JPS60123546A - Thermoplastic elastomer composition - Google Patents

Abstract

PURPOSE:The titled composition that is obtained by adding specific additives such as an organic phosphite to high-molecular-weight polymer composed of a vinyl chloride resin and partially crosslinked acrylonitrile-butadiene copolymer, thus being stabilized to show improved resistance to weathering discoloration and to heat. CONSTITUTION:(A) 100pts.wt. of a high polymer composed of 80-40wt% of a vinyl chloride resin of an average polymerization degree of higher than 2,000 and of 20-60wt% of partially crosskinked acrylonitrile-butadiene copolymer are combined with (B) 0.05-10, preferably 1-8pts.wt. of an organic phosphite such as triphenyl phophite, (C) 0.05-5, preferably 0.5-4pts.wt. of benzotriazole such as 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, (D) 0.05-5, preferably 0.5-4pts. wt. of a phenolic compound such as 2,6-ditert.-butyl-4-methylphenol, (E) 0.5- 10pts.wt. of titanium oxide and (F) a plasticizers.

Description

Detailed Description of the Invention The present invention comprises a vinyl chloride resin, a partially crosslinked acrylonitrile-butadiene copolymer, titanium oxide, and a plasticizer, in which an organic phosphite compound, a benzotriazole compound, and a phenol compound are blended. The present invention relates to stabilized thermoplastic elastomer compositions.

Traditionally, vinyl chloride fat has been used as feather material for flexible hoses, which can be colored freely by adding plasticizers, fillers, stabilizers, lubricants, colorants, etc., and has good moldability.
Widely used for soft applications such as gaskets, packing, leather, films, and wire coatings. However, this soft vinyl chloride resin has disadvantages such as inferior shape retention at high temperatures and large permanent deformation when deformed at high temperatures compared to 7JD me rubber.

As methods for improving this drawback, (1) a method of increasing the average degree of unity of the vinyl chloride resin used, and (2) a method of blending a partially crosslinked acrylonitrile-butadiene copolymer are known. On the other hand, the method according to (11) is generally very close to the production of sieve polymerization-extended vinyl chloride resin, and even if a vinyl chloride resin with an average polymerization IN of 10,000 or more is used, the shape at high temperature is not as expected. Not only is the retention property and water-retention strain during high-temperature deformation not improved, but even with the addition of open-cell plasticizers and other additives, it is the same as other crystalline molecular materials, such as ultra-high molecular weight polyethylene. The method according to (2) also has the fatal disadvantage of extremely poor molding processability, making it preferable.
sir+g of powdered NBR-PVC
po] yblend compounds j (Rub
ber chemist, ry and techno
logic45 (4+1111-1124 (1972),
or the basic properties of PVC formulations containing nitrile rubber powder (11i2+, (31 (polymer digest,
1980 5. b, June issue)
This is a method of blending h7 crylonitrile-zotadiene comonomer, for example, Chemigum N8BIA2 (product manufactured by Dandoyer), with a vinyl chloride resin and a plasticizer. , the permanent deformation resistance during high-temperature deformation is improved. However, according to this method, the weather resistance, heat resistance, and ozone resistance, especially the weather resistance and heat resistance, are deteriorated. Applications that require good shape retention at high temperatures and permanent set characteristics during high temperature deformation, such as residential window frame packing 7, etc.
There was a drawback that it could not be used for U-charges.

In order to improve the various drawbacks mentioned above, the inventors of the present invention, as a result of extensive studies, developed a vinyl chloride-based resin with a weight of 80 to 40 ml and a partially crosslinked acrylonitrile-butadiene copolymer of 20 to 60 ml.
IJ azole compounds, organic phosphite compounds, benozoone, etc.
By blending phenolic compounds, titanium oxide, and plasticizers, it has been stabilized with excellent weather resistance, heat resistance, shape retention at high temperatures, and high temperature deformation properties] water distortion properties and mechanical properties. discovered that it provides a thermoplastic elastomer composition,
We have arrived at the present invention.

That is, according to the present invention, 100 parts by weight of a heteromolecular polymer consisting of 80-40% by weight of a vinyl chloride resin, 20-60% by weight of a partially crosslinked acrylonitrile-butadiene copolymer, and 0.05 parts by weight of an organic phosphite compound. A thermoplastic elastomer composition containing 0.05 to 51i S of an IJ azole compound, 0.05 to 5 parts by weight of a phenolic compound, titanium oxide, and a plasticizer. .

