JPH06263947A - Chlorinated resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in resistances to heat and impact, useful for heat-resistant pipes, window frames, etc., comprising a chlorinated resin and a modified PP-based resin prepared by polymerization under kneading in a molten state between a propylene-based polymer and rubber-based polymer each in a molten state and a vinyl monomer. CONSTITUTION:This resin composition excellent in resistance to heat and impact, useful for the plastic molding area, esp. heat-resistant pipes, window frames, etc., can be obtained by blending (A) 1-50wt.% of a modified propylene- based polymer resin prepared by dry blending of (1) a propylene-based polymer and a rubber-based resin (e.g. ethylene-propylene-based rubber) each in a molten state with (2) a vinyl monomer (e.g. aromatic vinyl monomer such as styrene) followed by feeding the blend into an extruder where the blend is kneaded in a molten state to carry out graft polymerization and by pelletizing the resultant polymer through a pelletizer and (B) 99-50wt.% of a chlorinated resin (e.g. polyvinyl chloride-based resin), followed by addition of a stabilizer and then conducting kneading with an open rolling machine.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chlorine-containing resin composition containing a modified propylene polymer resin and a chlorine-containing resin and having excellent heat resistance and impact resistance.

[0002]

2. Description of the Related Art Chlorine-containing resins, of which polyvinyl chloride resins are excellent general-purpose resins having a good balance of price and physical properties, are produced in large quantities and used for various purposes. In particular, with the recent diversification of usage methods, improvement in heat distortion resistance and impact resistance, which are drawbacks of vinyl chloride resin, has been strongly desired for applications such as industrial members and building members.

On the other hand, a method of blending a vinyl chloride resin with a copolymer having a higher thermal softening temperature and a rubber-based resin, or a method of polymerizing a chlorine-containing monomer in the presence of the rubber-based resin to obtain the copolymer Several methods for improving heat distortion resistance and impact resistance by blending have been proposed (JP-A-60-248758 and JP-A-60-24876).
No. 1).

[0004]

However, in the case of these methods, in order to obtain the desired heat resistance and impact resistance, it is necessary to add a large amount of expensive copolymer resin, and the range of practical use is extremely limited. It had been.

In order to solve the problems of the conventional compositions, the present invention is a modified propylene-based polymer obtained by melt-kneading and polymerizing a molten propylene-based polymer or rubber-based resin with a vinyl monomer. Provided is a chlorine-containing resin composition in which the combined resin has improved compatibility with the chlorine-containing resin, and by blending the resin with the chlorine-containing resin, the heat distortion resistance and impact resistance, which are the drawbacks of the chlorine-containing resin, have been improved. The purpose is to do.

[0006]

As a result of intensive studies to solve the above-mentioned drawbacks of the conventional method, the present inventors have found that a propylene-based polymer and a rubber-based resin in a molten state are combined with a vinyl monomer. It has been found that the above object can be achieved by blending the modified propylene-based polymer resin obtained by the melt-kneading polymerization reaction, and the present invention has been completed.

That is, according to the present invention, a propylene-based polymer in a molten state, a rubber-based resin (a) and a vinyl monomer (b),
Preferably, a modified propylene polymer resin (A) obtained by subjecting an aromatic vinyl monomer or an aromatic vinyl monomer and a polar functional group-containing vinyl monomer to a melt-kneading polymerization reaction
A chlorine-containing resin composition containing, and a chlorine-containing resin (B), preferably a modified propylene-based polymer resin (A) 1 to
It is intended to provide a chlorine-containing resin composition containing 50% by weight and 99 to 50% by weight of a chlorine-containing resin (B).

The present invention will be described in detail.

(Constitution) The propylene-based polymer of the present invention is
A propylene homopolymer and a copolymer containing propylene as a main component and another olefin or an ethylenic vinyl monomer (each of which is a copolymer containing propylene at 75% by weight or more), and specifically, isotactic polypropylene, Examples include propylene-ethylene copolymer and propylene-butene copolymer. These propylene-based polymers can also be mixed and used. Further, other polymers can be used as long as the properties of the propylene polymer are not impaired.

The vinyl monomer of the present invention may be any monomer having a vinyl group, but is preferably an aromatic vinyl monomer, and further contains an aromatic vinyl monomer and a polar functional group. A combination of vinyl monomers is preferable.

It is preferable that the solubility coefficient of the vinyl monomer is 8.5 or more, which is close to the solubility coefficient of the chlorine-containing resin. When the solubility coefficient is lower than 8.5, the compatibility of the modified propylene-based polymer resin with the chlorine-containing resin decreases, which is not preferable.

