JPH0251387B2 - - Google Patents

Description

Detailed Description of the Invention The present invention combines the advantages of thermoplastic elastomers such as elasticity, extrudability and heat resistance, and the advantages of ionomers or 1-olefin/(meth)acrylic acid copolymer resins such as surface gloss and scratch resistance. The object of the present invention is to provide a material that has both the following and does not have the former disadvantage of matteness and the latter disadvantage of lack of heat resistance. Thermoplastic elastomers, which have traditionally been used as sealing materials, cushioning materials, or interior and exterior materials for vehicles, ships, etc., as well as home appliance parts, sporting goods, building materials, etc., have poor surface gloss and scratch resistance, so these are the focus of attention. Protective moldings, windshield gaskets, etc. for automobiles, which are used in the field of
It was rarely used as a bumper or other material. The present inventors have found that not only can the above-mentioned drawbacks of thermoplastic elastomers be substantially eliminated by laminating them with partial ionomers or 1-olefin/(meth)acrylic acid copolymer resins, but also the drawbacks of ionomers etc. The present invention has been completed based on the discovery that it can be removed. That is, the present invention has the following technology as its content. (1) A thermoplastic elastomer layer consisting of a polyolefin and an ethylene/α-olefin copolymer elastomer, at least one of which is partially crosslinked, and a partial ionomer resin layer containing free carboxyl groups or a 1-olefin・
A laminate with good surface gloss and scratch resistance, which is formed by strongly adhering a methacrylic acid copolymer resin layer. (2) A thermoplastic elastomer consisting of a polyolefin and an ethylene/α-olefin copolymer elastomer, at least one of which is partially crosslinked, and a partial ionomer resin layer or 1-olefin copolymer containing a free carboxyl group. A method for manufacturing a laminate in which a methacrylic acid copolymer resin is firmly adhered to the fused resin in a molten state. In addition, (meth)acrylic acid in the present invention is
It is a general term for acrylic acid and methacrylic acid. In the present invention, polyolefin and ethylene
Examples of the thermoplastic elastomer comprising a partially crosslinked α-olefin copolymer elastomer include the following compositions. () Various polyolefin resins (α ₁ ) represented by homopolymers of ethylene or propylene or copolymers of these with small amounts of other monomers
and a bipolymer elastomer of ethylene and an α-olefin copolymer having 3 to 14 carbon atoms, or a partially crosslinked product of a terpolymer rubber (b ₂ ) obtained by polymerizing these with various non-conjugated polyene compounds. (c ₂ ) Thermoplastic elastomer composition () consisting of polyolefin resin (a ₁ ) and ethylene α
- Thermoplastic elastomer composition () obtained by dynamically heat-treating a composition with olefin copolymer elastomer (b ₁ ) Polyolefin resin (a ₁ ) and ethylene α
- The same or different polyolefin resin (a ₁ ) or (a ₂ ) is added to the partially crosslinked product (c ₂ ) obtained by dynamically heat-treating the composition with the olefin copolymer elastomer (b ₁ ). A thermoplastic elastomer composition obtained by blending a peroxide crosslinked polyolefin resin (a 1 ) represented by a homopolymer of ethylene or a copolymer of ethylene with a small amount of other monomer (a ₁ ) and a monopolymer of propylene. A composition of a peroxide non-crosslinked polyolefin resin (a ₁ ) represented by a polymer or a copolymer of propylene and a small amount of other monomers and an ethylene/α-olefin copolymer rubber (b ₁ ) In the present invention, the ethylene/α-olefin copolymer rubber that is the raw material for the thermoplastic elastomer refers to, for example, ethylene-propylene copolymer rubber, ethylene-propylene-conjugated diene multi-component rubber,
Ethylene-butadiene copolymer rubber, ethylene-1
-butene copolymer rubber, ethylene-1-butene-nonconjugated diene multipolymer rubber, and other substantially amorphous elastomers containing 1-olefin as a main component, or mixtures thereof. Among these, preferred are ethylene-propylene copolymer rubber and ethylene-propylene-nonconjugated diene multipolymer rubber. Here, non-conjugated dienes include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, 2-ethylidene-5
-Norbornene, etc. Among them, a copolymer containing dicyclopentadiene and 2-ethylidene-5-norbornene as the third component is preferred. The Mooney viscosity [ML ₁₊₄ (100℃)] of these binary or polypolymers is usually 10 to 120, preferably 40.
