JP2000143822A - Polymer additive and vinyl chloride resin composition containing it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber-state polymer additive which allows small decrease in elongation at high speed stretching, allows a large amount of strain before reaching the yield point and exerts a wide range of elasticity, and a vinyl chloride resin composition containing this. SOLUTION: A rubber-state polymer additive (D-1), prepared by co- crosslinking from 1 to 99 pts.wt. at least one non-crosslinked or partially crosslinked acrylonitrile/butadiene copolymer (A) and from 99 to 1 pts.wt. chlorinated polyethylene resin (B), provided that the total of (A) and (B) is 100 pts.wt., and (C) from 1 to 100 pts.wt. vinyl chloride resin in the presence of a crosslinking agent and a crosslinking accelerator, or a rubber-state polymer additive (D-2), prepared by co-crosslinking from 20 to 50 pts.wt. at least one non-crosslinked or partially crosslinked acrylonitrile/butadiene copolymer (A) and from 80 to 50 pts.wt. chlorinated polyethylene resin (B) in the presence of a crosslinking agent and a crosslinking accelerator, is obtained. A vinyl chloride resin composition is prepared by mixing from 1 to 50 pts.wt. rubber- state polymer additive (D-1) or (D-2) against 100 pts.wt. vinyl chloride resin (E).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a non-crosslinked or partially crosslinked acrylonitrile-butadiene copolymer (hereinafter referred to as NB).
R) and three components of chlorinated polyethylene resin and vinyl chloride resin, or two components of non-crosslinked or partially crosslinked NBR and chlorinated polyethylene resin in the presence of a crosslinking agent and a crosslinking assistant, and a rubber-like polymer obtained by co-crosslinking. More specifically, it relates to an additive and a vinyl chloride-based resin composition containing the same, and more particularly to a vinyl chloride-based resin capable of exhibiting a wide elastic range and having excellent workability with little reduction in high-speed tensile strength and elongation. Composition.

[0002]

2. Description of the Related Art In order to improve the high-speed tensile properties of a vinyl chloride resin (hereinafter referred to as PVC), a predetermined amount of a plasticizer is blended into a soft vinyl chloride resin composition, or a thermoplastic resin is added to the vinyl chloride resin. It has been dealt with by blending resins. However, a soft vinyl chloride-based resin composition containing a plasticizer cannot be used for applications in an environment where dissolution due to migration of the plasticizer occurs and deterioration is severe. Further, even in the case of compositions using various vinyl chloride-based copolymer resins, the amount of the thermoplastic monomer component subjected to the copolymerization is generally smaller than the amount of the vinyl chloride-based monomer component. In many cases, it is not possible to improve the high-speed tensile properties by using the vinyl chloride copolymer resin composition alone, and it is usually devised to contain some plasticizer. Even in this case, the usage is limited as in the case of the soft vinyl chloride resin composition. Further, when the soft vinyl chloride resin composition was evaluated for high-speed tensile properties in accordance with JIS K-6723, the tensile strength was 11.8 MPa.
The rigidity cannot be given to the molded product because the strength is considerably low as follows. In the case of a vinyl chloride copolymer resin composition, the tensile strength may be equal to or higher than that of a hard vinyl chloride resin composition in a high-speed tensile evaluation shown in JIS K-6723, but the elongation is a soft vinyl chloride resin composition. Considerably lower than that. Further, in a blend of a vinyl chloride resin and a thermoplastic polyurethane elastomer, chlorinated polyethylene, or the like, either one of the strength and the elongation of the high-speed tensile property is exhibited, but both cannot be increased. Further, it is clear that the amount of strain up to the yield point of the soft or semi-hard vinyl chloride resin composition as described above decreases as the yield stress decreases due to plasticization.
Although knowledge about such a composition of a blend of a vinyl chloride resin and a thermoplastic polymer has been known, methods for evaluating tensile properties differ depending on the application to be used, and thus a device for improving both tensile strength and elongation has been devised. I didn't. In addition, conventional rigid polyvinyl chloride resin has been used for durable materials such as pipes and building materials, but the amount of strain before yielding is quite small, and once yielding occurs, cracks and voids are formed inside the material. It is generated and destroyed, and cannot withstand normal use.

