JPS63235355A - Chlorinated vinyl chloride polymer composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. having excellent processability and resistance to heat and impact, by blending a chlorinated PVC with a specific vinyl chloride copolymer. CONSTITUTION:PVC having an average degree of polymn. of 400-200 is chlorinated to obtain a chlorinated PVC (A) having a chlorine content of 60-70wt.%. 70-95pts.wt. component A is blended with 5-30pts.wt. vinyl chloride copolymer (B) composed of 70-95wt.% vinyl chloride units and 5-30wt.% N-substd. maleic acid imide units and having an average degree of polymn. of 500-1,500 and optionally an impact modifier, a stabilizer, a lubricant, a processing aid, a filler, an ultraviolet absorber, a pigment, etc. (C).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a chlorinated vinyl chloride resin composition that has good heat resistance, excellent processability, and high impact resistance.

(Prior Art) Vinyl chloride resin has high rigidity and tensile strength, and is excellent in weather resistance, flame resistance, and chemical resistance, so it is widely used for pipes, plates, films, sheets, and the like. However, vinyl chloride resin has a low softening point.

Lacks heat resistance. For example, it softens and undergoes thermal deformation at 70 to 80°C, so it cannot be used at higher temperatures. - To impart heat resistance to vinyl chloride resin.

Attempts have been made to further chlorinate the resin after its manufacture.

The heat resistance of such chlorinated vinyl chloride resins improves as the degree of chlorination increases. However, chlorinated vinyl chloride resins with a high degree of chlorination have poor flowability and therefore poor processability. In order to improve processability, it is also possible to add a lubricant such as stearic acid or its ester to this chlorinated vinyl chloride resin. These are used to improve the moldability of polyvinyl chloride. However, in order to obtain the desired processability, a large amount of lubricant must be added.

Therefore, the softening point of the obtained resin composition is lowered.

Moreover, the lubricant leaches out so much that it cannot be used as a molded product.

In order to solve these drawbacks, attempts have been made to blend modified resins with chlorinated vinyl resins. Modified resins include 1, for example, chlorinated polyethylene (Special Publication No. 38
-12175), polypropylene, or a combination of polypropylene and polyethylene (Japanese Patent Publication No. 42-8224)
, ABS, or a combination of ABS and MBS (Special Publication Act 1977-
5219), ethylene-vinyl acetate copolymer (Japanese Patent Publication No. 43-12010), and ethylene-ethyl acrylate copolymer (Japanese Patent Publication No. 18464-1972).

Acrylonitrile (Special Publication No. 45-1624), polyolefin rubber or epichlorohydrin rubber (Special Publication No. 45-1624)
7-45420). However, when such a modified resin is blended in a small amount, the desired processability cannot be obtained, and when blended in a large amount, the softening point of the resulting composition decreases and the heat resistance deteriorates.

(Problems to be Solved by the Invention) The present invention solves the above-mentioned conventional problems, and its purpose is to provide a material with good heat resistance, excellent workability, and impact resistance. An object of the present invention is to provide a highly chlorinated vinyl chloride resin composition.

(Means for Solving the Problems) The present invention involves blending a vinyl chloride copolymer having N-substituted maleic acid imide units into chlorinated polyvinyl chloride that has excellent heat resistance and impact resistance. Accordingly, processability can be improved while maintaining heat resistance. It was completed based on the inventor's knowledge.

The chlorinated vinyl chloride resin composition of the present invention comprises (1) 70 to 95 parts by weight of chlorinated polyvinyl chloride obtained by post-chlorinating polyvinyl chloride having an average degree of polymerization of 400 to 2,000.

and (2) 70-95% by weight of vinyl chloride units and N
- Vinyl chloride copolymer 5 to 5 with an average degree of polymerization of 500 to 1,500 and having substituted maleic acid imide units of 5 to 30% by weight
30 parts by weight, thereby achieving the above object.

The average degree of polymerization of polyvinyl chloride is 400 to 2000. Preferably it is 600-1400. When the average degree of polymerization of polyvinyl chloride is less than 400, the impact resistance of the chlorinated polyvinyl chloride decreases. When the average degree of polymerization exceeds 2000, the melt viscosity of the chlorinated polyvinyl chloride becomes high and the moldability becomes poor. The chlorine content of the chlorinated polyvinyl chloride is preferably 60 to 70% by weight.

