JPH04268355A - Antistatic vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To produce the title compsn. having permanent antistatic properties without detriment to the surface properties and printability. CONSTITUTION:The title compsn. is obtd. by compounding a vinyl chloride resin with a hydrotalcite-like compd. contg. perchloric acid. The compd. is prepd. by filtering. washing, and drying the reaction product which is obtd. by adding an aq. sodium hydroxide soln. dropwise to an aq. soln. of magnesium perchlorate and aluminum perchlorate and reacting them or by adding perchloric acid to a dispersion of magnesium hydroxide and/or basic magnesium carbonate and aluminum hydroxide, thereby reacting them with each other and then with an aq. sodium hydroxide soln.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin composition having antistatic properties.

0002

2. Description of the Related Art Molded articles made of vinyl chloride resin compositions, like molded articles made of other polymeric materials, exhibit a charging phenomenon in which static charges are generated on the surface due to contact, friction, peeling, etc. This causes dust to adhere and contaminate the surface, reducing the product value.Furthermore, in the case of film-shaped molded products, they stick together and are difficult to handle during peeling work. Improving these troubles has great advantages, as it increases the product value and improves the workability of handling molded products. Traditionally, such improvements have been made by applying various organic polar compounds, such as compounds in which a cationic, anionic, or nonionic polar group is bonded to a higher aliphatic compound, as an antistatic agent to the surface of the molded product. Alternatively, methods have been adopted in which they are added and kneaded into the kneading process during molding to assist and promote the leakage of electrostatic charges on the surface of the molded product. These methods have the following drawbacks, and improvements have been awaited. In other words, the method of applying an organic polar compound is effective in preventing static electricity for a short period of time because it can be touched by hand or washed off during washing, but it is not durable and cannot withstand long-term use. do not have. In addition, the method of kneading is such that the antistatic effect of these organic polar compounds is exerted when these compounds are arranged in a layer on the surface of the molded product. Therefore, the so-called ejection phenomenon (bleed, bloom phenomenon) deteriorates the surface properties, and when printing on the surface of a molded product, the ink may not adhere well or be easily peeled off after printing.

0003

[Problems to be Solved by the Invention] The present invention does not have the disadvantages caused by the method of applying the organic polar compound to the surface or the method of kneading it into the surface, has durability, has excellent printability, and has excellent surface properties. An object of the present invention is to obtain a molded article made of a vinyl chloride resin composition.

0004

[Means for Solving the Problem] As a result of intensive studies, the present inventors have found that in order to solve the problem, a vinyl chloride resin composition, a mixed aqueous solution of magnesium perchlorate and aluminum perchlorate, and a sodium hydroxide aqueous solution are added. or perchloric acid is added to a mixed suspension of magnesium hydroxide and/or basic magnesium carbonate and aluminum hydroxide to react, and then a sodium hydroxide aqueous solution is reacted. By adding a hydrotalcite-like compound containing perchloric acid, which is obtained by filtering, washing, and drying, a vinyl chloride resin composition with excellent durability, printability, and surface properties and antistatic ability is obtained. They discovered this and completed the present invention.

The present invention will be explained in more detail below. The vinyl chloride resin used in the present invention is a vinyl chloride homopolymer, a copolymer mainly composed of vinyl chloride, a mutual mixture of these vinyl chloride polymers, or a mixture of the above polymers and vinyl chloride. Mixtures with polymers, etc. Specifically, polyvinyl chloride, vinyl acetate-vinyl chloride copolymer, ethylene-vinyl chloride copolymer, propylene-vinyl chloride copolymer, ethylene-vinyl acetate-vinyl chloride graft copolymer, acrylic acid ester-chloride Examples of polymers that do not contain vinyl chloride include vinyl graft copolymers, ethylene-vinyl acetate copolymers, ethylene-vinyl acetate-carbon monoxide copolymers, acrylic ester polymers, and methacrylic ester polymers. -butadiene-styrene graft copolymer, chlorinated polyethylene, special urethane resin, etc. Further, it is a polymer obtained by copolymerizing and crosslinking a crosslinkable monomer such as allyl acrylate, allyl methacrylate, diallyl adipate, diallyl maleate, diallyl phthalate, etc. with vinyl chloride.

