JPH0665459A - Polyvinylchloride-based resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition excellent in permanent antistatic properties and moldability without impairing physical properties and useful for films, etc., by including a polyvinyl chloride-based resin and a specific copolymer at a specific ratio. CONSTITUTION:The objective composition contains (A) 100 pts.wt. polyvinyl chloride based resin and (B) 1-50 pts.wt. copolymer having 5000-5000000 weight- average molecular weight and obtained by copolymerizing a monomer mixture consisting of (i) 1-50wt.% monomer having a sulfonic acid group such as 2- sulfoethylmethacrylate, (ii) 1-50wt.% (meth)acrylate monomer having a polyoxyalkylene chain, (iii) 20-98wt.% (meth)acrylate monomer having 1-4C alkyl group and (iv) 0-70wt.% other copolymerizable monomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyvinyl chloride resin composition having antistatic properties, and more particularly to a polyvinyl chloride resin composition having permanent antistatic properties.

[0002]

2. Description of the Related Art Polyvinyl chloride resins are used for various purposes because they are relatively inexpensive and have excellent mechanical properties, heat resistance, transparency and electrical insulation.
However, this type of resin is apt to be charged with static electricity, which easily causes obstacles such as dust absorption, mutual attraction between films, and reduction of work efficiency due to repulsion.

In order to solve such drawbacks, various methods have been conventionally proposed. Method of applying antistatic agent (JP-A-61-240, JP-A-61-24)
No. 1) requires a coating step of an antistatic agent in addition to the molding step, and thus has a problem of reduced productivity, and also has a problem of reduced antistatic effect due to aging or washing.

The method of kneading an antistatic agent into a resin (Japanese Patent Laid-Open Nos. 63-277289 and 2-110154) solves the problem of reduced productivity in that no coating step is required. However, there are problems such as stains on the surface of the molded product due to bleed-out of the kneaded antistatic agent, deterioration of appearance, and deterioration of antistatic effect due to aging of the kneaded antistatic agent.

The method of kneading the polyoxyalkylene glycol (Japanese Patent Laid-Open No. 51-143049) has a problem that the permanent antistatic property is poor. As a chemical modification method, a method in which an N-polyoxyalkylene group-substituted acrylamide monomer is copolymerized during the production of a polyvinyl chloride resin (Japanese Patent Laid-Open No. 4-312058).
JP-A 8-750) has a problem of deteriorating the original physical properties of the polyvinyl chloride resin.

[0006]

As described above, in the case where the conventionally known antistatic treatment is applied, the antistatic performance, particularly the permanent antistatic performance is inferior or the physical properties inherent to the polyvinyl chloride resin are deteriorated. There was a problem and a solution was desired.

In view of the above circumstances, the present invention is a polyvinyl chloride resin having excellent antistatic performance, particularly permanent antistatic performance, and excellent moldability without deteriorating the original physical properties of the polyvinyl chloride resin. The purpose is to provide a composition.

[0008]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to achieve the above object. As a result, as a side chain, a sulfonic acid group, a polyoxyalkylene chain and a short chain are added to a polyvinyl chloride resin. A blend of a specific amount of a specific copolymer having a chain alkyl group has excellent antistatic performance, in particular, excellent antistatic performance, and does not deteriorate the physical properties inherent to the polyvinyl chloride resin, and mechanical properties and The inventors have found that the composition has excellent heat resistance and excellent moldability, and completed the present invention.

That is, the present invention comprises: a) 100 parts by weight of a polyvinyl chloride resin, b) 1 to 50% by weight of a monomer having a sulfonic acid group, and a (meth) acrylate unit having a polyoxyalkylene chain. 1 to 50% by weight, 1 carbon
20 to 98% by weight of (meth) acrylate monomer having 4 to 4 alkyl groups and other copolymerizable monomer 0
To 70 parts by weight of a monomer mixture, and 1 to 50 parts by weight of a copolymer having a weight average molecular weight of 5,000 to 500,000. It relates to a resin composition.