When it is less than 60% by weight, the heat resistance of the chlorinated polyvinyl chloride decreases. If it exceeds 70% by weight, the melt viscosity of the chlorinated polyvinyl chloride will increase and processability will deteriorate.

The N-substituted maleic acid imide unit, which is a constituent unit of the vinyl chloride copolymer, is 5 to 30% by weight, preferably 10 to 2% by weight.
The range is 5% by weight. When it is less than 5% by weight, the physical properties of the vinyl chloride copolymer become close to those of polyvinyl chloride,
The heat resistance of the copolymer decreases. If it exceeds 30% by weight, the impact resistance of the vinyl chloride copolymer will decrease, and
Since the melt viscosity increases, moldability also deteriorates. There is no transparency either. This N-substituted maleic acid imide is one example.

It is represented by the following formula: I where R1 and Rt are the same or different, hydrogen, chlorine, bromine, fluorine, a cyano group, or a carbon atom number of 1 to
Alkyl group of 3 R3 is an unsubstituted or substituted aliphatic group, a cycloaliphatic group, or an aromatic group having 1 to 30 carbon atoms. R3 is preferably a t-butyl group, isopropyl group, cyclohexyl group, phenyl 7J, or o-chlorophenyl group.

The chlorinated vinyl chloride resin composition of the present invention contains 70 to 95 parts by weight of chlorinated polyvinyl chloride, preferably 75 to 90 parts by weight, and 5 to 30 parts by weight of vinyl chloride copolymer, preferably 10 to 25 parts by weight. Contains parts. If the vinyl chloride copolymer is below this range, the desired processability of the chlorinated vinyl chloride resin composition cannot be obtained, and if it exceeds this range, the heat resistance and Impact resistance decreases.

In this chlorinated vinyl chloride resin composition, in the above composition range, when the chlorine content of the chlorinated polyvinyl chloride is low, the number of N-substituted maleic acid imide units in the vinyl chloride copolymer is increased, and the chlorinated A high chlorine content in polyvinyl chloride results in fewer N-substituted maleimide units. Thereby, the heat resistance of the chlorinated vinyl chloride resin composition.

A balance between impact resistance and formability is maintained.

If necessary, a monomer copolymerizable with vinyl chloride may be copolymerized with the vinyl chloride copolymer of the present invention within a range that does not impair the properties of the obtained chlorinated vinyl chloride resin composition. The vinyl chloride copolymer may be synthesized by any known polymerization method, including emulsion polymerization, suspension polymerization, solution polymerization, and precipitation polymerization.

Here, the method for producing post-chlorinated polyvinyl chloride used here is 9. For example, polyvinyl chloride is suspended in an aqueous medium containing a solvent such as chloroform, or in an aqueous medium containing no solvent. By photocatalytic chlorination method or gas phase flow method.

There is a method of chlorination using a photocatalyst or a peroxide catalyst. In the present invention, post-chlorinated polyvinyl chloride is
In addition to chlorinated vinyl chloride homopolymers, vinyl chloride
Ethylene copolymer, vinyl chloride-6 [vinyl copolymer,
It includes compositions obtained by chlorinating chlorinated vinyl chloride copolymers such as vinyl chloride-vinylidene chloride copolymers, or mixtures thereof.

The chlorinated vinyl chloride resin composition of the present invention contains known additives 9 conventionally blended with chlorinated polyvinyl chloride and vinyl chloride resins, such as impact modifiers, stabilizers, lubricants, processing aids,
Fillers, UV absorbers, pigments may also be used. Molding of this composition is carried out by conventional molding methods such as extrusion molding, injection molding, and calender molding.

(Example) The present invention will be described below with reference to examples.

11 ■ Top (1) Preparation of chlorinated polyvinyl chloride 300 g of polyvinyl chloride with an average degree of polymerization of 1000 obtained by suspension polymerization and 1500 g of demineralized water were placed in a glass reactor equipped with a stirrer, and the inside of the reactor was heated with nitrogen and gas. Replaced with.

Next, chlorine gas was flowed into the vessel at a rate of 7QIl/Hr.
The chlorination reaction was carried out for 5 hours by irradiating with a 100N mercury lamp at 0℃.
went. After the reaction was completed, the inside of the reactor was replaced with N2 gas to obtain chlorinated polyvinyl chloride. The chlorine content of this chlorinated polyvinyl chloride was 65%. Chlorine content was measured by oxygen flask combustion method.

