JP2005089569A - Antistatic film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic film excellent in antistatic properties and heat stability. <P>SOLUTION: The antistatic film contains (a) 50-90 wt.% polyvinyl chloride resin, (b) 1-50 wt.% antistatic plasticizer, (c) 0.5-7 wt.% quaternary ammonium salt compound, and (d) 0.05-6 wt.% anhydrous hydrotalcite compound. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a vinyl chloride resin antistatic film and sheet (hereinafter collectively referred to as “film”) having good antistatic properties and thermal stability and having no yellowing.

Polyvinyl chloride resin is a semi-rigid product to which a relatively small amount of plasticizer is added or a soft product to which a relatively large amount is added. Various packaging films or containers, agricultural films, industrial films, building material films, floors Widely used in materials.
Polyvinyl chloride resin generally has good electrical insulation, and this property is preferable in fields where insulation is required, such as wire coating materials, but when the surface of a product made of the resin is rubbed, static electricity is easily generated, Since the static electricity is charged as it is without leaking, it is so-called when used for packaging films such as partitions (curtains) for factories, computer rooms, etc., cases for transporting and protecting ICs, covering materials for electronic communication, etc. Often caused static damage.
In order to avoid electrostatic damage, non-ionic, anionic and cationic antistatic agents are generally kneaded into polyvinyl chloride resin at the time of processing or applied to the surface of the finished product. Is granted. However, when the antistatic agent is kneaded in a large amount and processed, there is a disadvantage that discoloration of the obtained product becomes large and the thermal stability is extremely poor.
As an improvement measure, JP-A-9-2733223 (see Patent Document 1) discloses a chlorine-containing resin, an aliphatic dibasic ester plasticizer such as bis (butoxyethyl) adipate, and a quaternary ammonium salt of perchloric acid. And additives usually added as a heat stabilizer to the composition to which the phosphate plasticizer is added, for example, carboxylates such as Ca, Ba, Mg, Zn, Cd, Sn, and Pb, phenolate, and organic phosphate Organic acid salts such as salts, inorganic metal compounds such as metal oxides, hydroxides, carbonates, silicates, phosphates, phosphites, aluminates or double salts thereof, organic tin compounds However, when these heat stabilizers are used, yellowing of the film occurs due to thermal deterioration during calendering, and even if the amount added is increased, yellowing can be improved. Result was not observed.

JP-A-9-2733223

  As a result of intensive studies to obtain a molded article such as an antistatic vinyl chloride resin film having good thermal stability and no discoloration such as yellowing, the present inventors have achieved the present invention.

The present invention
(1) (a) polyvinyl chloride resin 50 to 90% by weight, (b) antistatic plasticizer 1 to 50% by weight, (c) quaternary ammonium salt compound 0.5 to 7% by weight, (d) The antistatic film containing 0.05 to 6% by weight of an anhydrous hydrotalcite-based compound, (2) (c) The content of the quaternary ammonium salt compound is 1 to 5% by weight according to (1) above Antistatic film, (3) (d) Antistatic film according to (1) or (2), wherein the content of anhydrous hydrotalcite compound is 0.1 to 3% by weight, (4) ( b) The antistatic film according to any one of the above (1) to (3), wherein the volume resistivity of the antistatic plasticizer is less than 10 ¹¹ Ωcm, and (5) (b) the antistatic plasticizer. The above (which is an aliphatic dibasic acid diester and / or phthalic acid diester ( ) Antistatic film according to any one of the antistatic film according to any one of the - (4) and (6) the surface resistivity of the film is less than 10 ¹⁰ Omega above (1) to (5), Is to provide.

  The present inventors solved the above problem by further blending a specific amount of anhydrous hydrotalcite compound with a resin composition containing a vinyl chloride resin, an antistatic plasticizer and a quaternary ammonium salt compound. As a result, it has been found that a vinyl chloride resin product having good antistatic properties and thermal stability can be obtained, and the present invention has been achieved.

