JPS62149763A - Method for preventing vinyl chloride resin molding from being charged - Google Patents

Abstract

PURPOSE:To inexpensively obtain the titled molding having an antistatic effect over a long period of time, by coating or impregnating a vinyl chloride resin molding with a soln. obtd. by dissolving a specified vinyl chloride copolymer in an org. solvent. CONSTITUTION:A vinyl chloride polymer having an average degree of polymn. of 200-1,000, composed of 50-96wt% vinyl chloride unit (a), 1-10wt% (meth) acrylic ester derivative unit (h) having a substd. ammonio group, represented by formula I (wherein R1 is H or CH3; R2 is a 2-6 C lower alkylene; R3 to R5 are each a 1-4 C alkyl or alkenyl; X is halogen) and 3-40wt% (meth)acrylic acid/polyalkylene oxide ester unit (c) of formula II (wherein R4 is R1 R7 is R2; n is 1-23), is dissolved in an org. solvent (e.g., a solvent mixture of methyl ethyl ketone and toluene in a 1/1 weight ratio) to obtain a soln. (A). A vinyl chloride resin molding is coated or impregnated with the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for preventing static electricity on vinyl chloride resin molded bodies, and in particular, a method for preventing static electricity on vinyl chloride resin molded bodies that can be made inexpensive and maintain the antistatic effect. Regarding the method.

(Prior art) Vinyl chloride resin is inexpensive, has good moldability, and has excellent properties, so it is used in various molded products.

Widely used as sheets and films.

However, molded objects made of vinyl chloride resin are easily charged with electricity.
For this reason, it becomes the cause of various disorders. In order to prevent such charging, attempts have been made to impart electrical conductivity to the molded body.

Two different methods have been proposed for imparting conductivity to vinyl chloride resin molded bodies. For example, there is a method of applying a surfactant to the surface of the molded body. There is also a method of adding a surfactant, carbon blank, metal powder, tetraelectric fiber, etc. to a vinyl chloride resin, kneading it, and then molding it. However, since the surfactant easily bleeds and falls off the surface of the molded article, the antistatic effect is not maintained. Although the antistatic effect can be sustained by adding carbon blank, metal powder, conductive fibers, etc., it is necessary to add a large amount of these conductive substances in order to obtain the desired conductivity. Therefore, it is expensive. A method of attaching a noble metal or metal oxide to the surface of a vinyl chloride resin molded body by vapor deposition, sputtering, etc. has an excellent antistatic effect, but is expensive and has low productivity.

To solve these drawbacks, carbon blank,
There is a method of imparting electrical conductivity by using a conductive paint in which a conductive substance such as metal powder is dispersed in a resin solution and applying this to a vinyl chloride resin molded body. Although this method can provide a comparable antistatic effect at low cost, since the conductive substance is foreign to the resin, there is still a risk of bleeding or falling off.

(Problems to be Solved by the Invention) The present invention is intended to solve the above-mentioned conventional problems, and its purpose is to improve the charging of vinyl chloride resin molded articles that can provide a long-lasting antistatic effect. The purpose is to provide a method of prevention. Another object of the present invention is to provide a method for preventing static electricity on a vinyl chloride resin molded article, which can be done at low cost.

(Means for Solving the Problems) The present invention provides a method for eliminating bleed by applying a vinyl chloride copolymer containing one unit of a monomer having conductivity to a vinyl chloride resin molded body instead of a conductive paint. There is no falling off,
A long-lasting antistatic effect can be obtained at low cost. It was completed based on the inventor's knowledge.

The method for preventing static electricity of a vinyl chloride resin molded article of the present invention includes (
1) 50 to 90% by weight of vinyl chloride units, (2) 1 to 10% by weight of substituted ammonio group-containing (meth)acrylic acid ester derivative units represented by formula (I), and (31(II)
) A step of dissolving a vinyl chloride-based copolymer having 3 to 40% by weight of (meth)acrylic acid polyalkylene oxide ester units represented by the formula in an organic solvent, and applying the solution to a vinyl chloride-based resin molded article. Alternatively, the method includes a step of immersing the molded body in the solution, thereby achieving the above object.

R.

+CIIZ-C→- C-0+R70). -11... (IT) Here.

R1 and R6 are the same or different and are a hydrogen atom or a methyl group.

R2 and R7 are the same or different and have 2 carbon atoms
~6 lower alkylene groups.

R,, R4 and R3 are the same or different.

An alkyl or alkenyl group having 1 to 4 carbon atoms.

X is halogen, and n is an integer from 1 to 23.

In such an antistatic method, since a vinyl chloride copolymer is used as the conductive substance, it is compatible with the vinyl chloride resin and is almost integrated with the resin. Therefore, the conductive material will not bleed or fall off (
A long-lasting antistatic effect can be obtained.

The vinyl chloride copolymer contains 50 to 50 vinyl chloride units.
The content is 96%, preferably 75 to 94%. When it is less than 50% by weight, the copolymer tends to fall off from the vinyl chloride resin molding.

A lasting antistatic effect cannot be obtained. If it exceeds 96% by weight, the desired antistatic properties cannot be obtained.