The vinyl chloride resin used in the present invention includes vinyl chloride,
Or it is a combination of a mixture of vinyl chloride and a small amount of one or more monomers that can be combined together, and its production methods include bulk polymerization, powder turbidity polymerization, emulsion polymerization, solution polymerization, etc. Any manufacturing method may be adopted. Monomers copolymerizable with vinyl chloride include α-olefins such as ethylene and propylene, vinyl acetate, vinyl esters of vinyl stearate, methyl vinyl ether,
Vinyl ethers such as lauryl vinyl ether, esters of acrylic acid and methacrylic acid such as methyl acrylate and methyl methacrylate, amides such as methacrylamide and acrylonitrile, nitriles, styrene,
It contains styrenes such as α-methylstyrene, polyfunctional monomers such as diaryl phthalate, and ethylene glycol dimethacrylate.

The average degree of polymerization of the vinyl chloride resin is not particularly limited, but the higher the average degree of polymerization, the better the elastic properties at high temperatures will be exhibited, so the average degree of polymerization is preferably 2000 or more.

The partially cross-linked acrylonitrile-citadiene copolymer used in the present invention is not limited to its production method, as long as it contains a cross-linked acrylonitrile-butadiene copolymer that is insoluble in methyl ethyl ketone, and divinylbenzene, ethylene glycol dimethacrylate, etc. by copolymerization with polyfunctional monomers such as methyl ethyl ketone, or by increasing the reaction rate until a crosslinked acrylonitrile insoluble in methyl ethyl ketone is formed, or by using a small amount of crosslinking agent. Any production method may be used, such as a method of crosslinking an unvulcanized acrylonitrile-butadiene copolymer. In general, partially crosslinked acrylonitrile-butadiene copolymers available include Chemigam N
8BIA2 (Gundoyer Mm product) JSRN201 (
Product manufactured by Japan Synthetic Rubber Co., Ltd.) -Hycar 1422 (
B, F, Goodlynch products), etc.

The mixing ratio of the vinyl chloride resin and the partially crosslinked acrylonitrile-butadiene copolymer is 80 to 80% for the vinyl chloride resin.
40 weight ratio and partially cross-linked acrylonitrile 1 combination 20
In this invention, it is heavy equipment to be in charge every 60 to 60 times. When the vinyl chloride resin is more than 80 g% by weight and the partially crosslinked acrylonitrile-sitatsuene copolymer is less than 200 parts by weight, the heavy equipment of the present invention has poor shape retention at high temperatures and surface J permanent deformation properties during high temperature deformation. However, the desired thermoplastic elastomer composition could not be obtained. On the other hand, when the vinyl chloride resin is less than 401 parts by weight and the partially crosslinked acrylonitrile-butadiene copolymer is more than 600 parts by weight, the composition is thermoplastic, so that
This is unsuitable because the concentration of the vinyl chloride resin that maintains the tensile and tearing strength is reduced, and the mechanical properties such as the tensile and tearing strength are significantly reduced. Therefore,
The polymer rod of the present invention is made of a vinyl chloride resin of 80 to 40% and a partially crosslinked acrylonitrile-butadiene copolymer of 2 to 40%.
It is essential that the content be 0 to 60% by weight.

The organic phosphite compounds used in the present invention include:
For example, triphenyl phosphite, diphenyldecyl phosphite, tridecyl phosphite, didecyl phenyl phosphite, trioctyl phosphite, tridecyl phosphite, triotadecyl phosphite l-1
)IJ nonyl phosphite, tri(nonylphenyl) phosphite'to'self→(b)ji, etc.

Examples of the benzo) I) azole thread compounds used in the present invention include 2-(2'-hydroxy-5'-methyl-phenyl)benzotriazole/l/, 2-(2'-
Hydroxy-3',5'-ditylbutylphenyl)benzotriazole, 2-(2'-hydroxy-3
'-ter/coconut-butyl-5'-methyl-phenyl)-
5-10 Lobensotriazole, 2-(Cuhydroxy-3',5'-ditertiary-butylphenyl)-5-
Examples include chlorobenzotriazole, 2-(2'-hydroxy-4'-n-octoquinphenyl)benzotriazole, and the like.

The phenolic compound used in the present invention is 2.6
- Sheter 7, butyl-4-methylphenol, 2
, 4-dimethyl-6-tert-butylphenol,
2.2'-methylenebis(4-methyl-6-terthoarybutylphenol), styrenated phenol, 2,5
- Ditar7yarybutylhydroquinone, styrenated phenol, n-octadecyl-3-<4'-hydroxy-ro'.

