JPS60229938A - Thermoplastic elastomer composition - Google Patents

Abstract

PURPOSE:The titled composition, consisting essentially of a vinyl chloride based polymer containing a specific stabilizer added thereto during polymerization, partially crosslinked acrylonitrile-butadiene copolymer and plasticizer, and having improved heat and weather resistance and nonmigration property and shape retaining property at high temperatures and compression set characteristics. CONSTITUTION:A thermoplastic elastomer composition obtained by incorporating (A) 100pts.wt. high polymer consisting of (A) 80-40wt% vinyl chloride based polymer, prepared by adding 0.1-10pts.wt. N-(3-methacryloyloxy-2-hydroxypropyl)-N'-phenyl-p-phenylenediamine to 100pts.wt. vinyl chloride monomer or 100pts. wt. mixture thereof with vinyl based monomer copolymerizable therewith, e.g. ethylene or vinyl acetate during polymerization, and having >=2,000 average polymerization degree and (B) 20-60wt% partially crosslinked acrylonitrile- butadiene copolymer with (C) 20-200pts.wt. plasticizer.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention mainly consists of a vinyl chloride thread polymer, a partially crosslinked acrylonitrile-butadiene copolymer, and a plasticizer, which are obtained by adding a specific stabilizer during polymerization. The present invention relates to thermoplastic elastomer compositions that have properties such as heat resistance, weather resistance, and non-migration properties as components.

[Conventional technology]

Conventionally, vinyl chloride-based polymers have been used to make rigid scales such as pipes and corrugated plates, as well as flexible hoses, gaskets, packing, leather, films, etc. by adding plasticizers, fillers, stabilizers, lubricants, etc. It is also extremely widely used in soft applications such as silver coatings. but,
This soft vinyl chloride resin has disadvantages such as poor shape retention when heated to a cool temperature and large permanent deformation when deformed at high temperatures compared to vulcanized rubber.

Methods to improve this drawback include (1) a method of using vinyl chloride;
A method of blending a partially crosslinked acrylonitrile-citadiene copolymer is known. However, the method according to (1) generally has low productivity during the production of vinyl chloride yarns and polymers, and even if a vinyl chloride polymer with an average polymerization ratio of 10,000 or more is used, Not only does the shape retention at high temperatures and the permanent set during high temperature deformation not improve, but even if the amount of ordinary plasticizers and other additives is increased, it is the same as other vortex molecular materials, such as super-molecular capped polyethylene. This was also undesirable due to the fatal drawback that the moldability was poor (+=e). In addition, the method according to (2) is
sing of Powdered NBR-P'VC
Polyblend Compounds J (Rub
ber Chemistry and Technology
o-gy45.4.1111-1124 (1972))
, or the part introduced in "Basic properties of PVC formulations containing nitrile rubber powder (1), <2), C3) J (Polymer Digest, March 5, 1980 issue) Crosslinked acrylonitrile-butadiene copolymer, for example, Chemigum N8B I A2 (Gutdeyer #
) is blended with a vinyl chloride polymer and a plasticizer. According to this method, shape retention at still temperatures and water resistance during high temperature deformation are improved. However, this method deteriorates the weather resistance and fdm properties, which are the great advantages of soft vinyl chloride resin. To this end, methods are being considered to suppress the decline in weather resistance and heat resistance by incorporating stabilizers such as hindered phenol antioxidants, amine antioxidants, and Kyogai Sengiyozaku. Even when these stabilizers are added, their improvement effects are insufficient, and depending on the type of stabilizer, the stabilizer may migrate to other materials and cause contamination.

However, if a reactive anti-aging agent is added to a vulcanized rubber material, a covalent bond is formed between the reactive anti-aging agent and the rubber during the vulcanization reaction, resulting in the above-mentioned migration and contamination. Although properties such as properties are improved, such effects were not observed when molding a thermoplastic composition as the object of the present invention.

[Problems to be Solved by the Invention] In order to solve these problems ('heat resistance, weather resistance, non-migration properties, high temperature shape retention, compression set), the present inventor has developed a method using vinyl chloride monomer. A vinyl chloride polymer obtained by adding a stabilizer having a reactive group to the polymerized ψ of monomers as the main component,
The present invention has been achieved as a result of intensive study on various conditions and characteristics of a thermoplastic elastomer composition containing a partially crosslinked acrylonitrile-zotazoene copolymer and a plasticizer as main components.