Examples of the polyvinyl chloride resin used in the present invention include vinyl chloride homopolymers, copolymers of vinyl chloride and comonomers copolymerizable therewith, and mixtures thereof. The homopolymer or copolymer may be produced by any method among known production methods such as suspension polymerization method, bulk polymerization method, fine suspension polymerization method and emulsion polymerization method. . Examples of the comonomer include vinyl esters such as vinyl acetate, vinyl propionate and vinyl laurate, acrylic esters such as methyl acrylate, ethyl acrylate and butyl acrylate, methacrylic esters such as methyl methacrylate and ethyl methacrylate, and dibutyl. Maleates such as maleate and diethyl maleate, fumarates such as dibutyl fumarate and diethyl fumarate, vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether, cyan such as acrylonitrile and methacrylonitrile Vinyl halides, α-olefins such as ethylene, propylene and styrene, vinyl halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, or vinylidene halides , Diallyl phthalate, polyfunctional monomers such as ethylene glycol dimethacrylate and the like, may be used singly or in combination of two or more. Of course, the comonomer is not limited to those described above. The comonomer may be in the range of 30% by weight or less, preferably 20% by weight or less in the constituents of the vinyl chloride resin.
In addition, the category of vinyl chloride resins includes chlorinated vinyl chloride resins obtained by post-chlorination of vinyl chloride resins produced as described above.
Furthermore, in the present invention, it is preferable to use a vinyl chloride resin having an average degree of polymerization of 700 or more, preferably 800 or more, 3500 or less, preferably 1300 or less. You may mix and use 2 or more types. As a mixing method, a method of mixing two or more types of resins at the time of film formation processing is generally used, but by controlling the polymerization conditions at the time of polymerization of the vinyl chloride resin, an apparent average degree of polymerization of two or more types is obtained. A method in which different vinyl chloride resins are mixed may be used.
The compounding amount of the polyvinyl chloride resin is 50 to 90% by weight in the antistatic film.

Antistatic plasticizers include aliphatic dibasic acid diesters and / or phthalic acid diesters. The aliphatic dibasic acid diester is preferably an aliphatic dibasic acid dialkoxyalkyl, and the phthalic acid diester is preferably a dialkoxyalkyl phthalate.
Among the above-mentioned antistatic plasticizers, dialkoxyalkyl adipates such as bis (2-butoxyethyl) adipate are particularly preferable.
The antistatic plasticizer preferably has a volume resistivity of less than 10 ¹¹ Ωcm, more preferably 10 ⁸ to 10 ¹⁰ Ωcm.
The blending amount of the antistatic plasticizer is 1 to 50% by weight, preferably 3 to 35% by weight in the antistatic film.

  Further, other plasticizers can be blended with the antistatic plasticizer within the range not affecting the present invention. Examples of the other plasticizers include plasticizers that can be usually added to polyvinyl chloride resins, for example, phthalate ester plasticizers such as di-2-ethylhexyl phthalate and diisononyl phthalate, and bis (2- Ethylhexyl), diisononyl adipate ester plasticizer, polyester plasticizer, trimellitic ester plasticizer, pyromellitic ester plasticizer, sebacic acid plasticizer, chlorinated paraffin plasticizer, epoxy Epoxy plasticizers such as modified soybean oil, and phosphate ester plasticizers.

The compounding quantity of a quaternary ammonium salt compound is 0.5-7 weight% in an antistatic film, Preferably it is 1-5 weight%, More preferably, it is 1-3 weight%. If the amount of the quaternary ammonium salt compound is small, a sufficient antistatic effect cannot be obtained, and if it is too large, the quaternary ammonium salt compound may be ejected onto the film surface.
By combining the quaternary ammonium salt compound and the antistatic plasticizer within the above ranges, excellent antistatic properties can be imparted to the film without jetting out.
Quaternary ammonium salt compounds include dimethyl butyl hydroxyethylammonium perchlorate, dimethyl octyl hydroxyethylammonium perchlorate, dimethyl decyl hydroxylethylammonium perchlorate, dimethyl dodecylhydroxyethylammonium perchlorate, dimethyl stearyl.・ Hydroxyethylammonium perchlorate, trimethyl dodecyl ammonium perchlorate, dimethyl distearyl ammonium perchlorate, dimethyl dipalmityl ammonium perchlorate, methyl dodecyl dihydroxyethyl ammonium perchlorate, methyl stearyl dihydroxyethyl ammonium perchlorate , Distearyl dihydroxyethylan Nium perchlorate, distearyl dihydroxypropyl ammonium perchlorate, methyl stearyl dipoly (2-4) oxyethylene ammonium perchlorate, N-polyoxyethylene-N, N, N-methyl, dilauryl ammonium and N-poly Examples thereof include N-polyoxyalkylene-N, N, N-trialkylammonium hydrochlorides such as oxypropylene-N, N, N-methyl, octyl and decylammonium, perchlorates and chlorates.
Antistatic properties can be imparted by adding a quaternary ammonium salt compound to the polyvinyl chloride resin, but the quaternary ammonium salt compound has good antistatic performance, but the heat of polyvinyl chloride resin. Reduce stability. However, by adding an appropriate amount of an anhydrous hydrotalcite compound, a decrease in thermal stability is remarkably controlled, and a film having good antistatic properties without discoloration such as yellowing can be obtained.