Examples thereof include 5'-diter/yari-butylphenyl) propionate, tetrakis-[methylene-6-(ro/, 5/,,-ter'y-butyl-4'-hydroxophenyl) propionate comethane, and the like.

The amount of these compounds added is 80 to 4
Each island molecule consists of a partially crosslinked acrylonitrilutazoene copolymer with a weight center of 20 to 60%
Organic phosphite compound 0.05 to it part
10 parts by weight, benzotriazole compound 0.05-5
0.05 to 5 parts by weight of the phenolic compound is effective. If the added Mi゛ is less than 0.05 parts Ri, the effect of the present invention will hardly be obtained, and if the organic phosphite compound exceeds 10:i parts, or if the pensito-IJ azole compound exceeds 5 N R parts. Even if the amount of the phenolic compound exceeds 5 parts by weight, the effect will not be improved any further and it will be economically disadvantageous. A more preferable addition amount is 1 to 8 parts of organic phosphite compound,
In the range of 0.5 to 4 parts of the benzotriazole compound and 0.5 to 41 parts of the phenolic compound, a thermoplastic elastomer composition with improved dramatic flashiness and thermal properties as desired can be obtained. .

Titanium oxide is used in the compounding of conventional rubbers and plastics, and is not particularly limited, as long as it is in the rutile form or anatase form, and has an average particle size. It is preferably in the rutile form, with an average particle size of about 0.2 to 0.5μ, and the amount added is:
0.5 to 10 parts by weight of a polymer compound consisting of 80 to 40 M of vinyl chloride thread resin and 20 to 602% of partially crosslinked acrylonitrile-butadiene copolymer.
N: fjt portion is preferable.

There are no particular limitations on the plasticizer, and as with conventional soft vinyl chloride resins, fn', fn',
Examples of Th include di-2-ethylhexyl 7-talate, di-2-ethylhexyl 7-talate, dibutyl phthalate, etc.
Adipic acid esters such as ethylhexyl adipate, sepa7ic acid esters such as dibutyl sebacate, trimellitic acid esters such as tri-2-ethylhexyl trimellitate, and epoxy compounds such as epoxidized soybean oil are used. Attachment 7J[] The amount is not particularly limited. In other words, any type of plasticizer can be applied depending on the mixing ratio of the vinyl chloride resin used and the partially crosslinked acrylonitrile-butadiene composite, and the required hardness, flexibility, physical properties, and moldability of the product. The filling is good when used.

Further, other polymeric auxiliaries such as ethylene-vinyl acetate monomer, acrylic resin, chlorinated polyethylene, polyurethane, chlorosulfonated polyethylene, etc. may be added. heat stabilizers, fillers, lubricants, foaming agents,
Flame retardants, face 1, etc. may also be added as necessary.

A vinyl chloride resin, a partially crosslinked acrylonitrile-butadiene copolymer, an organic phosphite compound, for producing the stabilized thermoplastic elastomer composition of the present invention,
Benz) IJ A mixture of compounding agents whose main components are an azole compound, a phenol compound, titanium oxide, and a plasticizer,
Mixing and forming may be carried out by any method as long as the ingredients of the sonezone are substantially uniformly dispersed, mixed, and kneaded, and can be carried out using a treadmill, Henschel mixer, ribbon blender, etc. After blending, the tri-blend powder may be directly molded, or it may be melted and mixed using an extruder, rolls, etc., then pelletized, and then molded.

The molding method may be extrusion molding, injection molding, blow molding, calendar molding, vacuum molding, or the like, depending on the shape and properties of the desired product.

The stabilized thermoplastic elastomer composition of the present invention is specifically used for flexible hoses, gaskets, packing, leather, films, wire coatings, etc., and particularly has excellent weather resistance, heat resistance, and It is preferably used in fields that require elasticity and mechanical properties at high temperatures.

In order to further facilitate understanding of the present invention, the present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited by these.

In addition, in the example, "part" represents the N-position part 1''.

Examples 1-4. Comparative Examples 1 to 7 In a Henschel super mixer with a jacket temperature of 95°C, predetermined amounts of vinyl chloride flexure (Denka Vinyl 5H-250 manufactured by Denki Kagaku Kogyo Co., Ltd.) with an average degree of 1 degree of 2500 as shown in the table and Ba-Zn fatty acid were added. Salt complex stabilizer (BZ-10
0J Katsuta Kako Co., Ltd.) 6 parts, epoxidized soybean oil (Adekazai + 3″′-o-130p + Adeka Argus Chemical Co., Ltd.)
3 parts, and predetermined amounts of titanium oxide (R-820, manufactured by Ishikata Sangyo Co., Ltd.), tri(nonylphenyl) phosphite (Tsukrank TNP', Inunai Shinkosha JR), 2- (2'-
Hydroxy-5'-methylphenyl)benzotriazole (tinuvin P.