[0010]

In the present invention, as the polyvinyl chloride resin as the component a, a homopolymer of vinyl chloride, a copolymer of vinyl chloride and ethylene, propylene, vinyl acetate or the like, or a chloride Examples thereof include copolymers of vinyl and vinyl ethers, esters of acrylic acid or methacrylic acid, acrylamide, acrylonitrile, maleimide compounds, and the like. Among these, one kind thereof may be used alone or two or more kinds may be mixed. use. These resins are
Any production method such as bulk polymerization, suspension polymerization, emulsion polymerization and solution polymerization may be used. The degree of polymerization is not particularly limited, but those having a degree of polymerization of about 600 to 2,500 are usually preferable.

In the present invention, the copolymer as the component b is a monomer having a sulfonic acid group, a (meth) acrylate monomer having a polyoxyalkylene chain, and a carbon number of 1 to 1.
It is obtained by copolymerizing a monomer mixture containing a (meth) acrylate monomer having an alkyl group of 4 and optionally other copolymerizable monomer, and its molecular structure is random. It may be in the shape of a block, block or graft.

The above copolymerization can be carried out by utilizing a bulk polymerization method, a solution polymerization method or the like. Further, for the purpose of homogenizing the copolymer, the whole amount or a part of the monomer, the polymerization initiator and the chain transfer agent may be dropped and polymerized. Further, for the purpose of synthesizing a block copolymer or a graft copolymer, a polymerization initiator having a plurality of peroxide groups in the molecule may be used.

Examples of the monomer having a sulfonic acid group include 2-sulfoethyl (meth) acrylate and 2-sulfoethyl (meth) acrylate.
Examples thereof include sulfopropyl (meth) acrylate, methallyl sulfonic acid and styrene sulfonic acid. The sulfonic acid group contained in this monomer can be converted to a copolymer and then converted to an alkali metal salt if necessary.

The sulfonic acid group-containing monomer is contained in the monomer mixture in an amount of 1 to 50% by weight, preferably 5 to 30% by weight.
Used. If it is less than 1% by weight, the antistatic effect is small,
If it exceeds 50% by weight, the compatibility with the polyvinyl chloride resin deteriorates, and the original physical properties of the polyvinyl chloride resin deteriorate.

Having a polyoxyalkylene chain (meth)
The acrylate monomer is an ester of (meth) acrylic acid with a compound having a polyether moiety obtained by polymerizing oxyalkylene having 2 to 4 carbon atoms. Specifically, polyoxyethylene mono (meth) acrylate, polyoxypropylene mono (meth) acrylate, polyoxybutylene mono (meth) acrylate, polyoxyethylene polyoxypropylene mono (meth) acrylate , Methoxypolyoxyethylene mono (meth) acrylate, butoxypolyoxyethylene mono (meth) acrylate, phenoxypolyoxypropylene mono (meth) acrylate
And the like. The degree of polymerization of the oxyalkylene group of the polyoxyalkylene chain is not particularly limited, but it is usually preferably in the range of 2 to 90.

The (meth) acrylate monomer having this polyoxyalkylene chain is used in the monomer mixture in an amount of 1 to 50% by weight, preferably 5 to 30% by weight. 1% by weight
If it is less than 50% by weight, the antistatic effect is small, and if it exceeds 50% by weight, the compatibility with the polyvinyl chloride resin is deteriorated and the original physical properties of the polyvinyl chloride resin are deteriorated.

Examples of the (meth) acrylate monomer having an alkyl group having 1 to 4 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and butyl. There are (meth) acrylates. When a (meth) acrylate monomer having an alkyl group having 5 or more carbon atoms is used, the compatibility with the polyvinyl chloride resin becomes poor and the original physical properties of the polyvinyl chloride resin deteriorate. .

The (meth) acrylate monomer having an alkyl group having 1 to 4 carbon atoms is 20 to 20% in the monomer mixture.
98% by weight, preferably 30 to 70% by weight is used.
If it is less than 20% by weight, the compatibility with the polyvinyl chloride resin is poor, and if it exceeds 98% by weight, the antistatic effect is deteriorated.