[Means for solving problems]

That is, the present invention uses vinyl chloride monomer 1o.

Part by weight: N-(+-methacryloyloxy-2-hydroxypropyl) -N/ - 80 to 40 weight% of a clay-based vinyl polymer obtained by adding 0.1 to 10 parts of phenyl-paraphenylenecyamine, 20 to 60 weight of a partially crosslinked acrylonitrilutazoene copolymer, This is a thermoplastic elastomer composition whose main components are 100 parts by weight of a polymeric material consisting of 100% by weight and 20 to 200 parts by weight of a plasticizer.

The present invention will be explained in more detail below.

The vinyl chloride polymer used in the present invention can be produced by the following production method. That is, during the polymerization of 100 parts by weight of vinyl chloride monomer or 100 parts by weight of a mixture of vinyl chloride monomer and a vinyl monomer copolymerizable therewith, N-(3-methacryloyloxy- 2-
It can be produced by adding 0.1 to 10 parts of hydroxypropyl-N'-phenyl-paraphenylene diamine and polymerizing it. The reason for the addition during the polymerization reaction is
If N-(6-methacryloyloxy-2-hydroxypropyl)-N/-phenyl-paraphenylenediamine is present during charging, it will hardly polymerize with a practical degree initiator Mf, or the polymerization reaction rate will be extremely slow. It's for a reason.

The addition gate of thorny N-C5-methacryloyloxy-2-hydroxylpropylene-N'-phenyl-paraphenylenecyamine can be copolymerized with vinyl chloride monomer 1oo4 cap or vinyl chloride monomer and this. Mixture 1D of vinyl-based lid body.

It is preferably 0.1 to 1 parts by weight.

If it is less than 0.1 coulometric part, the effect of improving heat resistance and weather resistance will be small, and if it is more than 10 coulometric part, no further improving effect will be obtained and it is economically disadvantageous.

In the present invention, examples of vinyl monomers copolymerizable with vinyl chloride include α-olefins such as ethylene and propylene, vinyl esters such as vinyl acetate and vinyl stearate, methyl vinyl ether, and lauryl vinyl ether. vinyl ethers, acrylic and methacrylic acid esters such as methyl acrylate and methyl methacrylate, amides such as methacrylamide and acrylonitrile, nitriles, styrenes such as styrene and α-methylstyrene, and small amounts of sialyl phthalates. ,
It contains polyfunctional monomers such as ethylene glycol dimethacrylate, and reactive oligomers such as polyethylene glycol and 1,2-polybutadiene. Furthermore, a relatively small amount of ethylene-vinyl acetate copolymer, chlorinated polyethylene, thermoplastic polyurethane, etc. can be coexisted with the above monomers for polymerization. The average degree of polymerization of the vinyl chloride polymer is not particularly limited, but it exhibits good elastic properties at high temperatures when the average degree of polymerization is high, so the average degree of polymerization is 2000. It is preferable that it is above.

The partially cross-linked acrylonitrile-zotazoene copolymer used in the present invention is not limited to its manufacturing method as long as it contains a cross-linked acrylonitrile-IJ-rubutazoene copolymer that is insoluble in methyl ethyl ketone; A method of copolymerization with a polyfunctional monomer such as glycol dimethacrylate, a method of increasing the reaction rate until a crosslinked acrylonitrile-citadiene copolymer insoluble in methyl ethyl ketone is produced, or a method of suppressing a small amount of crosslinking. Any production method may be used, such as a method in which an unvulcanized acryloni l-IJ sil-tadiene copolymer is crosslinked using an agent to obtain a temperature of 0.degree. In general, partially crosslinked acrylonitrile-butadiene copolymers that are available include Chemigam N8B I A2 (product manufactured by Gutdeyer), J
8RN201 (Japan Synthetic Rubber Company H product), H7Car
1422 (B-J', a product manufactured by Gutdrich).

The mixing ratio of the vinyl chloride polymer and the partially crosslinked acrylonitrile-citadiene copolymer is 80 to 40% by weight of the vinyl chloride group type polymer and 20 to 60% by weight of the partially crosslinked acrylonitrile copolymer. is important in the present invention.