Ciba (manufactured by Iggy) and 2.6-mix by stirring at high speed until it becomes a jittery leave. Then, a predetermined amount of DOP
(di-2-ethylhexyl 7-talate) is added. When the contents become smooth, cooling begins and the temperature of the contents reaches approximately 50'C! At the point where the temperature reached 100%, a predetermined amount of Chemi Gum N8B IA, 2 (product manufactured by Gundeyer, partially crosslinked acrylonitrile-citadiene copolymer acrylonitrile %) was added, and after stirring for about 5 minutes, it was taken out.

Each of the taken out compositions was kneaded using two rolls with a surface temperature of 160° C. for 10 minutes after the compositions were wound around the rolls. Each test piece was prepared by press-molding this roll 7-t, and subjected to each test of hardness, tensile test, high temperature shape retention, compression set, weather resistance and heat resistance. Show the results to the light.

The test methods and evaluation methods in the table were as follows.

(1) Using a press sheet with hardness and thickness of 12 mm. Tl5K630
1' Measured using a type A spring type tester.

(2) Tensile strength and elongation According to JIS K6723. (Normal state) (3) High temperature shape retention A No. 6 dumbbell test piece with a thickness of 2 mm was suspended in a gear oven at 220'C, and the elongation (%) was measured after 60 minutes, and evaluated based on the following criteria. .

0-10%・・・・・・・・・Bigger than 010 cracks・
...△ (4) Permanent compression set according to JIS K6301 (70°C x 22 hours).

(5) When the heat-resistant gear is open, the tensile strength after heat aging at 1200CX168Hr is within ±10% of the normal tensile strength in (2). ○±10
Exceeds %... △ Toshida.

(6) Resistance to Weathering and Discoloration After aging a No. 3 dumbbell piece with a thickness of 2 mm at 50° C. for 300 hours using a Sun/Yain weather meter, the discoloration of the sample was evaluated by visual observation.

No discoloration・・・・・・・・・・・・・・・・・・
○ Slight discoloration...Δ Significant discoloration...... × From the table, Comparative Example 1 shows that the organic phosphite compound of the present invention , a be/citriazole yarn compound, a phenolic compound, and titanium oxide are not blended, and the heat resistance and weather resistance are insufficient. Comparative Examples 2 to 5 are cases in which any one of an organic phosphite compound, a benzotriazole compound, a phenol compound, or titanium oxide is insufficient, and the weathering resistance is poor. Comparative Example 6 has poor high-temperature shape retention and compression set because the amount of vinyl chloride resin is too large relative to the partially crosslinked acrylonitrile-butadiene copolymer. In Comparative Example 7, the ratio of the partially crosslinked acrylonitrile-butadiene copolymer was excessively high, so the tensile strength was extremely poor and the heat resistance was also low.

It can be seen that Examples 1 to 4 had excellent tensile properties, high-temperature shape retention, and compression set, and improved side heat resistance and surface discoloration.

Patent Applicant Denki Kagaku Kogyo Co., Ltd. Procedural Amendment January 13, 1980 B Director General of the Patent Office Kazuo Wakasugi 1, Indication of Case 1982 Patent Application No. 231794 2, Name of Invention Thermoplastic Elastic Composition 3. Relationship with the case of the person making the amendment Patent applicant address: 1-4-1 Yurakucho, Chiyoda-ku, Tokyo Column 5 of the detailed explanation of the invention in the specification, Contents of the amendment 1) Page 8, line 8 ``Tridecyl phosphite'' is ``
Tridodecyl phosphite,” he corrected.

Claims (1)

Scope of Claims (11) 100 parts by weight of a polymer consisting of a vinyl chloride resin of 80 to 40% weight and a partially crosslinked acrylonitrile-butadiene copolymer of 20 to 60% of copper, 0.0 parts by weight of an organic phosphite compound. A thermoplastic elastomer composition containing 0.05 to 5 parts by weight of an IJ azole compound, 0.05 to 5 parts by weight of a phenolic compound, titanium oxide, and a plasticizer. (2) The thermoplastic elastomer composition according to claim (1), wherein the vinyl chloride-based resin has an average degree of 1 degree of 2,000 or more.