Incidentally, the above solubility coefficient is obtained from Polymer Handbook
(INTERSCIENCE PUBLISHERS a division of John Wiley
and Sons issued).

As the aromatic vinyl monomer, for example, styrene, methylstyrene, vinyltoluene, vinylxylene, ethylvinylbenzene, isopropylstyrene,
Chlorostyrene, dichlorostyrene, bromostyrene and the like can be mentioned, and they can be used alone or in combination.

Further, as the polar functional group-containing vinyl monomer used in combination with the aromatic vinyl monomer, a copolymerizable alkyl ester group-containing vinyl monomer, an epoxy group-containing vinyl monomer, and a hydroxyl group-containing vinyl are used. Examples thereof include monomers and vinyl monomers having a carboxylic acid group. Preferred are alkyl ester group-containing vinyl monomers, epoxy group-containing vinyl monomers and carboxylic acid group-containing monomers.

Examples of the vinyl monomer containing an alkyl ester group include acrylic acid esters such as methyl methacrylate and ethyl methacrylate, which may be used alone or in combination. Methyl methacrylate is particularly preferable.

Examples of the epoxy group-containing vinyl monomer include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, and methacryl glycidyl ether, which may be used alone or in combination. Glycidyl methacrylate is particularly preferable.

Examples of the hydroxyl group-containing vinyl monomer include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and 2
-Hydroxybutyl methacrylate and the like can be used alone or in combination.

The carboxylic acid group-containing vinyl monomer includes, for example, acrylic acid, methacrylic acid, maleic anhydride, maleic acid, etc., which may be used alone or in combination. Maleic anhydride is particularly preferable.

The addition amount of the aromatic vinyl monomer or the aromatic vinyl monomer and the polar functional group vinyl monomer is 1 to 50% by weight, preferably 5 to 30% by weight of the propylene polymer.
% By weight. If it is less than 1% by weight, the compatibility with the chlorine-containing resin is impaired, and if it exceeds 50% by weight, the performance of polypropylene is impaired, which is not preferable.

The addition amount of the polar functional group-containing vinyl monomer used in combination is 0.2 times the amount of the aromatic vinyl monomer.
The amount is 5 times, preferably 0.5 times to 2 times.

As the radical initiator, it is easy to dissolve in the vinyl monomer due to the characteristics of the present invention, and for this reaction to carry out the polymerization at the melt-kneading temperature of the propylene-based polymer, a half-life of 1 minute is obtained. The decomposition temperature is preferably 130 to 250 ° C. Specific examples include t-butyl peroctate, bis (t-butyl peroxy) trimethylcyclohexane, cyclohexanone peroxide, benzoyl peroxide, dicumyl peroxide, t-.
Butyl perbenzoate, dimethyldi (t-butylperoxy) hexane, dimethyldi (t-butylperoxy) hexine and the like can be mentioned. The amount of the radical initiator used is usually 0.1 with respect to 100 parts by weight of the vinyl monomer.
1 to 10 parts by weight, preferably 1 to 5 parts by weight.

As other additives, polypropylene is a radical-disintegrating polymer unlike polyethylene, so that it is preferable to add a stabilizer. However, it is necessary to consider the kind and addition amount so as not to hinder the polymerization of the aromatic vinyl monomer. For example, pentaerythrityl-tetrakis ((di-t-butyl-hydroxyphenyl) propionate), octadecyl (di-t-butyl-hydroxyphenyl) propionate, thiobis (methyl t-butylphenol), trimethyl-tris (di-t-butyl). Hydroxybenzyl) benzene and other hindered phenol stabilizers, tetrakis (di-t-butylphenyl) biphenylene phosphite, tris (di-t-butylphenyl) phosphite and other phosphorus stabilizers, zinc stearate, calcium stearate, etc. There are antacid adsorbents such as metal soaps, magnesium oxide, and hydrotalcite. The amount of the stabilizer used is usually 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the propylene polymer.

The melt-kneading polymerization reaction of the propylene polymer and the rubber resin with the aromatic vinyl monomer or the aromatic vinyl monomer and the polar functional group-containing vinyl monomer is carried out in a closed container such as a Banbury mixer, extrusion. It is possible to use a continuous kneader such as a machine. The extruder is preferable when considering industrial production such as granulation. Further, the twin-screw extruder is easier to control the supply of reactants, kneading, polymerization time and the like.

