JPH073090A - Thermoplastic elastomer composition and method for producing the same - Google Patents

Abstract

(57) [Summary] [Structure] (1) Polypropylene resin, (2) Acrylic ester copolymer rubber, and (3) (i) 0.01 to 15% by weight of a carboxyl group or an acid anhydride group. 100 parts by weight of modified polyolefin, (ii) 1 to 500 parts by weight of acrylic acid ester copolymer elastomer containing 0.01 to 5% by weight of a carboxyl group, and (iii)
An olefin-based thermoplastic elastomer resin composition comprising an elastomer-modified polyolefin in which the metal salt is 0.1 to 30 equivalents of the amount of the carboxyl group or acid anhydride group of (i). And (1), (2) and (3) are heated and mixed while the crosslinking of (2) is carried out, the method for producing the olefinic thermoplastic elastomer composition. [Effect] Excellent mechanical properties.

Description

Detailed Description of the Invention

[0001]

The present invention relates to heat resistance, paintability, weather resistance, oil resistance, ozone resistance, compression set resistance, molding processability,
The present invention relates to a thermoplastic elastomer composition having excellent mechanical properties.

[0002]

2. Description of the Related Art Conventionally, as a polyolefin-based thermoplastic elastomer, one mainly composed of polypropylene and ethylene-propylene-based rubber is widely known, but it has poor oil resistance because it has no polar group in its molecular structure. Was mentioned as a drawback. In order to improve this drawback, a polypropylene / acrylonitrile-butadiene rubber (NBR) composite has been proposed. However, although it has excellent oil resistance, it has ozone resistance, that is, weather resistance because it has a diene in its molecular structure. The weakness was mentioned as a weakness. On the other hand, a material having heat resistance, weather resistance, and oil resistance has been desired in recent years mainly for automobile applications. Acrylic rubber has all of these characteristics, but since it is a crosslinked rubber, it has a major problem in that it requires a vulcanization step and is recyclable.

From these points, a thermoplastic elastomer composed of a polyolefin resin and acrylic rubber has recently been studied. However, these two are essentially incompatible, and a simple blend does not give a good material. Heretofore, a method of adding a compatibilizing agent in order to enhance the compatibility between the two (JP-A-60-156738), and a method of blending with an olefin rubber represented by EPDM (JP-A-62-280244). Gazette), a method of blending a partially crosslinked acrylic rubber and a polyolefin (Japanese Patent Publication No. 62-502897), and the like, but materials having good physical property values by adding a compatibilizer have been reported. However, when blended with EPDM or the like, the good oil resistance of the acrylic rubber is deteriorated, and in the blending with the partially crosslinked acrylic rubber, there is a problem such as deterioration of compression set due to insufficient crosslinking degree. There were many.

Further, according to our study, a thermoplastic polyolefin resin, an acrylic ester copolymer rubber containing a non-conjugated diene as a copolymerization component and a polyester plasticizer are contained, and these are subjected to peroxidation under heating and melt shearing. Although the resin composition obtained by cross-linking with a substance shows excellent physical property values, the compatibility between the polyolefin resin and the acrylic rubber is still insufficient, and the acrylic rubber aggregates when the kneading time is increased to obtain the object. In some cases, mechanical strength was not obtained. Further, the conventionally known compatibilizer is a graft polymer in which polypropylene and acrylic rubber are linked by a covalent bond, and the synthesis of the polymer is limited in the olefin and the acrylic rubber to be used. There is a problem that only a solubilizer can be obtained.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a thermoplastic elastomer composition having excellent heat resistance, paintability, weather resistance, oil resistance, ozone resistance, compression set resistance, molding processability, and mechanical properties. The purpose is to

[0006]

DISCLOSURE OF THE INVENTION The present inventors have completed the present invention as a result of intensive investigations in view of the above-mentioned current situation. That is, the present invention provides (1) polypropylene resin,
(2) Acrylic ester copolymer rubber and (3)
(I) 0.01 to 1 of a carboxyl group or an acid anhydride group
100 parts by weight of modified polyolefin containing 5% by weight,
(Ii) 1 to 500 parts by weight of an acrylic ester copolymer elastomer containing 0.01 to 5% by weight of a carboxyl group, and (iii) a metal salt of 0.1 of a carboxylic acid group or an acid anhydride group of (i). It is an olefin-based thermoplastic elastomer resin composition comprising an elastomer-modified polyolefin of about 30 equivalents. The details of the present invention will be described below.