Other copolymerizable monomers are not particularly limited, and examples thereof include acrylonitrile, maleic anhydride, phenylmaleimide and the like.
The amount of these monomers used is 0 to 70% by weight, preferably 0 to 50% by weight in the monomer mixture. If it exceeds 70% by weight, the antistatic effect is lowered, the compatibility with the polyvinyl chloride resin is deteriorated, and the physical properties are lowered.

The weight average molecular weight of the copolymer composed of such a monomer mixture is 5,000 to 500,000, preferably 20,000 to 200,000. 5,0
When it is less than 00, the original physical properties of the polyvinyl chloride resin are deteriorated, and when it exceeds 500,000, the compatibility with the polyvinyl chloride resin is deteriorated and the physical properties are also deteriorated.

In the present invention, the mixing ratio of the component a polyvinyl chloride resin and the component b copolymer is 100 parts by weight of the component a polyvinyl chloride resin and the component b copolymer. Is 1 to 50 parts by weight, preferably 5 to 30 parts by weight. If it is less than 1 part by weight, the antistatic effect is small,
If it exceeds 50 parts by weight, the original physical properties of the polyvinyl chloride resin will deteriorate.

As the method for mixing the polyvinyl chloride resin of the component a and the copolymer of the component b, the two are mixed by using a melt mixer such as a Banbury mixer, a single screw extruder or a twin screw extruder. Alternatively, they may be blended during injection molding or extrusion molding and mixed by utilizing the kneading effect of these molding machines.

The polyvinyl chloride resin composition of the present invention comprises
In addition to containing the above a and b components as essential components, if necessary, a heat deterioration inhibitor, an ultraviolet absorber, an anti-blocking agent, a lubricant, a nucleating agent, a pigment, a polymer alloy compatibilizer, General-purpose resins, other resins such as engineering plastics, fibers such as glass fibers, carbon fibers, polyamide fibers, silica, aluminum, calcium carbonate,
An inorganic filler such as talc, mica, titanium oxide, carbon black or potassium titanate may be included.

[0024]

INDUSTRIAL APPLICABILITY As described above, the polyvinyl chloride-based composition of the present invention contains the polyvinyl chloride-based resin as the component a
By blending a specific amount of the specific copolymer as a component, the antistatic property, particularly the permanent antistatic property is excellent without impairing the original physical properties of the polyvinyl chloride resin.

[0025]

EXAMPLES Next, the present invention will be specifically described with reference to Examples. The parts in the following production examples and examples are based on weight. The weight average molecular weight of the copolymer is a value determined by gel permeation chromatography.

Production Example 1 A 4-liter glass four-necked flask equipped with a stirrer was equipped with a reflux condenser, a thermometer, a dropping funnel, and a nitrogen gas blowing tube, and 100 parts of methyl isobutyl ketone was used as a solvent.
90 parts of methyl methacrylate was added, the reaction system was made a nitrogen gas atmosphere, and the temperature was raised to 50 ° C.

Next, 5 parts of 2-sulfoethyl methacrylate, 5 parts of polyoxyethylene (10 mol) monomethacrylate, and 1.0 part of diisopropyl peroxy dicarbonate as a polymerization initiator were dissolved. The mixed solution
After being uniformly added dropwise at 50 ° C. over 6 hours, the temperature was maintained for 1 hour.

The copolymer solution thus obtained was mixed with 14
The solvent was distilled off under reduced pressure at 0 ° C. for 2 hours, the mixture was cooled and then pulverized to obtain a copolymer A. This copolymer A was a white powder and had a weight average molecular weight of 60,000.

Production Example 2 Four kinds of copolymers B to B were prepared in the same manner as in Production Example 1 except that the monomer composition, solvent and polymerization initiator were changed as shown in Table 1.
I got E. The properties of the copolymers B to E (appearance and weight average molecular weight) are as shown in Table 1.

Production Example 3 Four kinds of copolymers F to F were prepared in the same manner as in Production Example 1 except that the monomer composition, the solvent and the polymerization initiator were changed as shown in Table 2.
Got I. Properties of the copolymers F to I (appearance and weight average molecular weight) are as shown in Table 2. The copolymers F to I are outside the scope of the present invention.