In the copolymer, there are 1 to 10 substituted ammonio group-containing (meth)acrylic acid ester derivative units represented by formula (I).
It is contained in a range of 2 to 6%, preferably 2 to 6%.

If it is less than 1% by weight, the desired antistatic properties cannot be obtained. When it exceeds 10% stirring.

Although the antistatic properties are good, the hydrophilicity increases.

Solubility in organic solvents decreases. For example, N.

It is only soluble in highly polar organic solvents such as N-dimethylformamide. Since N,N-dimethylbormamide has a strong dissolving power, it has an unfavorable effect on the physical properties of the vinyl chloride resin molded article, such as dissolving or deforming it.

The (meth)acrylic acid polyalkylene oxide ester unit represented by the formula (II) is present in the copolymer from 3 to
40% by weight.

It is preferably contained in a range of 5 to 20% by weight. When it is less than 3% by weight, hydrophilicity increases and solubility in organic solvents decreases. Even if the amount exceeds 40% by weight, the antistatic properties and solubility will hardly be improved. The compound represented by formula (II) is expensive, and if it is contained in a large amount in the copolymer, it will be wasted.

(I) Monomers that provide the substituted ammonio group-containing (meth)acrylic acid Si i position include 1, for example, 2-hydroxy-3-acryloyloxypropyltrimethylammonium chloride, 2-hydroxy-3
-methacryloyloxypropyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, and methacryloyloxyethyltrimethylammonium chloride. Also.

Examples of the monomer providing the (meth)acrylic acid polyalkylene oxide ester unit represented by the formula (II) include polypropylene glycol methacrylate, polyethylene glycol methacrylate polyethylene glycol polypropylene glycol methacrylate polyethylene glycol polybutylene gelicol methacrylate.

The vinyl chloride copolymer of the present invention has antistatic properties.
One unit of another monomer copolymerizable with vinyl chloride may be included within the range not included. Examples of seven polymers include ethylene and propylene.

vinegar! There are vinyl, vinylidene chloride, hydroxyethyl acrylate, and hydroxypropyl acrylate. One unit of such monomer is usually contained in an amount of 10% by weight or less.

As a method for synthesizing the copolymer, any known polymerization method can be used, such as emulsion polymerization, suspension polymerization, solution polymerization, and precipitation polymerization.

The organic solvent is preferably a solvent that dissolves the vinyl chloride copolymer, does not dissolve, deform or swell the vinyl chloride resin molded article in a short time, and is highly volatile. Such solvents include, for example, methyl ethyl ketone/
There is a toluene mixed solvent.

If the copolymer solution is a sheet-shaped molded product.

It is applied to the molded body by surface coating using a roll coater, doctor blade, etc. In the case of irregularly shaped products, a solution of the copolymer may be spray coated or the molded product may be immersed in the solution.

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

Vinyl chloride, methacryloyloxyethylene trimethylammonium chloride as a substituted ammonio group-containing (meth)acrylic ester derivative, and tetraethylene glycol monomethacrylate as a (meth)acrylic acid polyalkylene oxide ester are added to methanol, and lauroyl is added as a catalyst. Add peroxide, 5
Polymerization was carried out at 5°C for 10 hours. After removing methanol by centrifugation, vacuum drying was performed at 50° C. for 24 hours to obtain a copolymer. The copolymer contains 88% vinyl chloride units.
, (I) Substituted ammonio group-containing (meth) represented by formula
2% by weight of acrylic acid ester derivative units.

It contained 10% by weight of (meth)acrylic acid polyfulkylene oxide units represented by formula (U). This copolymer was dissolved in a mixed solvent of methyl ethyl ketone/toluene (weight ratio 1/l) to prepare a resin solution having a concentration of 15% by weight. Apply this solution for 21 hours using a doctor blade.
It was applied to a hard vinyl chloride plate with a thickness of 10 μm to form a film. The surface resistivity, adhesion and water resistance of the film were measured as follows.

Resistance value of surface hardness; After leaving the hard vinyl chloride plate coated with a film at 20℃ and 65% R11 for 24 hours, IIIGI
The resistance value was measured according to JISK-6911 using IMEGOIIM METERTl'l-8601 (manufactured by Takeda Riken Co., Ltd.).

Adhesion: Pockets were placed on the film at intervals of one square, and a peel test was performed using cellophane tape. The number of peeled pieces out of 100 stitches was used as a measure of adhesion.

Water resistance: The hard vinyl chloride plate coated with the film was immersed in water at 20° C. for 24 hours, air-dried at room temperature, and the 1-surface specific resistance value was measured. If it has good water resistance.

There is almost no increase in surface resistivity before and after immersion.

The results of these measurements are shown in the table below.

human blood charcoal 1 82% by weight of vinyl chloride units in the copolymer.

A copolymer was synthesized in the same manner as in Example 1, except that the substituted ammonio group-containing (meth)acrylic acid ester derivative unit represented by formula (1) was 8% by weight. Using this copolymer, a film was formed on a hard vinyl chloride board in the same manner as in Example 1.

Its surface resistivity, adhesion and water resistance were measured.

The results of these measurements are shown in the table below.