(2) Synthesis of vinyl chloride copolymer In a stainless steel autoclave with an internal volume of 251 cm and equipped with a stirrer, demineralized water containing 0.3% of partially saponified polyvinyl alcohol as a dispersant for suspension polymerization was placed.

0.92 kg of N-cyclohexyl maleic acid imide and 10 g of t-butylperoxyneodecanoate as a polymerization initiator were charged. After evacuation, 4.0 kg of vinyl chloride monomer was pressurized. Autoclave stirrer 6
While rotating at 6Or+sp, set the temperature to 50℃.
Polymerization was carried out during vf. After the polymerization reaction was completed, unreacted chloride and nyl monomers were removed, followed by filtration.

When the filtrate was vacuum-dried at 50° C. for 24 hours, 3.8 kg of white powdery copolymer was obtained. The copolymer contained 80% by weight of vinyl chloride units and 20% by weight of N-cyclohexylmaleimide units. The average degree of polymerization of the copolymer was 700. Maleic acid imide units were measured by oxygen flask combustion method. Moreover, the average degree of polymerization was measured according to JIS K-6721 (vinyl chloride resin test method).

(3) Preparation of chlorinated vinyl chloride resin composition 90 parts by weight of the chlorinated polyvinyl chloride obtained in (l) and 10 parts by weight of the vinyl chloride copolymer obtained in (2) were blended.

To 100 parts by weight of this formulation, octyltin mercapto double compound as a stabilizer, 1 part by weight of octyltin maleate polymer, 0.3 part by weight of fatty acid ester as a lubricant, and methyl methacrylate-butadiene as an impact modifier.
10 parts by weight of styrene copolymer (MBS) were mixed and kneaded for 4 minutes on a mixing roll with a surface temperature of 190°C. The obtained material sheet was crushed into two parts, and the outflow amount was measured using a Koka type flow tester. As a result, the outflow amount was 1.
5XIO-”cc/s.The remaining material sheets were:
After preheating at 190℃ press for 4 minutes, 9 surface pressure 75kg/cj
A test piece was prepared by pressing at G for 4 minutes. The flexibility temperature, tensile strength, and impact value of this test piece were measured. Flexibility temperature and tensile strength are JIS K-6745 (rigid vinyl chloride board)
Accordingly, the impact value was measured according to JIS K-7111.

As a result, the flexibility temperature was 93℃ and the tensile strength was 570kg/c.
J1 (20℃) and 450kg/cd (60℃),
And the impact value was 12 kg-cra/cd.

These results are shown in the table below.

New l crude 1 Except that N-phenylmaleimide was used instead of N-cyclohexylmaleimide, and this N-phenylmaleimide unit was contained in the copolymer at a ratio of 15% by weight. A vinyl chloride copolymer was synthesized in the same manner as in Example 1.

The average degree of polymerization of this vinyl chloride copolymer was 1,000. A chlorinated vinyl chloride resin composition was prepared in the same manner as in Example 1, except that 15 parts by weight of this vinyl chloride-based copolymer and 85 parts by weight of the chlorinated polyvinyl chloride of Example 1 were blended. When the physical properties of this chlorinated vinyl chloride resin composition were measured using the same method as in Example 1, the amount of outflow was ! , 8×10-”cc/s.

Flexibility temperature is 93℃2 Tensile strength is 580kg/aj (20
℃).

and 460 kg/ad (60°C), and the impact value was 10 kg·on/cd. These results are shown in the table below.

Chlorinated polyvinyl chloride was prepared in the same manner as in Example 1, except that polyvinyl chloride having an average degree of polymerization of 1200 was used and the chlorine content was 62% by weight. A chlorinated vinyl chloride resin composition was prepared in the same manner as in Example 1 except that 80 parts by weight of this chlorinated polyvinyl chloride and 20 parts by weight of the vinyl chloride copolymer of Example 1 were blended. When the physical properties of this chlorinated vinyl chloride resin composition were measured in the same manner as in Example 1, the outflow amount was 2.0 x 10-"
cc/s, flexibility temperature is 94℃, tensile strength is 600 kg
/crl (20℃), and '490kg/cd
(60°C), and the impact value was 13 kg-■/-.