[0003]

In view of the above circumstances, a vinyl chloride resin composition containing no plasticizer has a high-speed tensile elongation equivalent to that of a soft vinyl chloride resin composition using a plasticizer. And high-speed tensile strength has the same tensile strength as hard to semi-rigid vinyl chloride resin composition, furthermore, it is intended to obtain a vinyl chloride resin composition having a large strain amount up to the yield point, Non-crosslinked or partially crosslinked NBR, chlorinated polyethylene, three components of vinyl chloride resin, or non-crosslinked or partially crosslinked NBR and two components of chlorinated polyethylene co-crosslinked rubber-like polymer additive and a predetermined amount thereof And a vinyl chloride resin composition.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, completed the present invention.
That is, the present invention relates to at least one kind of (A) 1 to 9 non-crosslinked or partially crosslinked acrylonitrile-butadiene copolymers.
9 parts by weight, 99 to 1 part by weight of chlorinated polyethylene resin (B), total 100 parts by weight, and vinyl chloride resin (C) 1 to 1
100 parts by weight of a rubber-like polymer additive (D-1) characterized in that it is co-crosslinked in the presence of a crosslinking agent and a crosslinking accelerator.
(Claim 1) A crosslinking agent and a crosslinking accelerator of 20 to 50 parts by weight of at least one kind (A) of a non-crosslinked or partially crosslinked acrylonitrile-butadiene copolymer and 80 to 50 parts by weight of a chlorinated polyethylene resin (B). (D-2) (Claim 2) A non-crosslinked or partially crosslinked acrylonitrile-butadiene copolymer having an acrylonitrile content of 20 to 40% and Mooney The rubbery polymer additive according to claim 1 or 2, wherein the viscosity is in the range of 30 to 80. (Claim 3) The chlorinated polyethylene resin (B) has a chlorination degree of 30 to 40.
The rubber-like polymer additive according to any one of claims 1 to 3, wherein the co-crosslinking is carried out by heating and kneading. The rubber-like polymer additive according to any one of claims 1 to 4, wherein the co-crosslinking is performed by heating in an aqueous medium. The rubber-like polymer additive according to claim 6, wherein the rubber-like polymer additive has a core-shell structure.
2. The method according to claim 1, wherein the layer has a three-layer structure.
The rubber-like polymer additive according to any one of Claims 1 to 6 (Claim 7) The rubber according to any one of Claims 1 to 7 based on 100 parts by weight of the vinyl chloride resin (E). A vinyl chloride resin composition comprising 1 to 50 parts by weight of a polymer additive (D-1 or D-2) (Claim 8) The vinyl chloride resin (C), (E) Has a polymerization degree of 400
2. The method according to claim 1, wherein
The rubbery polymer additive or the resin composition according to any one of claims 3, 4, 5, 6, 7, and 8 (claim 9) is included in the content.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

A first aspect of the present invention is to provide at least one of a non-crosslinked or partially crosslinked acrylonitrile-butadiene copolymer.
Seed (A) / chlorinated polyethylene resin (B) = 1 to 99 /
99-1 part by weight, preferably (A) / (B) = 20-5
A rubbery polymer additive characterized by co-crosslinking 100 parts by weight of 0/80 to 50 parts by weight and 1 to 100 parts by weight of a vinyl chloride resin (C) in the presence of a crosslinking agent and a crosslinking accelerator. To obtain the agent (D-1).

The rubbery polymer additive is at least one kind of non-crosslinked or partially crosslinked acrylonitrile-butadiene copolymer (A) / chlorinated polyethylene resin (B).
= 20 to 50/80 to 50 parts by weight in the presence of a cross-linking agent and a cross-linking accelerator may be a rubber-like polymer additive (D-2). Here, NBR is 2
If the amount is less than 0 part, the skin phase becomes thin and there is no effect of improving the interfacial adhesion to the PVC matrix phase, and if it is more than 50 parts, the skin phase becomes thick and the expected physical properties are not expressed.

