylic acid esters such as ethyl (meth) acrylate, unsaturated carboxylic acid amides such as (meth) acrylic acid amide, maleic acid amide and maleamide,
Examples thereof include unsaturated carboxylic acid imides such as maleimide and N-butylmaleimide, and unsaturated carboxylic acid salts such as sodium (meth) acrylate. These may be used alone or in combination of two or more.

The amount of addition polymerization of the above-mentioned unsaturated carboxylic acid derivative decreases the adhesive strength of the finally obtained laminate even if it is small or large. Therefore, a styrene-ethylene / diene-styrene block copolymer or The amount is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyolefin elastomer.

The alkoxysilane derivative which is addition-polymerized to the styrene-ethylene / diene-styrene block copolymer or the polyolefin elastomer is a silane compound having an alkoxy group at least at one end, such as vinylmethoxysilane and vinyl. Alkoxyvinylsilanes such as ethoxysilane, vinyldimethoxysilane, vinyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, methylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane,
Ethyltrimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, methyltris (β-methoxyethoxy) silane, methyltris (β
-Hydroxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane , Γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, methyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, tri Chill silane, diethyl dimethoxy silane, triethyl silane,
Diethyldiethoxysilane, tripropylmethoxysilane, dipropylmethoxysilane, dipropyldimethoxysilane, tripropylethoxysilane, dipropyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, hexyltrimethoxysilane, methylhexyldimethoxysilane, hexyl Triethoxysilane, methylhexyldiethoxysilane, undecyltrimethoxysilane, undecyltriethoxysilane, methylundecyldiethoxysilane, octadecyltrimethoxysilane, methyloctadecyldimethoxysilane, octadecyltriethoxysilane, methyloctadecyldimethoxysilane, methyl Octadecyldiethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane Examples thereof include orchid, and alkoxyvinylsilane is particularly preferable. These may be used alone or in combination of two or more.

If the amount of the above-mentioned alkoxysilane derivative is small or large, the adhesive strength of the finally obtained laminate will be low. Therefore, the styrene-ethylene / diene-styrene block copolymer or the polyolefin elastomer 1
It is preferably 0.1 to 20 parts by weight with respect to 00 parts by weight.

The method for addition-polymerizing the above unsaturated carboxylic acid derivative or alkoxysilane derivative is not particularly limited,
Any conventionally known method can be used, for example, a monomer of an unsaturated carboxylic acid derivative or an alkoxysilane derivative and a styrene-ethylene / diene-styrene block copolymer are supplied to an extruder and kneaded while being heated and melted. Examples thereof include a reaction method, a method in which a styrene-ethylene / diene-styrene block copolymer or a polyolefin elastomer is dissolved in a solvent such as toluene or xylene, and the above monomer is added to this solution to react.

In the addition polymerization reaction, a radical initiator such as hydroperoxide, ketone peroxide or dialkyl peroxide may be added, if necessary. If the amount of the radical initiator increases, the styrene-ethylene / diene-styrene block copolymer or the polyolefin elastomer is decomposed.
The amount is preferably 2 parts by weight or less with respect to 100 parts by weight of the ethylene / diene-styrene block copolymer or the polyolefin elastomer.

The chlorinated polyolefin resin is obtained by post-chlorinating polyolefin such as polyethylene and polypropylene. If the degree of chlorination of the chlorinated polyolefin is low, the adhesive strength with the acrylic resin is low, and if it is high, the adhesive strength with the polyolefin resin is low.
It is preferably 20 to 40% by weight. When the amount of chlorinated polyolefin added is small, the adhesive strength with the acrylic resin is low, and when it is large, the adhesive strength with the polyolefin resin is low. Therefore, the addition amount is preferably 40 to 200 parts by weight with respect to 100 parts by weight of the polyolefin elastomer. is there.

The above-mentioned chlorinated polyolefin elastomer is obtained by post-chlorinating the above polyolefin elastomer. If the degree of salt chlorination of the polyolefin-based elastomer becomes low, the adhesive strength with the acrylic resin will decrease,
When it is higher, the adhesive strength with the polyolefin resin is lowered, so that it is preferably 20 to 40% by weight.

As the post-chlorination method, a conventionally known method can be used. For example, a polyolefin-based elastomer is dissolved in a chlorine-based organic solvent such as carbon tetrachloride, chloroform, trichloroethylene or the like to prepare a suspension, and an inert gas such as nitrogen is used. After the gas replacement, a method of introducing chlorine gas while irradiating with ultraviolet rays, a usual aqueous suspension chlorination method of introducing chlorine gas in an aqueous suspension state, and the like can be used.