Chlorinated polyvinyl chloride was synthesized in the same manner as in Example 1, except that polyvinyl chloride having an average degree of polymerization of 800 was used. On the other hand, except that N-phenylmaleimide was used in place of N-cyclohexylmaleimide and the N-phenylmaleimide unit was contained in the copolymer at a ratio of 10% by weight, Examples A vinyl chloride copolymer was synthesized in the same manner as in Example 1. The average degree of polymerization of this vinyl chloride copolymer was 1,200. A chlorinated vinyl chloride resin composition was prepared in the same manner as in Example 1, except that 5 parts by weight of this vinyl chloride-based copolymer and 95 parts by weight of the above-mentioned chlorinated polyvinyl chloride were blended. When the physical properties of this chlorinated vinyl chloride resin composition were measured in the same manner as in Example 1, the flow rate was 1.6XIQ-''cc/, the softening temperature was 94°C, and the tensile strength was 620kg/- (20°C). ,
and 500 kg/cj (60 °C), and the impact value was 16 kg-cm/aJ. These results are shown in the table below.

Using chlorinated polyvinyl chloride prepared in the same manner as in Example 1, a chlorinated vinyl chloride resin composition was prepared without blending a vinyl chloride copolymer. When the physical properties of this chlorinated vinyl chloride resin composition were measured by the same method as in Example 1, the flow rate was 0.7 x 10-''cc/s.

Soft temperature is 94℃, tensile strength is 590 to 1r/cd (2
0℃).

and 460 kg/cd (60°C), and the impact value was 8 kg·cs/cd. These results are shown in the table below.

Comparison Example 1 Chlorinated polyvinyl chloride was prepared in the same manner as in Example 1, except that polyvinyl chloride having an average degree of polymerization of 350 was used. On the other hand, the average degree of polymerization was 1000. A vinyl chloride copolymer was synthesized in the same manner as in Example 1, except that 15% by weight of N-cyclohexylmaleimide units were contained. A chlorinated vinyl chloride resin composition was prepared in the same manner as in Example I, except that 15 parts by weight of this vinyl chloride copolymer and 85 parts by weight of the vinyl chloride copolymer described above were blended. The physical properties of this chlorinated vinyl chloride resin composition were measured by the same method as in Example 1, and the flow rate was 3.5 x 10-''cc/s, the softening temperature was 94°C, and the tensile strength was 560 kg/ad (20°C). , and 450ktr
/cdl (60°C).

The impact value was 2 kg-cm/cni. These results are shown in the table below.

40% by weight of base N-cyclohexyl maleic acid imide units
A chlorinated vinyl chloride resin composition was prepared in the same manner as in Example 1 except for the following. The physical properties of this chlorinated vinyl chloride resin composition were measured in the same manner as in Example 1. The flow rate was 0.8 x 1 O-2 cc/s, the softening temperature was 95°C, and the tensile strength was 640 kg/aJ (20°C ), and 530 kg/- (60°C), and the impact value is 'l kg
-ell/crA. These results are shown in the table below.

Example 1 except that N-phenylmaleimide was used in place of N-cyclohexylmaleimide and the N-phenylmaleimide unit was contained in the copolymer at a rate of 20% by weight. A vinyl chloride copolymer was synthesized in the same manner. The average degree of polymerization of this vinyl chloride copolymer was 700. A chlorinated vinyl chloride resin composition was prepared in the same manner as in Example 1, except that 50 parts by weight of this vinyl chloride-based copolymer and 50 parts by weight of the chlorinated polyvinyl chloride of Example 1 were blended. When the physical properties of this chlorinated vinyl chloride resin composition were measured by the same method as in Example 1, the outflow rate was 1.0 x 10-''cc/s.

Flexibility temperature is 93℃, tensile strength is 590kg/aJ (20
℃).

and 450 kg/aJ (60°C), and the impact value was 3 kg·cs/aJ. These results are shown in the table below.

Chlorinated polyvinyl chloride was prepared in the same manner as in Example 1, except that polyvinyl chloride having a calibrated average degree of polymerization of 2500 was used and the chlorine content was 62% by weight. On the other hand, Example 1 except that N-phenylmaleimide was used instead of N-cyclohexylmaleimide and this N-phenylmaleimide unit was contained in the copolymer at a ratio of 20% by weight. A vinyl chloride copolymer was synthesized in the same manner.