The polypropylene resin (1) used in the present invention includes polypropylene homopolymer, propylene / ethylene block copolymer having an ethylene content of 3 to 45% by weight, and propylene / ethylene random having an ethylene content of 0.5 to 10% by weight. Examples thereof include copolymers.
Such polypropylene resin will be described below (2).
It is desired to compound 3 parts by weight or more and 50 parts by weight or less, more preferably 5 parts by weight or more and 30 parts by weight or less with respect to 100 parts by weight of an acrylic acid ester copolymer rubber (hereinafter referred to as an acrylic rubber). If it is less than 3 parts by weight, the molding processability may be significantly reduced. On the other hand, if it exceeds 50 parts by weight, the surface hardness becomes extremely high, and the rubber-like property may be impaired.

The (2) acrylic rubber used in the present invention has an acrylic acid alkyl ester or an acrylic acid alkoxyalkyl ester as a main component, and specific examples of the main component monomer include methyl acrylate and ethyl. Acrylate, propyl acrylate,
Butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, ethoxyethyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, ethoxypropyl acrylate, and the like. The homopolymers or the copolymers of two or more thereof are used. Further, a non-conjugated diene, acrylonitrile, styrene, 2-chloroethyl vinyl ether having active chlorine in the molecule as a copolymerization component, vinylbenzyl chloride, vinyl chloroacetate, vinyl chloropropionate, allyl chloroacetate, allyl chloroprote Pionate, glycidyl acrylate having an epoxy group in the molecule, glycidyl methacrylate, is a copolymer of allyl glycidyl ether and the like, in order to improve the physical properties of the resulting composition, a non-conjugated diene component is copolymerized, It is desirable to use this as a crosslinking point. At this time, as the non-conjugated diene component, dicyclopentadiene, tricyclopentadiene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 1,4-hexadiene,
As 1,6-octadiene, 1,7-octadiene, or dihydrodicyclopentadienyloxyethyl group-containing ester of unsaturated carboxylic acid, dihydrodicyclopentadienyloxyethylene and acrylic acid, methacrylic acid, itaconic acid, maleic acid Examples thereof include esters with acids or unsaturated carboxylic acids such as fumaric acid. Also,
The proportion of the above-mentioned non-conjugated diene in the acrylic ester copolymer rubber is not particularly limited, but is preferably 0.1% by weight or more and 20% by weight or less for the purpose of expressing the physical properties of the rubber.

When the non-conjugated diene is used as the crosslinking point in the (2) acrylic rubber used, a peroxide is used in the crosslinking reaction, but the type of the peroxide is not particularly limited. For example, benzoyl peroxide, p-chlorobenzoyl peroxide, azobisisobutyronitrile, 2,5-
Dimethyl-2,5-di (t-butylperoxy) hexyne, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,2'-bis (t-butylperoxy) -p- Diisopropylbenzene, 1,1-bis (t
-Butylperoxy) -3,3,5-trimethylcyclohexane, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, cyclohexanone peroxide, t-butylperoxybenzoate, dicumylper Examples thereof include oxide, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide and the like. The amount of this peroxide used is 10
The amount is usually 0.1 part by weight or more and 5 parts by weight or less with respect to 0 part by weight, but the amount used depends on the type of peroxide and the crosslinking point of the acrylic rubber, that is, the concentration of the non-conjugated diene. However,
After the reaction, the amount of peroxide used is 1 for uncrosslinked acrylic rubber.
It is preferable to adjust so as not to exist over 0%, and if uncrosslinked acrylic rubber exists over 10%, rubbery properties may be impaired. Further, a crosslinking accelerator and a crosslinking retarder, which are usually used for peroxide-crosslinked acrylic rubber, can be optionally used. The presence of uncrosslinked acrylic rubber can be confirmed by the following method. That is, the composition of the present invention or the acrylic ester copolymer rubber is pulverized by freeze pulverization, and then Soxhlet extraction is performed for 8 hours using acetone as a solvent. Then, the extraction residue is further subjected to Soxhlet extraction using xylene as a solvent, and the extraction component is evaluated by DSC (differential operation calorimeter) and IR (infrared spectroscopic spectrum). If uncrosslinked acrylic rubber is present, the glass transition temperature resulting from this is confirmed by DSC and the ester bond is confirmed by IR, respectively, and it is possible to quantify the uncrosslinked rubber by DSC.

Details of the (3) elastomer-modified polyolefin used in the present invention will be described below.

(3) The modified polyolefin (i) used in the preparation of the elastomer modified polyolefin includes
Maleic anhydride modified polypropylene, poly (ethylene-
Acrylic acid) copolymers are preferably used. The amount of the carboxyl group or acid anhydride group is 0.01 to 1
5% by weight is used, more preferably 1 to 10
Those with weight% are preferably used.

The (ii) carboxyl group-containing acrylic rubber used in the preparation of the (3) elastomer-modified polyolefin may have any copolymerization component of the acrylic rubber, but the carboxyl group content is from 0.01 to 5 wt% and more preferably 0.5 to 3 wt% are suitably used.