The perchloric acid-containing hydrotalcite-like compound used in the present invention can be prepared by the following method. That is, a sodium hydroxide aqueous solution is added dropwise to a mixed aqueous solution of magnesium perchlorate and aluminum perchlorate to cause a reaction, or perchloric acid is added to a mixed suspension of magnesium hydroxide and/or basic magnesium carbonate and aluminum hydroxide. is added and reacted, and then reacted with an aqueous sodium hydroxide solution, which is then filtered, washed, and dried.

Examples of other stabilizers used in combination include tin compounds of periodicity group IV elements, compounds of group II elements such as zinc, magnesium, calcium, barium, or strontium, epoxy compounds, and polyhydric alcohols. , organic phosphites, etc.

Examples of tin compounds include tin (II),
Monoalkyltin, dialkyltin carboxylate, maleate, alkylmaleate, aralkylmaleate, alkyloxynylalkylene mercapto salt,
Carboxyalkylene mercapto salts, etc., more specifically tin(II) octoate, monobutyltin trilaurate, dibutyltin di(tridecanate), dioctyltin dilaurate, monobutyltin tris(tridesiloxycarbonylmethylene mercaptide), dibutyltin Bis(3-octyloxycarbonylethylene mercaptide), dioctyltin bis(octyloxycarbonylmethylene mercaptide), dibutyltin
3-carbonylethylene mercaptide and the like.

Examples of compounds of group II elements such as zinc, magnesium, calcium, barium or strontium include their carboxylates, phenol salts,
They are inorganic salts or double salts, and examples of carboxylic acid salts include aliphatic carboxylic acids such as octyl acid, lauric acid, palmitic acid, stearic acid, isostearic acid, oleic acid, and ricinoleic acid, or benzoic acid, paratertiary acid, etc. It is a salt with an aromatic carboxylic acid such as butylbenzoic acid or m-toluic acid, and examples of the phenol salt include salts with phenol, dimethylphenol, tert-butylphenol, octylphenol, nonylphenol, dinonylphenol, etc. Further, examples of inorganic salts and double salts include basic carbonates, basic silicates, hydrotalcites, zeolites, and the like.

The epoxy compound used in the present invention is preferably a compound having oxirane oxygen in its structure and containing no nitrogen. For example, epoxidized products of unsaturated fats and oils of animals and plants, epoxidized products of unsaturated fatty acid esters,
These include aromatic and aliphatic glycidyl ethers and epoxidized products of unsaturated alicyclic compounds. Examples of epoxidized products of unsaturated fats and oils of animals and plants include epoxidized linseed oil, and examples of epoxidized products of unsaturated fatty acid esters include epoxidized octyl stearate and epoxidized butyl stearate. Aromatic glycidyl ethers include phenol, p-tertiary butylphenol, o-phenylphenol, resorcinol, cresol novolak, bisphenol A, bisphenol F
It is a glycidyl ether of phenolic compounds such as Examples of aliphatic glycidyl ethers include glycidyl of polyols such as diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitan, and mannitol. It is ether. Examples of epoxidized unsaturated alicyclic compounds include distearyl 3,4-epoxyhexahydrophthalate, di2-ethylhexyl 3,4-epoxyhexahydrophthalate, and bis(3,4-epoxyhexahydrophthalate). 9′,10′-epoxyoctadecyl),3,4-epoxycyclohexylmethyl-3′
, 4'-epoxycyclohexanecarboxylate, ethylene glycol bis(3,4-epoxycyclohexanecarboxylate), limonene dioxide, and the like.

Examples of polyhydric alcohols include neopentyl glycol, glycerin, diglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, polycondensed pentaerythritol, mannitol, sorbitol, diglycerin monoacetate, Diglycerin adipate, trimethylolpropane dimethylolpropionate, ditrimethylolpropane acetate, pentaerythritol adipate, pentaerythritol stearate, dipentaerythritol acetate, dipentaerythritol stearate, dipentaerythritol adipate, dipentaerythritol phthalate, mannitol These include acetate, sorbitol acetate, etc.

