JPS60139748A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:A resin composition having excellent rubber-like properties and good procesability, obtained by adding a plasticizer to a specified alkyl methacrylate polymer-vinyl chloride graft copolymer. CONSTITUTION:30-200pts.wt. plasticizer is added to 100pts.wt. alkyl methacylate polymer-vinyl chloride graft copolymer containing 30-90wt% vinyl chloride, made by the redical polymerization of a vinyl chloride monomer in the presence of an alkyl methacrylate polymer. If necessary, a filler, a modifier, an additive, etc. may also be added to the above resin composition. In the aforementioned graft copolymer, when the vinyl chloride content is less than 30wt%, mechanical strength will be reduced; while a graft copolymer containing more than 90wt% vinyl chloride can be obtaind only after a long polymerization time, resulting in poor productivity. When the amount of plasticize to be added is less than 30pts.wt., rubber-like elasticity will not be obtained; while when it exceeds 20pts.wt., it will be difficult to dry up, causing difficulty in molding.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a vinyl chloride resin, a composition, and a composition having rubber-like elasticity, which contains no methacrylic acid archylhetyl polymer! The present invention relates to a vinyl chloride resin composition obtained by adding a plasticizer to a copolymer obtained by force-polymerizing salt 1-1 to (2).

Soft salt, vinyl oxide chemical properties, physical properties,
It is a well-balanced resin and is used in a wide range of applications. , But Hose, Patsukin,! lines, soles,
, boots 1. Further improvements in rubber properties are required for applications such as leather, films, and automotive parts.

, as a method to improve and improve the quality of rubber,
To the next,. Two ways! ,Know:! are doing. That is, [1j, a method in which a polyvinyl chloride resin with a high degree of polyvinyl chloride is used as the base resin. (2) Is it a method based on the copolymer of salt y hibinyl 4 or prene 4 de 1? However, none of these methods can be called satisfactory. ,(
Regarding method 1), the physical properties are good in method 4. However, there are problems with processability, and method (2) has not yet produced satisfactory results, such as problems with compatibility between the vinyl chloride resin and the elastic material, which tends to cause deterioration of physical properties.

As a result of intensive research aimed at imparting rubber-like elasticity to vinyl chloride resin, the present inventors have discovered a methacrylic acid alkyl ester polymer obtained by graft polymerization of vinyl chloride monomer in the presence of methacrylic resin. - Vinyl chloride graft copolymer (hereinafter abbreviated as PMMA-f-VC)
It was discovered that a material with excellent rubbery properties and good processability could be obtained by adding a plasticizer to the material, leading to the present invention.

Graft polymerization of vinyl chloride is a known method for modifying vinyl chloride resin. For example, graft copolymers of vinyl chloride monomers having an ethylene-vinyl acetate copolymer as a backbone are known for improving impact strength. Graft copolymers are also available as non-plasticized softened vinyl resins intended to replace liquid plasticizers in order to improve the plasticizer transferability of soft vinyl chloride resins. As described above, graft copolymers of vinyl chloride have conventionally been used for purposes such as improving impact resistance and making plastic materials softer. However, PMMA-t-V
There are no known examples of softening C to impart rubbery properties.

The present invention will be explained in detail below.

That is, the present invention provides vinyl chloride-containing @
This is a vinyl chloride-based resin composition imparted with rubber-like elasticity, consisting of ~90% by weight of PMMA-t-VCloO, and 1g part of a plasticizing agent sO~20o'l. When a plasticizer is added to low-temperature polymerized PMMA-1-VC, the backbone polymer, which cannot absorb the plasticizer, acts as a kind of crosslinking point in the softened vinyl chloride resin, resulting in rubber-like elasticity. Conceivable.

The methacrylic resin used in the present invention may be in the form of powder or pellets and is not particularly limited.

The vinyl chloride content in PMMA-t-VC is 60-9
A range of 0% by weight is desirable. Pynylic chloride 30 heavy i
If it is lower than 90 M%, the mechanical strength decreases, and since vinyl chloride is used to obtain PMMA-r-vc higher than 90 M%, K requires a long polymerization time, resulting in poor productivity.