~80, and its iodine value (degree of unsaturation) is preferably 16 or less. The amount of each structural unit contained in these elastomers is such that in the 1-olefin portion, the ratio of ethylene units/α-olefin units is 50/50 to 90/10, preferably 70/30 to 85/15 (molar ratio). and
1-olefin (ethylene + α-olefin) units/non-conjugated diene units) in the case of a multicomponent polymer) is usually 98/2 to 90/10, preferably 97/3 to 94/6
(molar ratio). In the partially crosslinked thermoplastic elastomer constituting the base layer of the laminate of the present invention, the blending ratio of the polyolefin and the ethylene/α-olefin copolymer elastomer constituting the partially crosslinked product is usually based on the polyolefin/elastomer. hand,
The ratio is selected from 80/20 to 20/80, preferably from 70/30 to 30/70 (weight ratio). The above partially crosslinked product is prepared by blending organic peroxide in an amount of usually 0.1 to 2 parts by weight with respect to 100 parts by weight of the raw material elastomer, and dynamically heat-treating the mixture. Here, dynamic heat treatment means kneading in a molten state. As the kneading device, a mixing roll, a Banbury mixer, an extruder, a kneader, a continuous mixer, etc. can be used. Usually 150-280
℃ for 1 to 20 minutes. Organic peroxides used for partial crosslinking include dicumyl peroxide, di-tert-
Brutyl peroxide, 2,5-dimethyl-2;
5-bis(tert-butylperoxy)hexane,
2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane-3,1,3-bis(tert
-butylperoxyisopropyl)benzene,
1,1-bis(tert-butylperoxy)-3,
Examples include 3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, dibenzoyl peroxide, and tert-butylperoxybenzoate, among others, scorch stability due to low odor. Bisperoxide compounds are preferred because of their high properties,
1,3-bis(tert-butyloxyisopropyl)benzene is most suitable. During this partial crosslinking treatment, p, which is a crosslinking aid,
- Partially crosslinked products that achieve uniform crosslinking by using polyfunctional compounds such as quinone dioxime, p-p'-dibenzoylquinone dioxime, divinylbenzene (DVB), ethylene glycol dimethacrylate, etc. is more suitable as a raw material for the laminate of the present invention. When preparing thermoplastic elastomers, other organic peroxide non-crosslinked rubbers, such as polyisobutene and butyl rubber (isobutene-isoprene copolymers), mineral oil softeners, carbon black, talc, clay, antioxidants, and other additives may be added. Ingredients can be blended. In the present invention, polyolefin refers to a homopolymer of 1-olefin, a copolymer of two or more thereof, a copolymer of 1-olefin and a conjugated or non-conjugated diolefin, and a copolymer of 1-olefin and another polymerizable vinyl monomer. Copolymers with and modified polyolefins obtained by grafting one or more polymerizable vinyl monomers onto the above polyolefins, etc., which have a crystallinity of usually 50% or more as determined by X-ray diffraction measurement, a melt viscosity index [MI ( (190°C) or MFR (230°C)] usually about 0.1 to 50 g/10 min, preferably a peroxide decomposition type. For example, isotactic polypropylene, copolymers of propylene and up to 15 mol% of other α-olefins, such as propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-1-hexane copolymers. , propylene-4-methyl-1-pentene copolymer or blends thereof. The MFR (230°C) of these is preferably 5 to 20. The partial ionomer resin or 1-olefin/(meth)acrylic acid copolymer resin used in the present invention should have carboxyl groups present in the copolymer from the viewpoint of bondability with the thermoplastic elastomer and scratch resistance. The content is usually 4 to 15 mol%, preferably 6 to 10 mol%, and usually 60% or less, preferably 40% or less of the groups are alkali metal and/or alkaline earth metal ions, preferably calcium ions. Or, those bonded to zinc ions can be mentioned. In the present invention, the following methods can be exemplified as methods for laminating and molding a thermoplastic elastomer and a partial ionomer resin or a 1-olefin copolymer/(meth)acrylic acid copolymer resin. (a) Method of simultaneous multilayer extrusion of partial ionomer resin or 1-olefin/(meth)acrylic acid copolymer resin and thermoplastic elastomer (b) Partial ionomer resin or 1-olefin/(meth)acrylic acid copolymerization Method for multilayer injection molding of resin and thermoplastic elastomer (c) Ionomer resin or 1-
A method of inserting an olefin/(meth)acrylic acid copolymer resin molding and injecting and laminating a thermoplastic elastomer on its surface.