When the vinyl chloride copolymerization is more than 80% by weight and the partially crosslinked acrylonitrile-zotazoene copolymerization is less than 20 polymerization, the shape retention at high temperatures, which is a feature of the present invention, can be achieved.
The permanent deformation resistance during high-temperature deformation is poor, and the desired thermoplastic elastomer composition cannot be obtained. On the other hand, when the vinyl chloride polymer is less than 40% by weight and the partially crosslinked atarylonitrile-butadiene copolymer is more than 60% by weight, it is thermoplastic and therefore forms the matrix of the composition.
This is unsuitable because the concentration of the vinyl chloride polymer, which maintains tensile and tearing strength, decreases, and mechanical properties such as tensile and tearing strength are significantly reduced. Therefore, the disaster molecular rod of the present invention is made of the vinyl chloride polymer 80~
40% by weight and 20-60% by weight of partially crosslinked acrylonitrile-butadiene copolymer.

Next, what is important in the present invention is the above-mentioned molecular weight substance 1oo
This is a fixing agent lid for the xi part. That is, for 100 parts by weight of a polymer consisting of 80 to 40% by weight of the vinyl chloride polymer and 20 to 60% by weight of the partially crosslinked acrylonitrile-zotadine copolymer, 20 to 40 parts by weight of the plasticizer is used. 20
The content must be 0 parts by weight. If the plasticizer is less than 20 parts by weight, the flexibility of the resulting thermoplastic elastomer composition and
The permanent deformation resistance during high-temperature deformation is poor, and if it exceeds 200 kft, the mechanical strength is extremely low, which is not preferable.

Further, other polymeric auxiliaries such as ethylene-vinyl acetate copolymer, acrylic resin, chlorinated polyethylene, polyurethane, chlorosulfonated polyethylene, etc. may be added. Heat stabilizers, fillers, lubricants, foaming agents, flame retardants, pigments, etc. may be added as necessary.

In order to produce the thermoplastic elastomer composition of the present invention, the mixing, cross-wiring, and molding of the vinyl chloride polymer, the partially chestnut-bridged acrylonitrile-zotazoene copolymer, and the plasticizer as main components are carried out. Any method may be used as long as the respective ingredients are substantially uniformly dispersed, mixed, and kneaded. Industrially, for example, tri-blending with a Henschel super mixer, ribbon blender, etc.
This tri-blend powder can be directly shaped into a chisel, extruded, rolled, etc. into a bath. l! Mixed! After that, it may be pelletized and molded. For molding methods, extrusion molding,
Injection molding, blow molding, calendar molding, vacuum forming, etc. may be used depending on the shape and properties of the desired product.

〔Example〕

In order to further facilitate understanding of the present invention, the present invention will be specifically explained below using experimental examples, examples, and comparative examples, but the present invention is not limited by these.

Experimental example 1 Pure water was placed in a stainless steel autoclave with an internal volume of 12 mm.
Partially saponified polyvinyl alcohol with an average polymerization rate of 1f2400 and 80 mol% used as a J1 suspension stabilizer.
．． ! i', m As a coalescence initiator, 2-ethylhexyl peroxydicarbonate 0.9 F was charged and the inside of the autoclave was removed, and then 9 was added to the polyvinyl monolid 2.
After polymerizing at 40.0°C for 12 hours without stirring, N-(3
-methacryloyloxy-2-hydroxypropyl)
-N/-phenyl-paraphenylenediamine (manufactured by Ohmukai Shinko Kagaku Kogyo Co., Ltd., Tsukurak O-1) 60% was added.After the addition, the unreacted vinyl chloride single mass was collected after 4 hours. The slurry was dehydrated and dried in a conventional manner.

Yield 1560.9. A light purple powdery polymer with an average degree of polymerization of 2,540 was obtained.

Experimental Example 2 Polymerization and treatment were carried out in the same manner as in Example 1, except that vinyl chloride monomers 2 to 2 were replaced with vinyl chloride monomer j, '9Icp and vinyl acetate 0.1. . Yield 1520g
, the average degree of polymerization is 2510, and the vinyl acetate content in the polymer is 4.
, 2% by weight of a pale purple powdery mixture was obtained.

Experimental example 3 N-(6-methacryloyl-2-hydroxypropyl)
+ N/-phenyl-paraphenylenecyamine 60F
was charged in bulk with pure water etc. using the same recipe as in Example 1, and after 16 hours at a polymerization temperature of 1f40.0°C, unreacted monomers were collected and removed, resulting in a slurry containing polymer particles. I couldn't get it.