The rubbery polymer additive (D-1) containing the vinyl chloride resin (C) is characterized in that it is easily and uniformly dispersed in processing by blending with PVC, while the rubber polymer additive (D) contains the vinyl chloride resin (C). Rubber-like polymer additive (D-2)
Is uniformly dispersed by increasing the degree of kneading in the same manner as in (D-1), and is characterized in that the composition can be easily prepared by a usual rubber kneading method.

The non-crosslinked or partially crosslinked acrylonitrile-butadiene copolymer (A) used in the present invention includes:
An acrylonitrile content of 20 to 40%, preferably 25
~ 35% and Mooney viscosity is 30 ~ 80, preferably 5
Those having a range of 0 to 65 are preferred.

When the acrylonitrile content is less than 20% or more than 40%, the compatibility with PVC deteriorates, and the interfacial adhesion decreases.

When the Mooney viscosity is 30 or less, the skin phase becomes too soft as compared with the PVC matrix phase, and the interfacial peeling between the skin phase and the core phase occurs. On the other hand, if the Mooney viscosity is 80 or more, the skin phase becomes too hard than the core phase, resulting in a decrease in physical properties.

The chlorinated polyethylene resin (B) used in the present invention preferably has a chlorination degree of 30 to 40% by weight. When the degree of chlorination is less than 30% by weight or more than 40% by weight, when the additive is obtained, PVC is used.
Alternatively, the compatibility with NBR is reduced and a uniform co-crosslinked product cannot be obtained.

The degree of polymerization of the vinyl chloride resin (C) used in the present invention is preferably from 400 to 2,000, more preferably from 700 to 1500. Polymerization degree 4
If it is smaller than 00, it is dominated by the PVC matrix phase,
The expected elongation and strain cannot be obtained. Conversely, the degree of polymerization is 200
If it is larger than 0, it becomes difficult to gel PVC uniformly, and the rubbery polymer additive to be added is not uniformly dispersed.

As the cross-linking agent used for co-cross-linking, polyfunctional monomers such as triallyl cyanurate, traylyl isocyanurate, polyethylene glycol dimethacrylate and the like are used. As the crosslinking accelerator, a peroxide used for ordinary crosslinking of synthetic rubber and having a half-life temperature of 190 ° C. or less for 1 minute, for example, an organic peroxide such as dicumyl peroxide, butyl perester, dibutyl perester, etc. Is used.

The co-crosslinking method is performed by using a kneader such as a pressure kneader, a roll, or a boundary mixer in the presence of the resin, the cross-linking agent and the cross-linking accelerator. There is a method of heating and kneading in a range and pelletizing, or a method of heating in an aqueous medium, and is not particularly limited. The latter is co-crosslinked by heating in an aqueous medium, then dehydrated and dried to be used as a rubber-like polymer additive.

The rubber-like polymer additive preferably has a two-layer or three-layer structure having a core-shell structure from the viewpoint of deformation amount and energy absorption for high-speed deformation.

As a second aspect of the present invention, 1 to 50 parts by weight of the rubbery polymer additive (D-1 or D-2) described above is blended with 100 parts by weight of the vinyl chloride resin (E). The content is a vinyl chloride resin composition characterized by having been described above.

When the amount is less than 1 part by weight, the effect of addition is not exhibited, and when the amount is more than 50 parts by weight, the rigidity of PVC is impaired.
Cannot be used as a material.

At this time, a predetermined amount of stabilizers, lubricants, fillers, processing aids and the like used in the ordinary vinyl chloride resin is blended, and a pressure kneader, a roll, which is a usual method of kneading the vinyl chloride resin, is used. The pellets are prepared using a kneader such as a Banbury mixer.