Examples of the hydrotalcite compound include those represented by the following general formula (1), and the anhydrous hydrotalcite compound is a hydrotalcite compound containing such crystal water at, for example, 185 to 230 ° C. Obtained by heating.
^{_{M 2+ 1-x M 3+ x}} (OH) 2 A n- x / n · mH 2 O ··· (1)
(In the formula, M ²⁺ , M ³⁺ and m are as follows: M ²⁺ : divalent metal ion such as Mg ²⁺ or Zn ²⁺ , M ³⁺ : ³ such as Al ³⁺ A valent metal ion, an n-valent anion such as A ⁿ⁻ : CO ₃ ²⁻ or SO ₄ ²⁻ , x: 0 <x <0.5, n: a positive number from 1 to 4, m: 0 <m < 2)
As an anhydrous hydrotalcite-based compound, commercial products such as trade name Alkamizer 4-2 or Alkamizer 7-2 manufactured by Kyowa Chemical Industry Co., Ltd. can be used.

  The amount of the anhydrous hydrotalcite compound is 0.05 to 6% by weight in the antistatic film, but when the antistatic film of the present invention is used for transparent applications, the anhydrous hydrotalcite compound If the blending amount is 0.1 to 1.5% by weight, the transparency of the film may be good. The blending amount of the anhydrous hydrotalcite compound is preferably 0.1 to 3% by weight, particularly preferably 0.5 to 1.5% by weight.

Further, it is preferable to blend a β-diketone compound together with the anhydrous hydrotalcite compound. Moreover, the heat stabilizer generally mix | blended with a polyvinyl chloride-type resin can be mix | blended within the range which does not affect this invention.
Examples of the β-diketone compound include dehydroacetic acid, cyclohexane-1,3-dione, 2-acetylcyclopentanone, 2-benzoylcyclopentanone, 2-acetylcyclohexanone, 2-benzoylcyclohexanone, acetyl stearoylmethane, and benzoylacetone. , Palmitoylbenzoylmethane, stearoylbenzoylmethane, dibenzoylmethane, tribenzoylmethane, 4-methoxybenzoyl-benzoylmethane, bis (4-methoxybenzoylmethane), 4-chlorobenzoyl-benzoylmethane, benzoyltrifluoroacetone, palmitoyltetralone , Stearoyl tetralone, benzoyl tetralone and the like. Of these, dibenzoylmethane is preferred. The blending amount of the β-diketone compound is 0.05 to 0.5% by weight in the antistatic film, preferably 0.1 to 0.3% by weight, more preferably 0.12 to 0.2% by weight. .

  Examples of heat stabilizers that can be blended include metal carboxylates such as Ca, Ba, Zn, Cd, Sn, and Pb, organic acid salts such as stearates, phenolates, and organic phosphate salts, oxides of the above metals, Inorganic metal compounds such as hydroxides, carbonates, silicates, phosphates, phosphites, aluminates, or complex salts thereof, organic tin compounds, epoxidized soybean oil, epoxidized linseed oil, epoxy Examples include epoxy compounds such as resins and organic phosphite compounds.