The method for producing PMMA-f-VC is a dissolution graft polymerization method in which 5 to so parts by weight of PMMA are homogeneously dissolved in vinyl chloride monomer under suspension of an aqueous medium and a suspension stabilizer, and then a polymerization initiator is added and polymerized. Add an aqueous medium, an oil-soluble initiator, a suspension stabilizer, or an inert organic solvent to ~50 parts by weight of PMMA, and compare the pressure of the vinyl chloride monomer with the saturation pressure of the vinyl chloride monomer at the polymerization temperature. and the ratio is 0.4 to 0.
Any polymerization method including the method of polymerizing while holding as described in No. 99 may be used. In the former polymerization method, if the amount of PMMA used is less than 50% by weight, the processability of the target polymer composition is insufficient, and if it exceeds 50% by weight, the viscosity of the polymerization system increases, making it difficult to manufacture. This is undesirable since it causes various problems such as scale adhesion and foaming during recovery of unreacted vinyl chloride monomer. In the latter polymerization method, the ratio of the pressure of the vinyl chloride monomer to the saturation pressure of the vinyl chloride monomer at the polymerization temperature is preferably in the range of 0.4 to 0.99. When it exceeds 0.99, homopolymer formation is significant;
If it is less than 0.4, the polymerization rate will decrease, which is not preferable. Furthermore, when the relative pressure ratio is increased, the obtained polymer becomes powdery even when pellet-shaped raw materials are charged. This facilitates subsequent compounding, which is preferable in terms of workability.

The oil-soluble polymerization initiator used in this polymerization method is 2.2'-□
Azobis-2,4-dimethylvaleronitrile, 2°2'
- Azo compounds such as azobis-4-methoxy-2,4-dimethylvaleronitrile, 2,2'-azobisisobutyronitrile, lauroyl peroxide, bayyl peroxide, t-
Peroxides such as butyl peroxy pivalate, 1-butyl peroxy neodecanate, peroxy dicarbonates such as di-isopropyl peroxy dicarbonate, di-8ee-butyl peroxy dicarbonate, di-2-ethylhexyl peroxy dicarbonate, etc. Carbonates, acetylcyclohexylsulfonyl peroxide, acetelium 2
- Commonly used sulfur-containing peroxides such as ethylhexylsulfonyl peroxide can be used alone or in combination.

In this polymerization method, a dispersant may or may not be used, but when used, the amount used is 0.15 weight or less based on the aqueous medium, and the type of dispersant may be any known dispersant. For example, cellulose derivatives such as methylcellulose, ethylcellulose, propylcellulose, hydroxyethylcellulose, hydroxyethylcellulose, partially saponified polyvinyl alcohol, polyacrylic acid, maleic anhydride, synthetic polymers such as vinyl ether copolymers, propylene re&
Esters such as serine fatty acid ester, sucrose acid ester, and sorbitan acid ester can be used alone or in combination.

The polymerization temperature can be selected within the range of 20 to 60°C, preferably 20 to 50°C. If the polymerization temperature is high, the degree of polymerization will decrease and problems will arise in mechanical properties. Lower polymerization temperatures improve mechanical properties but reduce processability. In addition, the polymerization time is long and the productivity is poor.

The binder used in the composition of the present invention is not particularly limited, but
For example, phthalic acid esters such as dibutyl phthalate and dioctyl phthalate, dibasic acid esters such as dioctyl adipate and dioctyl sebacate, other phosphoric acid esters, polyhydric alcohols and their derivatives, epoxy fatty acid esters, chlorinated paraffins, polyesters, and polyethers. 30 parts by weight to 20 parts by weight per 100 parts by weight of the resin composition
0 parts by weight are used. The amount used can be selected depending on the purpose of use, but if it is less than 60 parts by weight, rubber-like elasticity will not be obtained, and if it exceeds 200 parts by weight, it will be difficult to dry up and cause difficulties in molding. To the composition of the invention, commonly used fillers, various modifiers, various additives, etc. are added as necessary.