- Method of injection lamination of olefin copolymer/(meth)acrylic acid resin Among these, method (a) is usually used. Reference example 1 (i) Ethylene-propylene-2-ethylidene-5
-Norbornene terpolymer elastomer [ethylene content 78 mol%, iodine value 15, Mooney viscosity
ML ₁₊₄ (100℃) 70〕75 parts, (ii) Crystalline polypropyne [MFR (230℃, 2.16Kg)
11, Density 0.91/cc, Yield stress 370Kg/cm ²
(ASTM-D-638) 15 parts (iii) Isobutene-isoprene copolymer elastomer [unsaturation degree 0.8 mol%, Mooney viscosity ML ₁₊₄ (100
°C) 45] 10 parts, (iv) Antioxidant: Tetrakis [methylene (3,5
-di-tert-butyl-4-droxyphenyl)
Propionate] methane 0.3 parts. The above (i) to (iv) were charged into a Banbury mixer, kneaded for 5 minutes at 180°C in a nitrogen atmosphere, passed through a roll to form a seal, and then cut into pellets using a sheet cutter. Next, a solution prepared by dissolving and dispersing 0.3 parts of 1,3-bis(tert-butylperoxy-iso-propyl)benzene in 0.5 parts of divinylbenzene is added to the pellets, and mixed using a Henschel mixer.
The solution was applied uniformly to the pellet surface. The pellets were then extruded using an extruder in a nitrogen atmosphere at 210°C for a residence time of 5 minutes, and the resulting extrudate was dynamically heat treated to obtain a thermoplastic elastomer. Reference example 2 (i) Ethylene-propylene-dicyclopentadiene terpolymer elastomer [ethylene unit content
79mol%, iodine value 10, Mooney viscosity ML ₁₊₄
(100°C) 70〕70 parts, (ii) 30 parts of the same polypropylene used in Reference Example 1
(iii) 0.3 parts of the same antioxidant used in Reference Example 1. The above steps (i) to (iii) were operated in the same manner as in Reference Example 1 to perform pelletization and partial crosslinking to obtain a desired thermoplastic elastomer. Reference example 3 (i) Elastomer 65 used in reference example 1
(ii) Polypropylene used in Reference Example 1
20 parts, (iii) Propylene-ethylene random copolymer [propylene unit content 55 mol%, MFR (230→)
0.5g/10min] 15 parts, (iv) 0.3 of the antioxidant used in Reference Example 1
Department. The above steps (i) to (iv) were operated in the same manner as in Reference Example 1 to perform pelletization and partial crosslinking to obtain a desired thermoplastic elastomer. The surface gloss, scratch resistance (surface strength), and interlayer adhesion of the laminate were evaluated as follows. Surface gloss: Gloss measured at a light incidence angle of 60° in accordance with JISZ-8741 (hereinafter sometimes referred to as "60° gloss") Scratch resistance: Using a scratch tester specified in JISK-5401 , pencil hardness HB, load
Scratch the surface of the molded product under 500g conditions and evaluate the marks using the following criteria. 5: No scratches observed at all 4: Slight scratches left 3: Scratches left but not scratches 2 : Shallow scratches remain 1: Deep scratches remain Interlayer adhesion: A test piece (width 20 mm x length 120 mm) is cut out from the molded product, and both layers are subjected to T-peeling at a peeling speed of 50 mm/min. Example 1 Partial ionomer resin [MI (190°C) 5g/
10mm, carboxyl group content 8mol%, neutralization degree 19%,
Zinc salt type] was melted in an extruder at 200°C in a nitrogen atmosphere, and the thermoplastic elastomer obtained in Reference Example 1 was melted in another extruder in a nitrogen atmosphere.