If necessary, a reinforcing material such as glass fiber, an inorganic filler such as calcium carbonate or talc, an ultraviolet absorber, an antioxidant, a pigment or the like may be appropriately added to the rubber-like resin. These may be used alone or in combination of two or more. The polyolefin resin constituting one layer of the laminate according to the present invention is a homopolymer of α-olefin, and a copolymer of α-olefin and a monomer having an unsaturated group copolymerizable therewith, For example, polyethylene, polypropylene, polybutene, polyisoprene, polypentene, polymethylpentene, chlorinated polyethylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-1-butene copolymer, 4-ethylene- Examples thereof include a 2-methylpentene copolymer, an ethylene-butadiene copolymer, an ethylene-ethyl acrylate copolymer, and an eletin-vinyl acetate copolymer.

Further, the polyolefin resin includes a cyclic olefin resin and a crosslinkable olefin resin.

The cyclic olefin resin is a resin excellent in rigidity, heat resistance and the like, specifically, a random copolymer of ethylene and cyclic olefin (ethylene content 40 to 90 mol%).
In order to improve impact resistance, ethylene-α
-A modified copolymer obtained by graft-polymerizing an olefin copolymer (ethylene content 30-95 mol%) with a polycyclic (meth) acrylate monomer, or an ethylene-α-olefin copolymer (ethylene content 30-95). (Mol%) can also be added (JP-A-3-95243).

The crosslinkable olefin resin is a resin having excellent heat resistance, specifically, a crosslinked product of a polyolefin resin such as polyethylene or polypropylene. Examples of the crosslinking method include an electron beam irradiation method and a chemical crosslinking method. As the chemical cross-linking method, a conventionally known method can be used, for example, after introducing a silanol group into a polyolefin-based resin and molding (introducing the silane compound, and optionally adding the peroxide), water (hot water, steam) , A humidity in the atmosphere) to crosslink, or a crosslinking agent for a polyolefin resin, specifically a compound having two or more amino groups in one molecule,
For example, aliphatic diamines such as hexamethylenediamine, 1,8-diaminooctane, and 1,10-diaminodecane, and aromatic diamines such as o-, m-, p-phenylenediamine, and 4,4'-diaminophenyl ether are used. Add
There is a method in which a resin is melt-kneaded and cross-linked.

These polyolefin resins may be used alone or in combination of two or more kinds.

The above polyolefin resin is appropriately selected depending on the molding method. For example, when the polyolefin resin layer is formed by extrusion molding, JIS K 72
When the melt flow rate at 230 ° C. of 10 is low, moldability is poor, and when the melt flow rate is high, resin leakage from a mold or the like is likely to occur, so this value is 0.5 to 5 g / 10.
It is preferable to use a resin in the range of minutes.

If necessary, a reinforcing material such as glass fiber, an inorganic filler such as calcium carbonate or talc, an ultraviolet absorber, an antioxidant, a pigment and the like may be appropriately added to the above polyolefin resin. These may be used alone or in combination of two or more.

The acrylic resin constituting the other layer of the laminate according to the present invention means a polymer of acrylic acid and its derivative, such as acrylic acid and its ester, acrylamide, acrylonitrile, methacrylic acid and its ester. Examples thereof include polymers and copolymers. The acrylic resin is appropriately selected depending on the molding method. For example, when the acrylic resin layer is formed by extrusion molding, if the melt flow rate at 230 ° C. according to JIS K 7210 becomes low, the moldability becomes poor,
If it becomes higher, resin leakage from the mold or the like is likely to occur, so it is preferable to use a resin having this value in the range of 0.5 to 5 g / 10 minutes.

If necessary, a reinforcing material such as glass fiber, an inorganic filler such as calcium carbonate or talc, an ultraviolet absorber, an antioxidant, a pigment or the like may be appropriately added to the acrylic resin. These may be used alone or 2
More than one type may be used.

The method for laminating the laminate of the present invention is not particularly limited, and any conventionally known method can be used. For example, melted polyolefin resin, rubber-like resin, and acrylic resin are melt-kneaded by separate extruders, and 200-250 in this order.
The layers may be formed by pouring the mixture into a mold at a temperature of ℃ to laminate the layers, cooling and solidifying. The melt-kneading temperature is 140 to 230 ° C. for polyolefin resin, and (a) styrene-ethylene which is obtained by addition-polymerizing an unsaturated carboxylic acid derivative or an alkoxysilane derivative as a rubber-like resin.
When a diene-styrene block copolymer is used, the temperature is 180 to 220 ° C., and a rubber-like resin (b) an unsaturated carboxylic acid derivative or an alkoxysilane derivative is subjected to addition polymerization to obtain a polyolefin elastomer, and (c) a chlorinated polyolefin. When a mixture of a resin and a polyolefin-based elastomer, and (d) a chlorinated polyolefin-based elastomer are used, the temperature is preferably 160 to 230 ° C, and the acrylic resin is preferably 180 to 260 ° C.

A solution prepared by dissolving a rubber-like resin in a solvent such as toluene or xylene is applied to one of the polyolefin resin layer or the acrylic resin layer, and the other resin layer is laminated on the applied surface. You may dry it.