Examples of fillers include calcium carbonate, palm sulfate, talc, clay, mica, silica, aluminum hydroxide, magnesium hydroxide, silicates, carbon black, etc., and the amount added is equal to that of the vinyl chloride graft copolymer. 100 parts by weight or less is used relative to 100 parts by weight.

In addition, “pigments, heat stabilizers, flame retardants, ultraviolet absorbers, lubricants,
Various additives such as an IE agent and an antifogging agent may be added during charging.

Next, as a method for producing the composition of the present invention, the composition is uniformly mixed using a conventionally known method using a super mixer, a Henschel mixer, etc., and then a kneading machine such as a roll mill or a Banbury mixer 1 kneading extruder is used. It is heated, kneaded, and molded into a shape suitable for each purpose. PMMA-F-V of the present invention
Composition C satisfies the physical properties required for rubber properties in addition to mechanical strength and impact modulus, and is useful for hoses, packing, electric wires, shoe soles, boots, leather, films, automobile industrial parts, etc. It is an industrially useful composition.

Next, the method for measuring physical properties used in the present invention will be described below.

' Hardness: Measured according to JIS K 63o1 (value after 10 seconds for type A).

Tensile properties: Measured according to JIS K 6725.

Repulsion elasticity modulus: Measured according to JISK6301.

Melt viscosity: Koka type flow tester (nozzle 1f x 10m
m, 180°C) η = τ, //r (value calculated from the T value of 'r = 10' se + "") Next, the present invention will be specifically explained with reference to Examples. However, beyond the scope and scope of the invention, the present invention is not limited to the following embodiments.

Example 1 (Production method of PMMA-tLVC) Purified water 60% was placed in a 2t autoclave. Of, methacrylic resin (Asahi Kasei @
Product name [Delpera] 6ONJ)' 00 tXa-
0.5 f of cumyl peroxyneodecanoate and 1 t of partially saponified polyvinyl alcohol were charged. After degassing and replacing with nitrogen, the pressure was reduced, and while stirring at low speed, the pressure of the vinyl chloride monomer was compared with the saturation pressure of the vinyl chloride monomer at the polymerization temperature, and the ratio was maintained at 0.96. Polymerization was carried out at °C. Polymerization was completed in 9 hours, unreacted monomers were purged, and the resulting polymer was taken out and dehydrated and dried. 3052 polymers having a vinyl chloride content of 68 were obtained.

(Composition) 4 parts by weight of a tin-based stabilizer were thoroughly mixed with 100 parts by weight of PMMA-y-VC obtained in this way using a super mixer. The mixture was heated to 150℃15 using a heated roll mill.
Minute plasticizer (DOP nidioctyl 7-talate ester) 7
It was kneaded with 0 parts by weight.

The obtained sheet was press-molded and its physical properties were measured.

The results are shown in Table 1.

Example 2 (PMMA-y-VC (D manufacturing method) PMM
Polymerization was carried out according to Example 1, except that the polymerization time was changed to 5 hours in order to change the vinyl chloride content of A-v-VC. As a result, 2472 polymers having a vinyl chloride content of 59 were obtained.

(Composition) Example 1 was followed.

Example 3 (PMMA-t-VC (D manufacturing method) PMM
Polymerization was carried out according to Example 1, except that the polymerization time was changed to 13 hours in order to change the vinyl chloride content of A-f-VC. As a result, 280f of polymer having a vinyl chloride content of 82% was obtained.

(Composition) According to Example 1 Example 4 10 parts by weight of PMMA-t-VC obtained in Example 1 was thoroughly mixed with 4 parts by weight of a tin-based stabilizer using a suit mixer. The mixture was kneaded with 100 parts by weight of a plasticizer (DOP) at 150° C. for 15 minutes in a heated roll mill. ,
The obtained sheet was press-molded and its physical properties were measured.

