JP3437466B2 - Olefin-based thermoplastic elastomer composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin-based thermoplastic elastomer composition which is excellent in slidability, abrasion resistance and scratch resistance and does not cause bleed-out.

[0002]

BACKGROUND OF THE INVENTION Olefinic thermoplastic elastomers are flexible and have excellent rubber-like properties and heat resistance. Therefore, they can be used as substitutes for vulcanized rubber and soft polyvinyl chloride resin for automobile parts, electronic / electrical equipment parts, and building materials. Widely used for parts.

[0003]

However, when an olefinic thermoplastic elastomer is used as a substitute for a soft polyvinyl chloride resin for an automobile part, an instrument cover, a horn pad, a crash pad, a glove box, a console box, a headrest, Interior parts such as armrests and door trims have poor wear resistance and scratch resistance, and have a sticky feeling, which makes them unsuitable as parts that come into contact with human hands, and even exterior parts such as glass run channels and wind moldings are not suitable for glass. Due to lack of slidability, wear resistance was poor and durability was poor. In order to solve this problem, some parts use a material made of a hard olefinic thermoplastic elastomer or a material with a large amount of a slip agent such as fatty acid amide or silicone oil added to the sliding part to improve the sliding property. Although improved wear resistance has been proposed, the former hard material, on the contrary, lacks flexibility and lacks elongation and rubber elasticity, impairing the function of the product. Since the material added in a large amount causes bleed-out to obtain slidability, the durability of sliding effect was poor and the appearance of the product was impaired.

Therefore, an object of the present invention is to obtain a molded article which is excellent in slidability, abrasion resistance and scratch resistance while retaining elongation and rubber elasticity and which does not cause bleed-out. It is to provide a plastic elastomer composition.

[0005]

Means for Solving the Problems As a result of intensive research for solving the above-mentioned problems, the present inventor has found that when an olefin-based thermoplastic elastomer to which an acrylic-modified organopolysiloxane is added is molded, slidability is improved. However, since the compatibility between the olefinic thermoplastic elastomer and the acrylic modified organopolysiloxane is not very good, further research was conducted to improve this, and either stearic acid or higher fatty acid amide was added. Further, they have found that it is sufficient to add an appropriate amount of both, and completed the present invention.

That is, the olefinic thermoplastic elastomer composition of the present invention contains 1 to 100 parts by weight of an acrylic-modified organopolysiloxane, 100 parts by weight of an olefinic thermoplastic elastomer, and either one of stearic acid and higher fatty acid amide, or Both of them are mixed in an amount of 0.01 to 5 parts by weight.

In this olefinic thermoplastic elastomer composition, the acrylic modified organopolysiloxane (a) is used.
Following general formula: into organopolysiloxane represented by 3, (b) a mixture of acrylic ester or acrylic ester which is copolymerizable monomer, those made by emulsion graft copolymerization is there. General formula:

[Chemical 3] [Wherein R ¹ , R ² and R ³ are the same or different
C1-C20 hydrocarbon group or halogenated hydrocarbon
Group Y is radically reactive group, SH group or both
Two organic groups, Z ¹ and Z ² are the same or different water
Elemental atom, lower alkyl group or general formula:

[Chemical 4] A triorganosilyl group represented by (in the formula, R ⁴ and R ⁵
Are the same or different hydrocarbon groups having 1 to 20 carbon atoms
Or a halogenated hydrocarbon group, R ⁶ is a carbon atom having 1 to 20 carbon atoms
Hydrogen fluoride group or halogenated hydrocarbon group, radical reaction
A functional group, an SH group or an organic group having both of them), m
Is a positive integer of 10,000 or less, n is a positive integer of 1 or more
In addition, the olefinic thermoplastic elastomer is
Ethylene copolymer rubber is dynamically separated into
It is a polymer that has been dispersed and kneaded and partially crosslinked.
Is preferred.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The olefinic thermoplastic elastomer composition of the present invention will be described in detail below. The olefin-based thermoplastic elastomer used in this olefin-based thermoplastic elastomer composition is a polyolefin-based resin in which an ethylene-based copolymer rubber is dispersed, and is dynamically mixed by a kneader in the presence of an organic peroxide or sulfur. It is preferably a partially crosslinked polymer obtained by kneading.