Taiko plate owner 90% by weight of vinyl chloride units in the copolymer.

Other than containing 4% by weight of substituted ammonio group-containing (meth)acrylic acid ester derivative units represented by formula (1) and 6% by weight of (meth)acrylic acid polyalkylene oxide ester units represented by formula (■) A copolymer was synthesized in the same manner as in Example 1. Using this copolymer, a film was formed on a hard vinyl chloride board in the same manner as in Example 1.

Its surface resistivity, adhesion and water resistance were measured.

The results of these measurements are shown in the table below.

Comparative Example 1 89.5% by weight of vinyl chloride units in the copolymer,
A copolymer was synthesized in the same manner as in Example 1, except that the amount of the substituted ammonio group-containing (meth)acrylic acid ester derivative represented by formula (1) was 0.5% by weight. Using this copolymer, a film was formed on a hard vinyl chloride plate by the same method as in Example 1, and the surface specific resistance value,
Adhesion and water resistance were measured. The results of these measurements are shown in the table below.

comparison 1 78% by weight of vinyl chloride units in the copolymer.

A copolymer was synthesized in the same manner as in Example 1, except that the substituted ammonio group-containing (meth)acrylic acid ester derivative unit represented by formula (I) was 12% by weight. Since this copolymer did not dissolve in a mixed solvent of methyl ethyl ketone/toluene (weight ratio 1/1), it was not possible to form a film on the hard vinyl chloride board.

This 'M (M shadow) 93% by weight of vinyl chloride units in the copolymer.

A substituted ammonio base represented by the formula (1) is combined with 4% by weight of (meth)acrylic acid ester derivative units and 2% by weight of (meth)acrylic acid polyalkylene oxide ester units represented by the formula (n). A copolymer was synthesized in the same manner as in Example 1 except for this. Since this copolymer did not dissolve in a mixed solvent of methyl ethyl ketone/toluene (weight ratio 1/1), it was not possible to form a film on the hard vinyl chloride board.

Comparative Example 4 In place of the vinyl chloride copolymer, 100 parts by weight of vinyl chloride-vinyl acetate copolymer (manufactured by VYIIH, UCC, the proportion of vinyl acetate units is 14% by weight), a cationic surfactant ( A copolymer was prepared in the same manner as in Example 1, except that a mixture of 5 parts by weight of cation BB (manufactured by NOF Corporation) and 10 parts by weight of a nonionic surfactant (Nonion L-41 manufactured by NOF Corporation) was used. Synthesized. Using this copolymer, a film was formed on a hard vinyl chloride plate in the same manner as in Example 1, and its surface resistivity, adhesion, and water resistance were measured. The results of these measurements are shown in the table below.

As is clear from the Examples and Comparative Examples, according to the antistatic method of the present invention, a vinyl chloride resin molded article having a low surface resistivity value and excellent conductivity can be obtained. Therefore, the antistatic effect is high. The obtained molded product has excellent film adhesion and water resistance. Even if a copolymer containing substituted ammonio group-containing (meth)acrylic acid ester BM'J unit represented by ([)2 in an amount of only 0.5 weight and 1% is used to prevent static electricity.

The obtained vinyl chloride resin molded article has a high 9 surface specific resistance value, and the desired antistatic property cannot be obtained. Copolymers containing 12% by weight of one monomer unit represented by formula (I) and
A copolymer containing only 2% by weight of monomer units represented by formula r) cannot be used in the method of the present invention because it is insoluble in the methyl ethyl ketone/toluene mixed solvent. In the conventional antistatic method using a surfactant, the obtained vinyl chloride resin molded article lacks adhesiveness and water resistance.

(The following is a blank space) (Effects of the Invention) According to the present invention, as described above, the vinyl chloride resin molded article is effectively prevented from being charged. Moreover.

The antistatic property of the molded body is maintained over a long period of time.

It has sustainability. As a result 1, the antistatic method of the present invention is as follows:
It can be effectively used for vinyl chloride resin molded articles.

that's all

Claims (1)

[Claims] 1, (1) 50 to 90% by weight of vinyl chloride units, (2) (
I) 1 to 10% by weight of substituted ammonio group-containing (meth)acrylic acid ester derivative units represented by formula (3) and 3 to 40% by weight (meth)acrylic acid polyalkylene oxide ester units represented by formula (II) A vinyl chloride resin molding comprising the steps of: dissolving a vinyl chloride copolymer having the following in an organic solvent; and applying the solution to a vinyl chloride resin molded article or immersing the molded article in the solution. How to prevent static electricity on your body. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) Here, R_1 and R_6 are the same or different, and are hydrogen atoms or methyl groups. , R_2 and R_7 are the same or different, lower alkylene groups having 2 to 6 carbon atoms, R_3, R_4 and R_5 are the same or different,
an alkyl or alkenyl group having 1 to 4 carbon atoms; X is halogen; and n is an integer of 1 to 23. 2. The average degree of polymerization of the vinyl chloride copolymer is 200
The method for preventing static electricity of a vinyl chloride resin molded article according to claim 1, wherein the antistatic charge is in the range of 1,000 to 1,000.