They were melted at 230°C and both were extruded into the same mold to perform simultaneous two-layer molding. Table 1 shows the evaluation results of the obtained two-layer laminate. From the same table, it can be seen that the surface gloss and scratch resistance of the partial ionomer layer of the product of the present invention are equivalent to those of the normal ionomer (Comparative Example 2), and the interlayer adhesion strength of the product of the present invention is comparable. It can be seen that it far exceeds that of Example 2 and is substantially equivalent when compared with the thermoplastic elastomer (Comparative Example 1). In other words, since both layers in Comparative Example 1 are made of the same thermoplastic elastomer, the interlayer adhesion force should be the maximum, and the value
Interlayer adhesion strength of the present invention product for 3.5Kg/cm
3.3Kg/cm is almost the same. Comparative Example 3 is an evaluation result of a laminate of EVA (ethylene-vinyl acetate copolymer), which has a reputation for excellent interlayer adhesion, and the thermoplastic elastomer in Reference Example 1. This is an example to show that even though the adhesive strength between the adhesive and the adhesive is equivalent to that of the product of the present invention, the scratch resistance may be significantly inferior. Example 2 A two-layer laminate was obtained in the same manner as in Example 1 using the same partially ionomer resin used in Example 1 and the thermoplastic elastomer of Reference Example 2. Table 1 shows the evaluation results of the obtained laminate. From the same table, it can be seen that the 60° gloss and scratch resistance on the glossy side of the laminate are exactly the same as those of ordinary ionomer resin, and the interlayer adhesion strength far exceeds that of Comparative Example 2. I understand. Example 3 A two-layer laminate was obtained using the same partial ionomer resin as used in Example 1 and the thermoplastic elastomer of Reference Example 3 and operating as in Example 1. Table 1 shows the evaluation results of the obtained laminate. From the same table, it can be seen that the 60° gloss and scratch resistance on the glossy side of the laminate are exactly the same as those of ordinary ionomer resin, and the interlayer adhesion strength far exceeds that of Comparative Example 2. I understand. Comparative Example 1 A laminate was obtained by simultaneous two-layer extrusion using the thermoplastic elastomer obtained in Reference Example 1 for both layers. The evaluation results are shown in Table 1. Comparative example 2 Ionomer resin [MI (190°C) 10g/10min,
Carboxy group content 10 mol%, neutralization degree 72%, sodium ion type] was melted in an extruder at 200°C in a nitrogen atmosphere, and the following operations were performed in the same manner as in Example 1 to obtain a two-layer laminate. . Table 1 shows the evaluation results of the obtained laminate. Comparative Example 3 Ethylene-vinyl acetate copolymer [vinyl acetate unit content 14 wt%, density 0.93 g/cc, MI (190°C)
1.4 g/10 min] was melted during extrusion at 200° C. in a nitrogen atmosphere, and the following operations were performed in the same manner as in Example 1 to obtain a two-layer laminate. Table 1 shows the evaluation results of the obtained laminate. 【table】

Claims (1)

[Scope of Claims] 1. A thermoplastic elastomer layer consisting of a polyolefin and an ethylene/α-olefin copolymer elastomer, at least one of which is partially crosslinked, and a partial ionomer resin layer containing free carboxyl groups. or 1-olefin (meta)
A laminate with good surface gloss and scratch resistance, which is formed by strongly bonding an acrylic acid copolymer resin layer. 2. A thermoplastic elastomer consisting of a polyolefin and an ethylene/α-olefin copolymer elastomer, at least one of which is partially crosslinked, and a partial ionomer resin layer containing a free carboxyl group or a 1-olefin (meth) elastomer. ) A method for producing a laminate with good surface gloss and scratch resistance, characterized by strongly bonding the acrylic acid copolymer resin with an acrylic acid copolymer resin in a molten state.