Examples of the polyolefin resin used here include polypropylene, polyethylene, and a copolymer resin of propylene and an α-olefin having 2 or more carbon atoms. Specific examples of the α-olefin having 2 or more carbon atoms include ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 1-decene, 3-methyl-1-pentene, 4 -Methyl-1-pentene, 1-octene and mixtures thereof. The ethylene copolymer rubber is ethylene
Examples thereof include propylene copolymer rubber, ethylene / propylene / diene copolymer rubber, and ethylene / butene copolymer rubber.

In addition to the above-mentioned two components, the olefin-based thermoplastic elastomer may further contain a rubber other than the olefin-based rubber, if necessary. Examples of such rubber include styrene-butadiene rubber, nitrile rubber, natural rubber, and butyl rubber (Isobutylene Isoprene
Rubbers) and other diene rubbers, polyisobutylene rubber and the like.

The above-mentioned olefinic thermoplastic elastomer is commercially available, and for example, commercially available products such as Mirastomer (trade name, manufactured by Mitsui Chemicals, Inc.) and Sumitomo TPE (trade name, manufactured by Sumitomo Chemical Co., Ltd.) are known.

The acryl-modified organopolysiloxane used as the second component in the olefinic thermoplastic elastomer composition is (a) an organopolysiloxane represented by the above general formula: (3), and (b) an acrylic ester or acryl. It is preferable that a mixture of an acid ester and a monomer copolymerizable therewith is emulsion-grafted and copolymerized.

This organopolysiloxane is represented by the general formula: ## STR3 ## where R ¹ , R ² and R ³ are:
Carbon groups having 1 to 20 carbon atoms such as alkyl groups such as methyl group, ethyl group, propyl group and butyl group, phenyl group, tolyl group, xylyl group, aryl groups such as naphthyl group, which may be the same or different from each other. A hydrogen group or a halogenated hydrocarbon group having 1 to 20 carbon atoms in which at least one of hydrogen atoms bonded to carbon atoms of these hydrocarbon groups is substituted with a halogen atom, Y represents a vinyl group, an allyl group, γ-acryl group Roxypropyl group, γ-methacryloxypropyl group, γ-mercaptopropyl group and other radical reactive groups, SH group or organic groups having both, Z ¹ and Z ²
Are each a hydrogen atom, a lower alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, which may be the same or different, or a triorganosilyl group represented by the general formula:

In the general formula: R ⁴ and R ⁵ in formula 4 are the same or different, each being a hydrocarbon group or a halogenated hydrocarbon group having 1 to 20 carbon atoms, and R ⁶ is a hydrocarbon group having 1 to 20 carbon atoms. Or an organic group having a halogenated hydrocarbon group, a radical reactive group, an SH group, or both, which are the same as those exemplified in connection with R ¹ , R ² , R ³ and Y above. You can Furthermore, m is 10,0
It is a positive integer of 00 or less, preferably an integer in the range of 500 to 8,000, and n is an integer of 1 or more, preferably an integer in the range of 1 to 500.

Examples of the acrylic ester of the component (b) which is emulsion-grafted and copolymerized with the above-mentioned organopolysiloxane include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate. Acrylic acrylates such as 2-ethylhexyl acrylate, lauryl acrylate, and stearyl acrylate; alkoxyalkyl acrylates such as methoxyethyl acrylate and butoxyethyl acrylate; cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, etc., which may be used alone or in combination of two or more. Used in combination.

The monomer used together with the acrylic ester and copolymerizable therewith is, for example, a hydroxyl group-containing unsaturated monomer such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate. Examples thereof include a monomer, and these are used alone or in combination of two or more.

In this emulsion graft copolymerization, the above-mentioned organopolysiloxane as the component (a) and the acrylic ester as the component (b) or the mixture of the acrylic ester and the monomer copolymerizable therewith are blended. The ratio [(a) / (b)] is in the range of 2/8 to 8/2, particularly 4/6 to 7/3 by weight, and is copolymerizable with this used together with the acrylic ester. The different monomers are
It is preferably less than 30% by weight of acrylate.