The average degree of polymerization of this vinyl chloride copolymer was 700. Except for blending 15 parts by weight of this vinyl chloride copolymer and 85 parts by weight of the above chlorinated polyvinyl chloride,
A chlorinated vinyl chloride resin composition was prepared in the same manner as in Example 1. When the physical properties of this chlorinated vinyl chloride resin composition were measured by the same method as in Example 1, the flow rate was 0.
3X10-”cc/s, flexibility temperature is 95℃, tensile strength is 6
10kg/a! (20℃), and 480kg/ad
(60° C.) and the impact value was 11 kg·cm/−. These results are shown in the table below.

The procedure was carried out except that N-phenylmaleimide was used in place of N-cyclohexylmaleimide, and this N-phenylmaleimide unit was contained in the copolymer at a ratio of 20% by weight. A vinyl chloride copolymer was synthesized in the same manner as in Example 1.

The average degree of polymerization of this vinyl chloride copolymer was 400. A chlorinated vinyl chloride resin composition was prepared in the same manner as in Example 1, except that 20 parts by weight of this vinyl chloride-based copolymer and 80 parts by weight of the chlorinated polyvinyl chloride of Example 1 were blended. When the physical properties of this chlorinated vinyl chloride resin composition were measured in the same manner as in Example 1, the flow rate was 2.3 x 10-''cc/s.

Flexibility temperature is 94℃, tensile strength is 580kg/cd (20
℃).

and 440 kg/aJ (60°C), and the impact value was 6 pupils/011/aJ. These results are shown in the table below.

A vinyl chloride homopolymer was synthesized in the same manner as in Example 1, except that N-cyclohexylmaleimide was not used. The average degree of polymerization of this vinyl chloride homopolymer was 1,000. Except that 10 parts by weight of this vinyl chloride homopolymer and 90 parts by weight of the chlorinated polyvinyl chloride of Example 1 were blended.

A chlorinated vinyl chloride resin composition was prepared in the same manner as in Example 1. When the physical properties of this chlorinated vinyl chloride resin composition were measured by the same method as in Example 1, the flow rate was 3.
0×10-”cc/s, softening temperature 84°C.

Tensile strength is 580kg/d (20℃) and 320k
g/aJ (60℃), and the impact value is 15kJZ-3/
-It was.

These results are shown in the table below.

(Left below) As is clear from the Examples and Comparative Examples, the chlorinated vinyl chloride resin composition of the present invention has good heat resistance and excellent processability. It also has high impact resistance. Average degree of polymerization is 3
A chlorinated vinyl chloride resin composition using a chlorinated polyvinyl chloride with an average degree of polymerization of 400, a chlorinated vinyl chloride resin composition using a vinyl chloride copolymer with an average degree of polymerization of 400, and N-cyclohexyl maleic acid imide. All chlorinated vinyl chloride resin compositions using a vinyl chloride copolymer containing 40% by weight of units lack impact resistance. Average degree of polymerization is 2500
Chlorinated vinyl chloride resin compositions using chlorinated polyvinyl chloride and resin compositions (mainly composed of chlorinated polyvinyl chloride) that do not contain a vinyl chloride copolymer have low runoff values. Poor workability. Even if 50 parts by weight of vinyl chloride copolymer is blended with 50 parts by weight of chlorinated polyvinyl chloride,
This results in a composition with low impact resistance. Compositions containing vinyl chloride homopolymers have good processability but lack heat resistance.

(Effect of the invention) The chlorinated vinyl chloride resin composition of the present invention thus has the following properties:
Since it is made by blending a vinyl chloride copolymer having N-substituted maleic acid imide units with chlorinated polyvinyl chloride, it has good heat resistance, excellent processability, and high impact resistance. Excellent heat resistance of chlorinated polyvinyl chloride,
Workability is significantly improved while maintaining impact resistance. the result.

The chlorinated vinyl chloride resin composition of the present invention is suitably used as a thermoplastic material for hard molded products such as pipes and plate calender films through processes such as extrusion, injection, compression, and transfer molding.

that's all

Claims (1)

[Claims] 1. (1) Chlorinated polyvinyl chloride obtained by post-chlorinating polyvinyl chloride having an average degree of polymerization of 400 to 2000.
and (2) 5 to 30 parts by weight of a vinyl chloride-based copolymer having an average degree of polymerization of 500 to 1500 and having 70 to 95 weight % of vinyl chloride units and 5 to 30 weight % of N-substituted maleic acid imide units, A chlorinated vinyl chloride resin composition containing. 2. The chlorine content of the chlorinated polyvinyl chloride is 60 to 7.
The chlorinated vinyl chloride resin composition according to claim 1, which has a content of 0% by weight.