Further, (3) metal salts used in the preparation of the elastomer-modified polyolefin (iii) are metal alkoxides such as titanium tetrabutoxide, titanium tetraisopropoxide, zirconium tetrabutoxide, dibutyltin dilaurate, zinc acetate, lead acetate. , Metal acetates such as magnesium acetate and calcium acetate, metal hydroxides such as zinc hydroxide, iron hydroxide, aluminum hydroxide, magnesium hydroxide and calcium hydroxide, iron oxide, calcium oxide, titanium oxide, zinc oxide, Valence number 2 of metal oxides such as aluminum oxide, metal halides such as zinc chloride, calcium chloride, magnesium chloride, magnesium chloride, etc.
The salts of the above-mentioned metals are used, and the metal salts are not limited to ligands. The (iii) metal salt is used in an amount of 0.1 to 30 equivalents of the amount of the carboxyl group or acid anhydride group of the modified polyolefin (i).

These (3) elastomer-modified polyolefin may be prepared by reacting in an organic solvent, or may be reacted during melt mixing of (2) acrylic rubber and (1) polypropylene resin.

(3) The elastomer-modified polyolefin is (2) 1 part by weight or more and 50 parts by weight or less, more preferably 3 parts by weight or more and 30 parts by weight, based on 100 parts by weight of acrylic rubber.
It is desirable to add less than or equal to parts by weight. If it is less than 1 part by weight, preferable physical properties may not be exhibited, and if it exceeds 50 parts by weight, the surface hardness may be high and the rubbery property may be impaired.

Oil may be added to the composition of the present invention to improve the fluidity. This oil is not particularly limited, and any oil such as paraffin-based process oil, naphthene-based oil, aroma-based oil, ester-based plasticizer, ether-based plasticizer can be used. Also, two or more kinds of oil may be used at the same time. Among them, it is preferable to use the paraffin-based process oil and the polyester-based plasticizer at the same time in order to further improve the fluidity.

The amount of oil added is (2) acrylic rubber 10
It is desirable that the amount is 3 parts by weight or more and 50 parts by weight or less relative to 0 parts by weight. If it is less than 3 parts by weight, moldability may be impaired, and if it exceeds 50 parts by weight, bleed-out may occur.

When a polyester plasticizer is used, its production method is not particularly limited, but for example, it has 4 to 10 carbon atoms.
It can be obtained by condensation polymerization of the dicarboxylic acid of 1 with a glycol having 2 to 10 carbon atoms and / or a glycol having an repeating unit of 5 or less obtained by ring-opening polymerization. Of these, glycols having 2 to 10 carbon atoms include, for example, 1,2-ethanediol, 1,4-butanediol,
1,2-propanediol, butenediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,10-decamethylenediol, 1,9-nonanediol, 2-methyl-1,8 -Octanediol,
2,5-dimethyl-2,5-hexanediol, neopentyl glycol, 1,4-cyclohexanediol,
Diethylene glycol etc. are mentioned. On the other hand, examples of the compound having an epoxy group include cyclic ethers such as ethylene oxide, propylene oxide and tetrahydrofuran. Further, one or two or more of these are used as a glycol obtained by ring-opening polymerization of these to form a glycol having a repeating unit of 5 or less. Further, the dicarboxylic acid having 4 to 10 carbon atoms used for producing the polyester plasticizer includes, for example, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid and the like. Alternatively, two or more kinds are used.
Such a polyester plasticizer is (2) 3 parts by weight or more and 50 parts by weight or less, preferably 3 parts by weight or more and 40 parts by weight or less, and more preferably 3 parts by weight or more and 35 parts by weight or less with respect to 100 parts by weight of acrylic rubber. It is desirable to add. If it exceeds 50 parts by weight, bleeding may occur, and if it is less than 3 parts by weight, moldability may be significantly deteriorated. The molecular weight of the plasticizer added is 500 or more 3
0000 or less, preferably 600 or more and 5000 or less is desirable. If it is less than 500, bleeding may occur, and if it is 30,000 or more, it becomes difficult to obtain a material having excellent moldability.

When a paraffinic process oil is used as the above oil, the amount of the paraffinic process oil to be added is 3 parts by weight or more and 20 parts by weight or less, preferably 5 parts by weight or more and 15 parts by weight, based on 100 parts by weight of the acrylic rubber. The following is desirable. If it is less than 3 parts by weight, the moldability may be remarkably deteriorated, and if it exceeds 20 parts by weight, bleeding may occur.