The vinyl chloride resin (E) used at this time
Has a polymerization degree of 400 to 2000, preferably 700 to 15
A range of about 00 is preferable. By using a material having a high degree of polymerization, improvement in high-speed tensile properties can be expected, but processing using a method of kneading and molding an ordinary vinyl chloride resin composition becomes difficult, so that the degree of polymerization is in the range of about 700 to 1500. Are preferred. The heat stabilizer is used in an amount of 1 to 7 parts, preferably 2 to 5 parts, per 100 parts of the vinyl chloride resin. Specifically, for example, a Ba-Zn-based stabilizer, Ca
-Zn stabilizer, Sn stabilizer, Pb stabilizer, Mg-
Commonly used heat stabilizers such as an Al stabilizer and a hydrotalcite-based stabilizer are listed, and they may be used alone or in combination of two or more. The lubricant is used in an amount of 0 to 10 parts, preferably 0 to 5 parts, per 100 parts of the vinyl chloride resin. Specifically, for example, commonly used lubricants such as higher fatty acid metal salts such as calcium stearate, higher alcohols, and polyethylene waxes may be used alone or in combination of two or more. The filler is added in an amount of 0 to 20 parts, preferably 1 to 10 parts, per 100 parts of the vinyl chloride resin. Specifically, for example, commonly used fillers such as calcium carbonate, magnesium carbonate, calcium sulfate, magnesium sulfate, and talc are used, and they may be used alone or in combination of two or more. The processing aid is added in an amount of 0 to 10 parts, preferably 1 to 5 parts, per 100 parts of the vinyl chloride resin. Specifically, there are usually used processing aids such as an MMA-based processing aid mainly composed of methyl methacrylate and a polyester-based processing aid mainly composed of adipic acid, which may be used alone or in combination of two or more. May be. In addition, other colorants and ultraviolet absorbers, other thermoplastic resins and the like may be blended, and the type and amount of addition may be appropriately selected and used depending on the purpose within a range that does not impair the purpose of the present invention. .

[0021]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited only to these examples. (Examples 1 to 9) 100 parts of a vinyl chloride resin, 50 parts of a partially crosslinked acrylonitrile-butadiene copolymer, and 50 parts of a chlorinated polyethylene resin were blended, and triallyl isocyanurate (TAIC) was used as a crosslinking agent. 2 parts of dicumyl peroxide (DCP) was blended as an agent and heated and kneaded with a roll at 180 ° C. to prepare a rubber-like polymer additive D-1A of a co-crosslinked resin, which was pelletized with a sheet cutter. did. Further, 100 parts of a vinyl chloride resin and 10 parts of a partially crosslinked acrylonitrile-butadiene copolymer were further added.
Parts of D-1B, 100 parts of a vinyl chloride resin, 90 parts of a partially crosslinked acrylonitrile-butadiene copolymer, and 10 parts of a chlorinated polyethylene resin, D-1C.
In the same manner as in the above, a crosslinking agent and a crosslinking accelerator were blended to prepare three types of rubbery polymer resin sheets. Next, the rubbery polymer additive obtained above was blended with 5, 10 parts and the following other compounding agents per 100 parts of a vinyl chloride resin having a degree of polymerization of 700, and kneaded again at 180 ° C. with a roll. A sheet of vinyl chloride resin was prepared. Thereafter, the mixture was pelletized with a sheet cutter to obtain a vinyl chloride resin composition. In Examples 1 and 2, the compounding amount of the rubber-like polymer additive of D-1A was 5,
10 parts. In Examples 3 and 4, D-1B was used in Examples 5 and 6.
Are each prepared by blending 5, 10 parts of a rubber-like polymer additive D-1C. Example 8.9 is a case of a combined use system of a rubber-like polymer additive of D-1A and MBS which is a reinforcing agent usually used for a vinyl chloride resin. MBS is 5 parts, and in Example 9, 10 parts of a rubbery polymer additive and 5 parts of MBS are blended. Example 7 is a commercially available chlorinated polyethylene (MR-1).
04, manufactured by Daiso Corporation) and 10 parts of a commercially available vinyl chloride resin having a polymerization degree of 700 (S1007, manufactured by Kanegafuchi Chemical Co., Ltd.) were reslurried in a 25% aqueous suspension slurry, and the NBR latex was solidified. 20 parts in conversion,
After adding 4 parts of TAIC and 2 parts of azobisisobutyronitrile, deaerated, reacted at a polymerization temperature of 70 ° C. for 8 hours, washed with water, dried and mixed with 10 parts of a granular rubber-like polymer additive. It is.

The other composition is as follows. Based on 100 parts of the vinyl chloride resin, 5 parts of an Sn stabilizer, 1.2 parts of a total of two types of polyethylene wax, 0.3 part of calcium stearate, and 2 parts of a processing aid were used. Injection molding is performed using the pellets to form a 3 mm thick JISK-711.
3 No. 1 dumbbell was made.