Examples 1 to 4, Comparative Examples 1 to 6 A predetermined vinyl chloride complex shown in the table, a powdered stabilizer, epoxidized soybean oil, and carbon black were added to a Henschel super mixer, and the mixture was heated at a local speed for about 2 minutes. Stir to mix. Then, a predetermined amount of DOP (di-2-ethylhexyl phthalate) is added.

When the contents became smooth, cooling was started, a predetermined partially crosslinked acrylonitrile-citadiene coelectrolyte was added with nitrification, and after stirring for 5 minutes, the contents were 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. This roll sheet G was molded into 7'less pieces to prepare test pieces, which were subjected to tests for hardness, tensile aging, open shape retention, compression set, heat resistance, weather resistance, and migration properties. The results are shown in the table.

In addition, in the table, "S" is worn by Keijuto.

Test method (1) Hardness thickness 12? Using a printed press sheet, J'l5K660
1. Measured with a type A spring type hardness tester.

(2) Tensile strength, elongation According to JIS K 6723.

(3) Shape retention at still temperature A No. 6 dumbbell test piece with a thickness of 2 mm was suspended in a gear open state at 220°C, and the elongation (%) was measured after 60 minutes and evaluated using the following criteria. .

0~5%・・・・・・・・・0 5～10%・・・・・・△ Greater than 10%...X (4) Ball shaft permanent strain Jxs K 6301 (70℃X 22 Hr) Yes.

(5) In heat-resistant gear ogun, 10 [7'CX 120 Hr
The tensile strength was evaluated using the following criteria based on the rate of change from the tensile strength in (2).

Within ±15%...○ Exceeding ±15%...× (6) Black panel temperature 86'''Oz 200 Hr, tensile strength after aging using weather resistant sunshine carbon weather meter. Therefore, evaluation was made using a different criterion than the rate of change from the tensile strength in (2).

Within ±15%...○ Exceeding ±15%...
2 x 25 mm, 1 mbz thick Tanimeki-sou sheet was fixed with a thread, and after keeping the black panel temperature at 8680124 hours using a Zanshine carbon water meter, each compounded sheet was removed, the material to be migrated was washed with water, and the M of the migration was determined. I searched for nothing. A case where the transfer was significant was marked as ×, and a case where the transfer was barely noticeable was marked as ○.

According to the table, Comparative Example 1 uses a conventional formulation and has poor heat resistance and weather resistance. In Comparative Example 2, as an additive,
In the example in which N-(3-methacryloyloxy-2-hydroxypropyl)-N/-phenyl-paraphenylenecyamine was blended, the heat resistance and weather resistance were improved, but the non-migration property was poor. In Comparative Example 3, the plasticizer DOP is too small, so the hardness is affected, and the compression set is large, making it unsuitable.

Comparative Example 4 had too much plasticizer DOP, so the rope had poor shape retention and low tensile strength. Comparative Example 5 has poor high temperature shape retention and compression set due to an excessively large proportion of vinyl chloride polymer. Comparative Example 6 has poor heat resistance because the proportion of the partially crosslinked Ac IJ O nitrile-butadiene copolymer is too large.

It can be seen that Examples 1 to 4 of the present invention all have excellent heat resistance, weather resistance, and non-migration properties, and are highly balanced in properties such as tensile strength, local temperature shape retention, and compression set. .

〔Effect of the invention〕

Hontsuromei's thermoplastic elastomer composition has heat resistance, weather resistance,
It has excellent non-migration properties, as well as excellent heat retention and compression set properties, so it is suitable for applications that require these properties, such as flexible hoses, gaskets, packings, resins, films, and casings. Used cleverly.

Patent applicant: Kamekikagaku Kogyo Co., Ltd.

Claims (2)

[Claims] (1) N-(6-methacryloyloxy- 80 to 40% by weight of a vinyl chloride polymer obtained by adding 0.1 to 10 parts by coul of N/-phenyl-paraphenylenecyamine (2-hydroxynolopyl) and 20% by weight of a partially crosslinked acrylonitrile-citadiene copolymer. ~6
0% by weight of polymer sample 100% by weight and plasticizer 2
A thermoplastic elastomer composition whose main component is a 0-200-layer lid. (2) The thermoplastic elastomer composition according to claim (1), wherein the vinyl chloride polymer has an average degree of polymerization of 2000 or more.