Example 5 (Production method of PMMA-r-VC by suspension method) A 2-t autoclave was charged with 900 f of pure water, 502 methacrylic resin, 49 partially saponified polyvinyl alcohol, and 5002 vinyl chloride monomer, and heated at 60°C for 2 hours. Stir at high speed. After cooling to 40° C., 0.4 f Kl of α-cumylbaroxyneodecanoate was injected to initiate polymerization.

The polymerization was terminated when the polymerization pressure decreased to 36 to 9/cd g.-d pressure, and the unreacted monomer was purged and the 111° compound was taken out and dehydrated and dried to obtain a polymer of L vinyl chloride & fta 2%. I got it.

(Composition) Example 1 was followed.

Comparative Example 1 (Blend system of vinyl chloride homopolymer and methacrylic resin) 100 parts by weight of vinyl chloride homopolymer (P 1,500), 60 parts by weight of methacrylic resin, 4 parts by weight of tin-based stabilizer, and L as a plasticizer. )OP (dioctyl phthalate esterification)
70 parts by weight were added and mixed using a super mixer. The resulting mixture was kneaded at 150° C. for 15 minutes, but no uniform sheet was obtained, and insoluble matter was observed on the rolled sheet.

Comparative Example 2 (System in which a plasticizer is added to a vinyl chloride polymer with a high degree of polymerization) 100 parts by weight of a vinyl chloride polymer polymerized at low temperature by a suspension method, 4 parts by weight of a tin-based stabilizer, and 70 parts of DOP as a plasticizer. was added and mixed using a super mixer.

The resulting mixture was kneaded at 160° C. for 10 minutes using a heated roll mill, and then taken out in the form of a sheet. After press molding, physical properties were measured according to Example 1.

Table 1 shows the physical property results of Examples and Comparative Examples. 'Table 1 From the above results, when cross-cutting with the same hardness, the blend system (Comparative Example 1) takes time to cross-wire the rolls, and there are insoluble matters on the roll sheet, which is not preferable. A system in which a plasticizer is added to a highly polymerized vinyl chloride polymer (Comparative Example 2) has excellent mechanical strength, but has a high melt viscosity. Therefore, the PM of the main strike
Since the MA-f-VC composition has a high rebound modulus and a low melt viscosity, it is clear that it is useful as a vinyl chloride elastomer with well-balanced physical properties and processability.

Patent Applicant: Toyo Soda Kogyo Co., Ltd. Procedural Amendments February 21, 1980 Mr. Kazuo Nobuwakasugi, Director of the Special RR Agency 1 Case Indication 1982 Patent Application No. 245526 2 Name of the Invention IIA Vinyl Layer Nyl-based Resin The relationship between those who make composition positive and sharecropping! Patent Applicant Telephone Number (585) 3B+1 4. Date of Amendment Order Immediately 5. Number of Inventions Increased by Amendment 0. 6. Detailed Explanation of the Invention in the Specification Subject to Amendment 7. Contents of Amendment iu Description No. The description in lines 2 and 3 on page 7 is corrected as follows.

"About the suspension stabilizers used in this polymerization method" (2) On page 7, line 4, "known dispersants" is corrected to "known stabilizers."

(3) Same page 10, line 5 [] The phrase "from the τ value" is corrected to "from the τ value."

(4) Page 11, line 7 and page 12, line 9 and 13
In the 11th line of the text, ``150℃'' is corrected to ``1160℃''.

that's all

Claims (1)

[Claims] +1) By radical polymerizing vinyl chloride monomer in the presence of a methacrylic acid alkyl ester polymer #)
100 parts by weight of the produced methacrylic acid alkyl ester polymer-vinyl chloride graft copolymer having a vinyl chloride content of 30 to 90 parts by weight and 3 parts by weight of a plasticizer. : 1 to 200 parts by weight of a vinyl chloride-based resin composition imparted with rubber-like elasticity. (2) The alkyl methacrylate-saving ester polymer-vinyl chloride graft copolymer is a copolymer obtained by graft polymerizing vinyl chloride monomer in a substantially liquid phase state and in the absence of the vinyl chloride monomer. Claim 1 characterized in that
Compositions and products described in section.