Examples of the organic phosphite used in the present invention include triphenyl phosphite, trisnonylphenyl phosphite, diphenyldecyl phosphite, phenyldodecyl phosphite, tridecyl phosphite, and tris(2-ethylhexyl). phosphite,
Examples include tributyl phosphite, diphenylbutoxyethoxyethyl phosphite, tris(dinonylphenyl) phosphite, distearylpentaerythritol diphosphite, 4,4'-isopropylidene diphenyltetraalkyl (C12-C15) phosphite, and the like.

The vinyl chloride resin composition according to the present invention contains a plasticizer, a higher fatty acid and its ester, or a lubricant containing a metal salt, an antifogging agent, a polymer modifier, and a polymer in an amount depending on the purpose of use. Molecular processing aids, ultraviolet absorbers, light stabilizers,
Antioxidants, anti-blocking agents, flame retardants, antistatic agents, coloring agents, etc. are used in combination.

Plasticizers that can be used in the present invention include phthalic acid, trimellitic acid, pyromellitic acid, sebacic acid, azelaic acid, maleic acid, malic acid, tartaric acid, malonic acid, etc.
Esters of one or more carboxylic acids selected from monovalent to tetravalent carboxylic acids and alcohols having one or two hydroxyl groups, one type selected from monovalent to tetravalent phenols or alcohols These include organic phosphoric acid esters consisting of 1 to 3 types and phosphoric acid, chlorinated paraffins, and the like.

More specifically, examples of esters of carboxylic acid and alcohol include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, dicetyl phthalate, diisododecyl phthalate, ditridecyl phthalate, butylbenzyl phthalate, Dimethyl adipate, diethyl phthalate adipate, dibutyl adipate, dioctyl adipate, dicetyl adipate, diisononyl adipate, diisodecyl adipate, dibutyl sebacate, dioctyl sebacate, dimethyl azelate, dibutyl azelate, dioctyl azelate, dibutyl malonate, dioctyl malonate , dibutyl tartrate, dioctyl tartrate, dibutyl maleate, dioctyl maleate, tributyl citrate, trioctyl citrate, tributyl citrate acetate, trioctyl citrate acetate, trioctyl trimellitate, tetraoctyl pyromellitate, ethylene Polyesters of glycol and adipic acid, polyesters of propylene glycol and adipic acid, polyesters of propylene glycol and adipic acid, terephthalic acid, and esters of phosphoric acid such as triphenyl phosphate, tricresyl phosphate, tricylenyl phosphate, and tris. These include isopropenyl phosphate, bis{[bis((mono,di)methylphenoxy)phosphoryloxy]phenyl}propane, tris-1,2-dichloropropyl phosphate, and various chlorinated paraffins with different chlorination rates.

[0016]

EXAMPLES The excellent effects of the present invention will be explained with examples, but the present invention is not limited to the examples shown below. Example 1. Perchloric acid visceral hydrotalcite-like compound [
Synthesis Example of I] A freshly prepared aluminum perchlorate aqueous solution prepared from 156 g of commercially available magnesium perchlorate and aluminum hydroxide, equivalent to 120 g of aluminum perchlorate, was dissolved in ion-exchanged water to make a total of about 1 liter, and the mixture was heated at room temperature. While stirring, add 1 liter of 1N sodium hydroxide aqueous solution to 7
Add at a rate of 0-80 cc/min. After the addition was completed, the mixture was stirred at room temperature for about 2 hours, and then the crystals were filtered out and washed with about 2 liters of ion-exchanged water. Dry at 60°C until constant weight. Yield: 87g. (Analysis value MgO33.5%, Al
2O3 13.9%, Cl 7.1%)

Example 2. Synthesis example of hydrotalcite-like compound [II] containing perchloric acid 29.12 g of basic magnesium carbonate and 7.8 g of aluminum hydroxide were dissolved and dispersed in 200 cc of ion-exchanged water and mixed with 70% perchloric acid 96.0 g while stirring. Add 1g, 2
Mix at room temperature for an hour. 1N sodium hydroxide aqueous solution 2
Add 00 cc at a rate of 70-80 cc/min. After stirring at 50° C. for about 2 hours after the addition, the formed crystals are collected, washed with about 1 liter of ion-exchanged water, and dried at 60° C. until a constant weight is reached. Yield: 38.1g. (Analysis value
MgO 32.8%, Al2O39.9%, Cl
3.9%)