The acrylic modified organopolysiloxane is used in an amount of 1 to 100 parts by weight, preferably 2 to 50 parts by weight, based on 100 parts by weight of the olefinic thermoplastic elastomer. If this amount is less than 1 part by weight, the slidability of the resulting molded article will not be improved, and if it exceeds 100 parts by weight, the compatibility with the olefinic thermoplastic elastomer will be poor.
It is not preferable because it impairs the mechanical properties and appearance of the molded product.

The stearic acid or higher fatty acid amide used as the third component in the above olefinic thermoplastic elastomer composition may be a commercially available one. Examples of the higher fatty acid amide include, for example, lauric acid amide, valmitic acid amide, stearic acid amide, saturated fatty acid amide such as behenic acid amide, erucic acid amide, oleic acid amide, and bridic acid amide,
Examples thereof include unsaturated fatty acid amides such as elaidic acid amides, bis fatty acid amides such as methylenebisstearic acid amide, methylenebisoleic acid amide, ethylenebisstearic acid amide, and ethylenebisoleic acid amide.

Stearic acid or higher fatty acid amide is
0.01 to 5 parts by weight of either or both of them, relative to 100 parts by weight of the olefinic thermoplastic elastomer,
It is preferably used in the range of 0.5 to 2 parts by weight. This is
If it is less than 0.01 parts by weight, the compatibility between the olefinic thermoplastic elastomer and the acrylic modified organopolysiloxane cannot be obtained, and if it is used in excess of 5 parts by weight, bleeding out occurs and the appearance is spoiled, which is not preferable.

In addition to the above-mentioned three components, the olefin-based thermoplastic elastomer composition of the present invention may further contain, if necessary, other components generally used in olefin-based thermoplastic elastomers. Examples of such components include various additives such as softeners such as process oil, fillers such as talc, carbon black and calcium carbonate, ultraviolet absorbers, antioxidants, processing stabilizers and colorants.

[0022]

EXAMPLES Specific embodiments of the present invention will be described below with reference to Examples and Comparative Examples, but the present invention is not limited to the description of these Examples.

(Examples 1 to 7 and Comparative Examples 1 to 6) The components (parts by weight) of the formulations shown in Tables 1 and 2 were kneaded in a Labo Plastograph having a volume of 60 cc, and the kneaded products were mixed. A 3.5-inch test roll (two rolls) was used for kneading at 160 ° C. for 7 minutes to obtain a roll sheet molded product. This was held by a mirror plate, preheated at 180 ° C. for 5 minutes, and then pressed at a pressure of 100 kg / cm ² for 4 minutes to obtain a sample (sheet). This was tested by the following method, and the results are shown in Table 1 and Table 2. The details of each component used are shown below.

(Test Method) Compatibility (Dispersibility): A roll sheet molded product prepared from the above sample (sheet) was observed for the dispersion state of the acrylic-modified organopolysiloxane in the olefinic thermoplastic elastomer. The compatibility was evaluated according to the following criteria. (Evaluation Criteria) ○: Well dispersed △: Small particles remained ×: Large particles remained

Bleed property: A sample (sheet) was irradiated with a sunshine weatherometer at 63 ° C. for 800 hours, and the stickiness of the surface was observed and evaluated according to the following criteria. (Evaluation criteria) ◎: No bleed out at all ○: Slight bleed out △: Bleed out ×: Very bleed out

Sliding property: Haydon 14D as a friction tester
-Using ANL (Shinto Kagaku Co., Ltd., trade name), the static / dynamic friction coefficient of the sample (sheet) was measured under the conditions of 10φSUS steel ball, load of 50 g, and pulling speed of 100 mm / min to evaluate the slidability. .

Abrasion resistance: A taper abrasion tester (manufactured by Toyo Seiki Co., Ltd.) was used under the conditions of a rotating disk 60 rpm, a grinding wheel CS10, a weight 4.9 N, and a continuous 1000 revolutions, before and after the test of the sample (sheet). The amount of wear was calculated from the change in weight, and the abrasion resistance was evaluated.