The manufacturing method by the extruder is as follows. The propylene-based polymer in the form of powder or pellets is fed to the extruder and heated to 130 to 250 ° C. under pressure to melt the propylene-based polymer and the rubber-based resin to give an aroma. After the melt-kneading polymerization reaction of the group vinyl monomer or the aromatic vinyl monomer and the polar functional group-containing vinyl monomer, the strand discharged from the die is cooled and pelletized by using a pelletizer. If necessary, the pellets are cooled and ground into powder.

The vinyl monomer may be mixed with the propylene polymer and the rubber resin in advance and then supplied to the extruder, or the propylene polymer and the rubber resin in a molten state may be fed by using a liquid feeder. However, it is preferable that the propylene polymer and the rubber resin are mixed and impregnated in advance.

The radical initiator may be dissolved in the vinyl monomer in advance and added, or may be added to the mixture of the propylene polymer and the rubber resin and the vinyl monomer using a liquid feeder. good. The stabilizer is preferably mixed in advance with the propylene polymer using a Henschel mixer or the like.

Since the propylene-based polymer is a radical-disintegrating polymer unlike the ethylene-based polymer, if the polymer is simply melt-heated, the molecular weight is apt to decrease due to the breaking of the main chain.
Therefore, a modified propylene-based polymer having a low molecular weight can be obtained by melt-kneading only a polar functional group-containing vinyl monomer in the presence of an organic peroxide. However, according to the melt-kneading reaction method of the present invention, the aromatic vinyl monomer or the aromatic vinyl monomer and the polar functional group-containing vinyl monomer are efficiently reacted by reacting in the presence of a stabilizer. A modified propylene-based polymer resin containing a rubber-based resin that has been graft-reacted and has no decrease in molecular weight and has improved compatibility with a chlorine-containing resin can be obtained.

During the melt-kneading polymerization reaction, the vinyl monomer does not always 100% graft-react to modify the propylene polymer or the rubber resin, and the vinyl monomer and the propylene polymer react with each other. In addition to those bonded, those in which a vinyl monomer and a rubber resin are reactively bonded, those in which a propylene polymer and a rubber resin are reactively bonded, a propylene polymer resin, a homopolymer of a vinyl monomer A rubber-based resin is by-produced. Therefore, the modified propylene polymer resin referred to in the present invention also includes these non-grafted polymers.

The rubber resin in the present invention means a styrene thermoplastic elastomer such as SBS resin, SIS resin, SEBS resin, SBR resin, MBS resin, ABS resin, N
Butadiene rubber such as BR resin, EPM resin, EP
Ethylene-propylene rubber such as DM resin, ethylene-
It is a known rubber-based resin such as a vinyl acetate copolymer-based resin.

The chlorine-containing resin in the present invention means a polyvinyl chloride resin and a vinyl chloride-based copolymer comprising vinyl chloride and a known monomer such as ethylene, allyl chloride, 1-butene, propylene and vinyl acetate. In addition, a chlorinated polyvinyl chloride resin obtained by chlorinating a polyvinyl chloride resin or a polyvinyl chloride copolymer resin, a polyvinylidene chloride resin and the like can be mentioned.

The chlorine-containing resin composition of the present invention contains a rubber-based resin in an amount of 1 to 50% by weight based on the propylene-based polymer.
Modified propylene polymer resin (A) blended in the proportion of
1 to 50% by weight, preferably 5 to 30% by weight, and chlorine-containing resin (B) 99 to 50% by weight, preferably 95 to 70%
% By weight.

In addition to these essential components, additional components can be added to the chlorine-containing resin composition of the present invention within a range that does not impair the effects of the invention. Examples of the additional component include other thermoplastic resins, rubbers, inorganic fillers, pigments, various stabilizers (antioxidants, light stabilizers, antistatic agents, antiblocking agents, lubricants) and the like.

The chlorine-containing resin composition of the present invention is produced by dry blending these components with a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, etc., and then mixing this mixture with a single-screw or twin-screw extruder, roll, It is melt-mixed with a kneading machine such as a Banbury mixer, pelletized or crushed, and then subjected to molding. For the molding, any method such as injection molding, hollow molding, extrusion molding and the like can be adopted.

Thus, the present invention can provide a chlorine-containing resin composition having excellent heat distortion resistance and impact resistance.

[0035]

EXAMPLES Next, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following, all parts and% are based on weight unless otherwise specified.

The method for testing the physical properties of the composition is as follows. Thermal deformability: Measurement JIS K7206 (Vicat temperature load 1k
g) Impact strength: Measurement ASTM D256 Dispersion state: Dispersion state of the molded product was visually judged.