Acrylic rubber is usually added with a filler such as carbon, but the composition of the present invention may also be added with a filler represented by carbon black, white carbon, clay, mica, calcium carbonate, talc and the like. good.
The amount of addition is (2) 10 per 100 parts by weight of acrylic rubber.
It is desirable that the amount is from 200 parts by weight to 200 parts by weight, preferably from 20 parts by weight to 150 parts by weight, more preferably from 30 parts by weight to 100 parts by weight. If it is less than 10 parts by weight, mechanical properties may decrease, and if it exceeds 200 parts by weight, moldability may be poor. Further, a stabilizer such as an antioxidant, an ultraviolet absorber, an antistatic agent, a lubricant, a flame retardant, a pigment, a processing aid and the like can be added to the composition of the present invention.

[0021]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

Example 1 A carboxyl group was added to a 500 ml beaker.
28.6 g of a copolymer elastomer containing 0% by weight of ethyl acrylate, butyl acrylate, and acrylonitonil, and a molecular weight of 5% by weight of an acid anhydride group (M
w) 15,000 maleic anhydride modified polypropylene 1
0.0 g and 200 ml of o-dichlorobenzene were added and dissolved at 90 ° C. under stirring to obtain a polymer solution. To this solution, a 10% aqueous solution of zinc acetate dihydrate was slowly added in an amount 7 times equivalent to the number of moles of carboxylic acid.
A white precipitate formed with the addition of the aqueous metal salt solution. The precipitate was filtered, washed with water, and then dried under reduced pressure at 60 ° C. for 24 hours to obtain an elastomer-modified polyolefin.

Separately from this, an acrylic acid ester copolymer rubber containing a non-conjugated diene as a copolymerization component (Nisshin Acrylic Rubber RV-2540 (Nisshin Chemical Industry Co., Ltd.)
100 parts by weight, HAF carbon 60 parts by weight, polyester plasticizer (Adeka Sizer PN-170 (Asahi Denka Kogyo KK, molecular weight: about 1100)) 10 parts by weight, paraffin-based process oil (Diana Process) 10 parts by weight of oil PW-90 (manufactured by Idemitsu Kosan Co., Ltd.),
Antioxidant (NAUGARD445 (UNIROYAL
CHEMICAL))) 2 parts by weight, stearic acid 1
A part by weight was sufficiently kneaded with a roll kneader to obtain an acrylic rubber compound. Next, acrylic rubber compound 80
g and polypropylene resin (Tosoh Polypro J5100A
(Manufactured by Tosoh Corporation) 15 g, and the elastomer-modified polyolefin obtained above is 3 g and the internal volume is 10 g.
The mixture was put into a Brabender mixer of 0 cc and a temperature of 180 ° C., and kneaded at a rotation speed of 140 rpm for 5 minutes. This was taken out and was then cooled with a water roll forming machine to remove the peroxide (C-13
(Shin-Etsu Chemical Co., Ltd.)) and 1.5 g of a vulcanization aid (Sumifine BM (Sumitomo Chemical Co., Ltd.)) were sufficiently kneaded.
The material thus obtained was again charged into a Brabender mixer having a temperature of 180 ° C., and was peroxide-crosslinked while being melt-kneaded at a rotation speed of 140 rpm. After 15 minutes, it was taken out of the mixer and again formed into a sheet by a roll forming machine, and then press-formed into a plate having a thickness of 1 mm for a tensile test.

Comparative Example 1 A composition was obtained and evaluated in the same manner as in Example 1 except that the elastomer-modified polyolefin was not used.

[0025]

[Table 1]

[0026]

Industrial Applicability As described above, the composition of the present invention is a material having excellent mechanical properties, and the elastomer-modified polyolefin used in the present invention can be easily prepared. It becomes possible to efficiently improve the physical properties.

Claims (3)

[Claims] 1. A modified polyolefin containing (1) a polypropylene resin, (2) an acrylic ester copolymer rubber and (3) (i) a carboxyl group or an acid anhydride group in an amount of 0.01 to 15% by weight. Parts, (ii) 1 to 500 parts by weight of an acrylic ester copolymer elastomer containing 0.01 to 5% by weight of a carboxyl group, and (ii
An olefin-based thermoplastic elastomer resin composition comprising i) an elastomer-modified polyolefin in which the metal salt is 0.1 to 30 equivalents of the amount of the carboxyl group or acid anhydride group of (i). (2) The acrylic ester copolymer rubber has a non-conjugated diene as a crosslinking point, and the uncrosslinked rubber after the crosslinking reaction is 10% or less of the added acrylic ester copolymer rubber. The olefinic thermoplastic elastomer resin composition according to claim 1. 3. Crosslinking (2) acrylic ester copolymer rubber while heating and mixing (1) polypropylene resin, (2) acrylic ester copolymer rubber, and (3) elastomer-modified polyolefin. The method for producing the olefinic thermoplastic elastomer composition according to claim 1 or 2, which is characterized in that.