[0031]

[Table 1]

[0032]

[Table 2]

Example 1 Sumitomo Chemical Co., Ltd.'s Summit SX-11F (degree of polymerization: 1,050) was used as the polyvinyl chloride resin.
This and the copolymers A to E were blended in the proportions shown in Table 3,
The following components were further added to this blend: Lubricant (Hoechst-Wax OP manufactured by Hoechst Japan) 0.5 part Lead stearate 1.0 part Barium stearate 0.7 part Tribasic sulfate 1.9 parts , A Hensiel mixer to obtain 5 kinds of resin compositions, which are kneaded for 5 minutes with a heat roll heated to a surface temperature of 185 ° C. to form a sheet, and then flat plate pressed. 1 at 190 ° C and 100 kg / cm ²
After press molding for 0 minutes, sample No. 1 for measuring physical properties was used. 1-5
The test piece of was produced.

[0034]

[Table 3]

Comparative Example 1 As the polyvinyl chloride resin, the same Sumitrite SX-11F as in Example 1 was used, and the copolymers D to I and polyoxyethylene (10 mol) glycol were prepared as shown in Table 4. , The ingredients shown in Table 5 were added, and the same ingredients as in Example 1 were further added to this mixture, and the ingredients were mixed in a Henschel mixer.
A seed resin composition was obtained. Using this composition, in the same manner as in Example 1 below, Sample No. 1 for measuring physical properties was used. 6-13
The test piece of was produced.

[0036]

[Table 4]

[0037]

[Table 5]

Specimen No. prepared in Example 1 and Comparative Example 1 above. The surface resistivity, Bicatus softening point, flexural modulus, tensile strength, and Izod impact strength of the test pieces 1 to 13 were examined in the following manner. The results are shown in Tables 6 and 7 below.

<Surface specific resistance> Using a surface specific resistance measuring device [Hirest-Tester manufactured by Mitsubishi Petrochemical Co., Ltd.], the surface after 1 minute under the conditions of 20 ° C., humidity of 50% and applied voltage of 500 volts. The specific resistance (Ω) was measured. "Untreated" in the table means that a test piece of 10 cm x 10 cm x 2 mm is 20
It is a value measured after conditioning for 1 day at 50 ° C and 50% humidity, and "washing treatment" means that the test piece is 1 ° C at 20 ° C.
It is a value measured by adjusting the condition after ultrasonic cleaning for a period of time.

<Vicat Softening Point> JIS K7206,
According to the A report, it was measured.

<Flexural Modulus> Measured according to JIS K6740.

<Tensile Strength> The tensile strength was measured according to JIS K6740.

<Izod impact strength> JIS K711
It was measured according to 0 (with a notch).

[0044]

[Table 6]

[0045]

[Table 7]

As is clear from the results shown in Tables 6 and 7, the polyvinyl chloride resin composition of the present invention (Sample No.
Nos. 1 to 5) have a small surface specific resistance value and excellent antistatic properties without deteriorating the physical properties of the resin. Also,
Even after washing with water, there is almost no change in the value, and the permanent antistatic performance is excellent. On the other hand, the polyvinyl chloride resin compositions (Sample Nos. 6 to 13) outside the scope of the present invention are inferior in any of physical properties, antistatic properties and permanent antistatic properties.

Claims (1)

[Claims] 1. A) 100 parts by weight of a polyvinyl chloride resin, b) 1 to 50% by weight of a monomer having a sulfonic acid group,
1 to 50% by weight of a (meth) acrylate monomer having a polyoxyalkylene chain, 20 to 98% by weight of a (meth) acrylate monomer having an alkyl group having 1 to 4 carbon atoms, and other copolymers 1 to 50 parts by weight of a copolymer having a weight average molecular weight of 5,000 to 500,000 obtained by copolymerizing a monomer mixture of 0 to 70% by weight of possible monomers. And a polyvinyl chloride resin composition.