(Comparative Examples 1 to 7) The blending composition of the rubbery polymer additive of the above example was obtained by blending 100 parts of a vinyl chloride resin and 100 parts of a partially crosslinked acrylonitrile-butadiene copolymer as a crosslinking agent. Two parts each of triallyl isocyanurate (TAIC) and dicumyl peroxide (DCP) as a cross-linking accelerator are blended,
A rubber-like polymer additive of a co-crosslinked resin obtained by heating and kneading at 80 ° C. was prepared and pelletized with a sheet cutter. In addition, a rubber-like polymer additive of a co-crosslinked resin obtained by similarly blending a crosslinking agent and a crosslinking accelerator with 100 parts of a vinyl chloride resin and 100 parts of a chlorinated polyethylene resin and kneading the mixture at 180 ° C. It was created. Each of these two types of rubbery polymer additives was added to 100 parts of the vinyl chloride resin in an amount of 1 part.
0 parts were blended. (Comparative Examples 1 and 2) 30 parts of plasticizer DOP to 100 parts of vinyl chloride resin,
50 parts of the soft vinyl chloride resin composition (Comparative Examples 3 and 4) was kneaded with a pressure kneader to a resin temperature of 150 ° C., and then pelletized through a granulator. Further, the MBS of the impact modifier was 0 to 3 with respect to 100 parts of the vinyl chloride resin.
A mixture of 0 parts (Comparative Examples 5 to 6) was extruded and pelletized.

At this time, the other composition was formulated in the same manner as in the example. In these comparative examples, injection molding was performed in the same manner as in the above-mentioned example to prepare the first dumbbell. The injection conditions were appropriately changed according to each material, and a molded article was obtained in an optimal state.

Table 1 summarizes the evaluation results of the molded bodies produced by the examples and comparative examples.

[0026]

[Table 1]

[0027]

As can be seen from Table 1, according to the present invention, a molded article of a hard vinyl chloride resin composition having excellent high-speed tensile properties can be obtained without obstructing the advantages of the hard vinyl chloride resin. .

Claims (9)

[Claims] 1. A non-crosslinked or partially crosslinked acrylonitrile-butadiene copolymer (A) 1 to 9
9 parts by weight, 99 to 1 part by weight of chlorinated polyethylene resin (B), total 100 parts by weight, and vinyl chloride resin (C) 1 to 1
100 parts by weight of a rubber-like polymer additive (D-1) characterized in that it is co-crosslinked in the presence of a crosslinking agent and a crosslinking accelerator. 2. An at least one non-crosslinked or partially crosslinked acrylonitrile-butadiene copolymer (A)
50 parts by weight and chlorinated polyethylene resin (B) 80 to 50
(D-2) a rubber-like polymer additive characterized in that it is co-crosslinked in the presence of a crosslinking agent and a crosslinking accelerator. 3. The non-crosslinked or partially crosslinked acrylonitrile-butadiene copolymer (A) has an acrylonitrile content of 20 to 40% and a Mooney viscosity of 30 to 80. Rubber-like polymer additives described 4. The rubbery polymer additive according to claim 1, wherein the chlorinated polyethylene resin (B) has a degree of chlorination of 30 to 40% by weight. 5. The rubber-like polymer additive according to claim 1, wherein the co-crosslinking is carried out by heat kneading. 6. The method according to claim 1, wherein the co-crosslinking is performed by heating in an aqueous medium.
Rubber-like polymer additive described in item 7. The rubber-like polymer additive according to claim 1, wherein the rubber-like polymer additive has a two-layer or three-layer structure having a core-shell structure. Agent 8. The rubber-like polymer additive (D-1 or D-2) according to any one of claims 1 to 7, based on 100 parts by weight of the vinyl chloride resin (E). A vinyl chloride-based resin composition characterized by being blended in an amount of 50 to 50 parts by weight. 9. The method according to claim 1, wherein the degree of polymerization of the vinyl chloride resins (C) and (E) is in the range of 400 to 2,000. The rubbery polymer additive or resin composition according to claim 1