The thickness of each resin layer of the present invention is not particularly limited and may be appropriately set according to the melting performance of the product, but if the layer made of rubber-like resin is thin, adhesion of the obtained laminate is achieved. Since the strength is low, the thickness is preferably 30 μm or more, and when the acrylic resin layer is thin, sufficient weather resistance cannot be obtained, so the thickness is preferably 50 μm or more.

[0036]

EXAMPLES The details of the present invention will be described below with reference to examples.

Example 1 A predetermined amount (part by weight) of a styrene-ethylene / butadiene-styrene block copolymer shown in Table 1 (trade name: H1041, manufactured by Asahi Kasei Corporation, ethylene / butadiene content 70% by weight, molecular weight 50000, (Hereinafter abbreviated as SEBS),
Maleic anhydride and hydroperoxide (manufactured by NOF CORPORATION, trade name; Park Mill H) are supplied to the hopper of a twin-screw extruder and melt-kneaded at 190 ° C to extrude the kneaded product.
SEBS obtained by addition polymerization of maleic acid (hereinafter referred to as MSEBS
Abbreviated).

Then, from three extruders, polypropylene resin (manufactured by Mitsubishi Yuka Co., Ltd., trade name; EC-8, ethylene-
Propylene block copolymer, melt flow rate at 230 ° C. 1.5 g / 10 min) at 200 ° C.
SEBS at 210 ° C, polymethylmethacrylate resin (manufactured by Sumika Hearth Co., Ltd., trade name; HFI-10, 230 ° C)
Melt flow rate at 4 g / 10 min) at 210 ° C
Then, in this order, extruded into a mold at a mold temperature of 230 ° C., a polypropylene resin layer having a thickness of 1.3 mm, an adhesive layer made of a rubber-like resin having a thickness of 50 μm, and a polymethylmethacrylate resin layer having a thickness of 100 μm A laminated body was obtained.

Example 2 Instead of SEBS, styrene-ethylene / isoprene-styrene block copolymer (Kuraray Co., trade name; Septon 2043, ethylene / isoprene content 87% by weight, molecular weight 50000, hereinafter abbreviated as SEPS). ) Was used to obtain a rubber-like resin pellet made of SEPS in which maleic acid was addition-polymerized, to obtain a laminate in the same manner as in Example 1.

Comparative Examples 1 and 2 SEBS (Comparative Example 1) or SE instead of MSEBS
A laminate was obtained in the same manner as in Example 1 except that PS (Comparative Example 2) was used.

Examples 3 to 4 Polypropylene resin (trade name; EC-manufactured by Mitsubishi Yuka)
A laminate was obtained in the same manner as in Example 1 and Example 2 except that a cyclic olefin (trade name; manufactured by Mitsui Petrochemical Co., Ltd .; Abel 130R, melt flow rate at 260 ° C., 5 g / 10 minutes) was used instead of 8). It was

Examples 5 to 6 Polypropylene resin (trade name; EC-manufactured by Mitsubishi Yuka)
In the same manner as in Example 1 and Example 2 except that a crosslinkable olefin (trade name; manufactured by Mitsubishi Yuka Co., Ltd .; Rinklon XPM-800H, melt flow rate at 230 ° C., 11 g / 10 minutes) was used instead of 8). A laminated body was obtained.

Performance Test For each laminate obtained in Examples and Comparative Examples, the polypropylene-based resin layer and the polymethylmethacrylate-based resin layer were gripped at the ends of the laminate to separate the laminate, and the test was conducted by autograph. Temperature 23 ℃, tensile speed 5mm / m
A 180 ° peel test was performed in. The peel strength thus obtained was taken as the adhesive strength of the laminate.

The heat distortion temperature was measured by the method according to JIS K 7207, and this was taken as the heat resistance of the laminate.

The results of these tests are summarized in Table 1.

[0046]

[Table 1]

[0047]

In the present invention, since the above-mentioned specific rubber-like resin is used as the resin for the adhesive layer, it is possible to provide a laminate in which the polyolefin resin layer and the acrylic resin layer are firmly adhered. Therefore, the laminate of the present invention takes advantage of each of the advantages of the polyolefin resin and the acrylic resin, molding processability, mechanical properties, chemical resistance, ozone resistance,
Not only excellent in heat resistance and water resistance, but also excellent in decorativeness, surface hardness, weather resistance, oil resistance, etc., so it is a rain gutter, window frame, corrugated board, deck board, automobile molding. It can be used for various outdoor applications such as wood and bumpers.

Claims (1)

[Claims] 1. A laminate comprising a polyolefin resin layer and an acrylic resin layer laminated via an adhesive layer, wherein the adhesive layer has (a) an unsaturated carboxylic acid derivative or an alkoxysilane derivative added thereto. A styrene-ethylene / diene-styrene block copolymer obtained by: (b) a polyolefin elastomer obtained by addition polymerization of an unsaturated carboxylic acid derivative or an alkoxysilane derivative; (c)
A laminate comprising a mixture of a chlorinated polyolefin-based resin and a polyolefin-based elastomer, and (d) at least one rubber-like resin selected from the group consisting of chlorinated polyolefin-based elastomers.