Example 1 <Production of Modified Polypropylene Polymer Resin> A 20 mm twin-screw extruder manufactured by Brabender (Germany) was used at a barrel temperature of 19
0 ℃ (However, 170 ℃ feeder part), Die temperature 200
It was set to ° C. 78 parts of Hipol B200P (powdered polypropylene manufactured by Mitsui Petrochemical Co., Ltd.), 0.05 parts of Irganox 1010 (made by Ciba-Gaiki), 0.05 parts of phosphite 168 (made by Ciba-Gaiki), 0.1 part of calcium stearate, SEBS 10 parts of resin (G1650, Shell Chemical Co.) was mixed. A mixture of 12 parts of styrene and 0.36 part of Perhexin 25B (manufactured by NOF CORPORATION) was dry blended with the above-described Hypol B200P and SEBS blend. The obtained dry blend was supplied to an extruder, melt-kneaded at 15 rpm to carry out a graft reaction, and pellets were obtained through a pelletizer. The pellets were cooled and ground into powder.

<Production of Chlorine-Containing Resin Composition> 10 parts of the modified propylene-based polymer resin obtained above and a polyvinyl chloride resin (manufactured by Nippon Zeon Co., 103EP, degree of polymerization 1050)
90 parts and 1.8 parts of a stabilizer were mixed, and this was kneaded for 5 minutes at 180 ° C. using an open roll machine to form a sheet. The temperature of the obtained sheet is 180 ° C with a press molding machine.
A test piece was prepared under conditions of 5 minutes and evaluated for various physical properties. The results are shown in Table 1.

(Examples 2 to 6) A modified propylene polymer resin was produced in the same composition as shown in Table 1 in the same manner as in Example 1 (Perhexin 25B was 3% by weight based on the vinyl monomer). The chlorine-containing resin composition shown in Table 1 was produced, and various physical properties were evaluated in the same manner as in Example 1.

Comparative Example 1 The physical properties of a polyvinyl chloride resin (103EP manufactured by Nippon Zeon Co., Ltd., 1050 polymerization degree) were evaluated. The results are shown in Table 2.

(Comparative Examples 2 to 3) Polyvinyl chloride resin (manufactured by Nippon Zeon Co., 103EP, degree of polymerization: 1050), Hypol B200P (polypropylene resin, manufactured by Mitsui Petrochemical Co., Ltd.) and MBS resin were used in the composition shown in Table 2 in Examples. 1
A chlorine-containing resin composition was produced in the same manner as described above, and various physical properties were evaluated in the same manner, but the compatibility was extremely poor and a test piece could not be prepared.

The following can be seen from Tables 1 and 2. By blending the modified propylene-based polymer resin with the chlorine-containing resin,
Improves heat resistance and impact resistance. Further, unless modified with a vinyl monomer, the propylene polymer resin and the rubber resin cannot be added to the chlorine-containing resin.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

INDUSTRIAL APPLICABILITY According to the present invention, an aromatic vinyl monomer or an aromatic vinyl monomer and a polar functional group-containing vinyl monomer (particularly an alkyl ester group-containing vinyl) are added to a molten propylene polymer and a rubber resin. Monomer, vinyl monomer containing epoxy group or vinyl monomer containing carboxylic acid group)
It is a chlorine-containing resin composition characterized by comprising a modified propylene-based polymer resin obtained by melt-kneading polymerization reaction of and a chlorine-containing resin, and can provide a molding material excellent in heat distortion resistance and impact resistance.

Claims (5)

[Claims] 1. A modified propylene-based polymer resin (A) and a chlorine-containing resin obtained by melt-kneading and polymerizing a molten propylene-based polymer and a rubber-based resin (a) with a vinyl monomer (b). A chlorine-containing resin composition comprising (B). 2. The chlorine-containing resin composition according to claim 1, wherein the rubber resin is blended in a proportion of 1 to 50% by weight with respect to the propylene polymer. 3. Modified propylene polymer resins (A) 1 to 5
The chlorine-containing resin composition according to claim 1 or 2, comprising 0% by weight and 99 to 50% by weight of the chlorine-containing resin (B). 4. The chlorine-containing resin composition according to any one of claims 1 to 3, wherein the vinyl monomer (b) is an aromatic vinyl monomer. 5. The chlorine-containing product according to claim 1, wherein the vinyl monomer (b) is an aromatic vinyl monomer and a polar functional group-containing vinyl monomer. Resin composition.