-Scratch resistance: Haydon 14D-ANL (previously mentioned)
Use a felt cloth wrapped around a 30 × 30 mm flat indenter
The surface condition of the sample (sheet) was observed by reciprocating 100 times at 50 g, a pulling speed of 100 mm / min, and a moving distance of 5 cm, and evaluated according to the following criteria. (Evaluation criteria) ○: Scratches are not noticeable Δ: Scratches are noticeable ×: Scratches are noticeable

Tensile test: Sample (pellet) A 3.5-inch test roll (2 rolls) was used to knead at 150 ° C. for 7 minutes to obtain a roll sheet molded product. Hold this with a mirror plate 1
After preheating at 70 ° C. for 4 minutes, a pressure of 100 kg / cm ² was applied for 4 minutes to obtain a sample (sheet) of 120 × 120 × 1.0 mm. This sample (sheet) was punched out with JIS K 6301 dumbbell No. 1 type and marked with a 25 mm marked line to obtain a test piece. Tensile strength and elongation were calculated by pulling this with a Shopper type tensile tester at a speed of 200 mm / min, measuring the maximum load required to break the test piece and the distance between marked lines at break, and calculating the tensile strength and elongation. And shown in Table 2.

Hardness: According to JIS K 6301 (JIS A).

(Details of components: In the table, the components and characteristics are described) ・ Olefinic thermoplastic elastomer: Mirastomer 7030N [trade name, hardness, manufactured by Mitsui Toatsu Chemicals, Inc.
70 (JIS A), partially cross-linked] Sumitomo TPE WT-312 [Sumitomo Chemical Co., Ltd., trade name, hardness 85
(JIS A), partially crosslinked type]

Acrylic modified organopolysiloxane: Charine R-1 [manufactured by Nissin Chemical Industry Co., Ltd., trade name, (a) /
(B) = 5/5] Charine R-2 [Same as above, (a) / (b) = 7/3]

Other components: F-3 (Kawaken Fine Chemical Co., trade name, stearic acid) Amide-O (Nitto Chemical Co., trade name, oleic acid amide) Amide-E (same as above, erucic acid) Amide) KF-96 (Shin-Etsu Chemical Co., Ltd., trade name, silicone oil)

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

According to the present invention, it is possible to obtain a product which is excellent in slidability, abrasion resistance and scratch resistance while retaining elongation and rubber elasticity and which does not cause bleed-out.

Claims (2)

(57) [Claims] 1. An olefin-based thermoplastic elastomer 10
1 to 100 parts by weight of acrylic modified organopolysiloxane and 0.01 to 5 parts by weight of one or both of stearyl acid and higher fatty acid amide are blended with 0 part by weight , and said acrylic modified organopolysiloxane.
Is (a) an organopolysiloxa represented by the following general formula:
(B) acrylic acid ester or acrylic acid ester
The mixture of the tellurium and a monomer copolymerizable therewith
An olefin-based thermoplastic elastomer composition, characterized in that it is formed by raft copolymerization . The general formula: ## STR1 ## [Wherein R ¹ , R ² and R ³ are the same or different
C1-C20 hydrocarbon group or halogenated hydrocarbon
Group Y is radically reactive group, SH group or both
Two organic groups, Z ¹ and Z ² are the same or different water
Atom, a lower alkyl group, or the general formula: ## STR2 ## A triorganosilyl group represented by (in the formula, R ⁴ and R ⁵
Are the same or different hydrocarbon groups having 1 to 20 carbon atoms
Or a halogenated hydrocarbon group, R ⁶ is a carbon atom having 1 to 20 carbon atoms
Hydrogen fluoride group or halogenated hydrocarbon group, radical reaction
A functional group, an SH group or an organic group having both of them), m
Is a positive integer of 10,000 or less, n is a positive integer of 1 or more
] 2. An olefinic thermoplastic elastomer,
The olefin-based thermoplastic elastomer composition according to claim 1, which is composed of a polymer in which an ethylene-based copolymer rubber is dynamically dispersed and kneaded in a polyolefin-based resin to partially crosslink.