Example 3. 100 parts by weight of vinyl chloride resin (Sumilit RSX-11F: manufactured by Sumitomo Chemical Co., Ltd.), dioctyl phthalate 3
0 parts by weight, 3 parts by weight of Alcamizer 1 (Hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.), and the additives shown in [Table 1] were added, and after mixing, two 6-inch rolls were heated to 160°C. The mixture was kneaded and rolled for 4 minutes to produce a sheet. After cutting this sheet into a specified size, it is placed in a constant temperature and humidity chamber (2
After being left at 0°C (95%) for 48 hours, Shishido Electrostatic Co., Ltd.
Corona discharge (applied voltage 8k
v) After charging for 2 minutes, stop the discharge, measure the decay of the charged voltage, and measure the time until the charged voltage reaches half its value.The half-life is the ease with which the electrostatic charge of the test piece leaks, that is, the half-life. It was determined that the shorter the value, the better the antistatic ability. The results are shown in [Table 1].

[0019]

[Table 1]

Example 4. Vinyl chloride resin (Zeon 103EP: Nippon Zeon Co., Ltd.)
) 100 parts by weight, 30 parts by weight of dioctyl phthalate,
KV-67M-1 (Ba-Zn liquid composite stabilizer: Ba
The additives shown in Table 2 were added to 2 parts by weight of the product containing salt, Zn salt, organic phosphite, diketone, and phenolic antioxidant (manufactured by Kyodo Yakuhin Co., Ltd.), and the test was carried out in the same manner as in Example 1. A strip was prepared, the antistatic ability was evaluated, and the printability was evaluated.
Red ink (VCH-3: manufactured by Toyo Ink Co., Ltd.) was printed with a bar coder, and after drying overnight (approximately 12 hours), cellophane tape (manufactured by Nichiban Co., Ltd.) was attached, and after crimping, it was peeled off. The degree of adhesion of the red ink to the cellophane tape was visually inspected and rated as ◯ if there was no adhesion, △ if there was little adhesion, and × if there was a lot of adhesion. The results are shown in [Table 2].

[0021]

[Table 2]

Example 5. 100 parts by weight of polyvinyl chloride (Sumilit RSX-13: manufactured by Sumitomo Chemical Industries, Ltd.), 60 parts by weight of adipic acid polyester plasticizer (CSP-210: manufactured by Chisso Corporation), lubricant (LX-40A-2: Kyodo Yakuhin Co., Ltd.) 0.2
Parts by weight, 0.6 parts by weight of KS-41A-5 (dibutyltin mercapto liquid stabilizer: manufactured by Kyodo Yakuhin Co., Ltd.), epoxidized soybean oil (Sansocizer E-2000: Shin Nippon Chemical (
A test piece was prepared in the same manner as in Example 1 by adding the additives shown in Table 3 to 3.0 parts by weight of the sample (manufactured by Co., Ltd.), and the charging voltage and half-life due to corona discharge were measured using an honest meter. In addition, the test piece was heated at 40°C and 90% to 95% relative humidity.
After standing for a day, the surface properties were visually judged, and the printability was judged in the same manner as in Example 2. The results are shown in [Table 3].

[0023]

[Table 3]

[0024]

[Effects of the Invention] As explained above, the vinyl chloride resin composition containing the hydrotalcite-like compound containing perchloric acid of the present invention exhibits a durable and excellent antistatic effect.
In addition, it is possible to obtain a molded product that maintains good surface properties and printability, so the commercial value can be significantly improved.

Claims (1)

[Claims] Claim 1: A mixed aqueous solution of magnesium perchlorate and aluminum perchlorate is reacted with a sodium hydroxide aqueous solution dropwise on a vinyl chloride resin, or magnesium hydroxide and/or basic magnesium carbonate and aluminum hydroxide are reacted. It is characterized by adding a hydrotalcite-like compound containing perchloric acid, which is obtained by adding perchloric acid to a mixed suspension and reacting it, and then reacting it with an aqueous sodium hydroxide solution, which is then filtered, washed, and dried. A vinyl chloride resin composition with antistatic properties.