  Furthermore, the antistatic film of the present invention includes additives such as UV stabilizers, hindered amine light stabilizers, pigments, dye-based pigments, colorants, lubricants, etc. Acrylic acid such as acrylic acid, methyl acrylate, ethyl acrylate, acrylic acid-n-butyl, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate such as PMMA (polymethyl methacrylate), ethyl methacrylate Copolymers mainly composed of methacrylic acid esters such as methacrylic acid-n-butyl and methacrylic acid-2-ethylhexyl, and processing aids and reinforcing agents such as NBR (nitrile butadiene rubber) can be blended.

  Examples of the ultraviolet absorber include various ultraviolet absorbers such as benzotriazole, benzophenone, salicylic acid ester, hydroquinone, and cyanoacrylate, and these can be used alone or in combination of two or more. . The ultraviolet absorber can be blended in an amount of 0.1 to 5% by weight, preferably 0.5 to 3% by weight.

  Examples of the colorant include phthalocyanine blue, phthalocyanine green, Hansa yellow, alizarin lake, titanium oxide, zinc white, permanent red, quinacridone, and carbon black. These colorants can be used alone or in combination of two or more.

  Examples of the lubricant include various lubricants such as fatty acid lubricants, fatty acid amide lubricants, ester lubricants, polyethylene wax, and liquid paraffin. These lubricants can be used alone or in combination of two or more. The lubricant can be blended in an amount of 0.01 to 3% by weight, preferably 0.05 to 1% by weight.

If transparency is not important, lead-based and Ba-Zn-based inorganic powder stabilizers, antimony-based, magnesium hydroxide-based inorganic flame retardants and fillers may be blended. .
In the antistatic film of the present invention, for example, a vinyl chloride resin and various additives are weighed in necessary amounts, and then mixed using a ribbon blender, a super mixer, a Banbury mixer, or other conventionally known blenders and mixers. The obtained vinyl chloride resin composition is produced using a conventionally known method such as a calender molding method, a melt extrusion molding method (including a T-die method and an inflation method), a solution flow stretching method, and the like. It is obtained by filming. The thickness of the film is usually about 0.05 to 5 mm, preferably about 0.07 to 3 mm.

An appropriate amount of (a) polyvinyl chloride resin, (b) antistatic plasticizer, (c) quaternary ammonium salt compound and (d) anhydrous hydrotalcite compound should be blended in an appropriate amount. Thus, an antistatic film having a surface resistivity (measured under the conditions described in the examples according to JIS K 6911) of less than 10 ¹⁰ Ω can be obtained. When the surface resistivity is less than 10 ¹⁰ Ω, the antistatic performance is remarkably improved because it becomes a semiconductor region. Accordingly, it can be suitably used as a packaging film for partitions such as factories, computer rooms, clean rooms, curtains, cases for transporting and protecting ICs, covering materials for electronic communication, and the like.
The antistatic film of the present invention may be used as a film as it is or as a laminate in which a woven fabric, a nonwoven fabric, a plastic film or the like is laminated on the film, and the film or laminate is used as a surface of a product such as a sound insulating material. It can be used for other shapes by laminating the film or by further processing the film or laminate.
Hereinafter, the present invention will be described in detail by way of examples.

(Examples 1-3, Comparative Examples 1-2)
The formulation shown in Table-1 was kneaded and formed into a film with a test calendar at a temperature of about 170 ° C. for 6 minutes to obtain a film having a thickness of 0.3 mm. The presence or absence of discoloration (yellowing) and transparency of the obtained film were visually evaluated.

Furthermore, according to JIS K 6911, the volume resistivity (Ωcm) and the surface resistivity (Ω) were measured according to JIS K 6911 and the surface resistivity (Ω) was 4329A made by Yokogawa Hutec Packard. Measurement was made with a resistance meter (measurement range: 10 ⁸ to 10 ¹⁵ Ω, Ωcm).

Next, the film was put in a 170 ° C. gear oven and tested for thermal stability (time (minutes) until blackening was measured).
(Reference example)
A thickness of 0 was obtained in the same manner as in Example 1 except that hydrotalcite (Alkamizer 2 manufactured by Kyowa Chemical Co., Ltd.) was blended instead of anhydrous hydrotalcite (Alkamizer 4-2 manufactured by Kyowa Chemical Co., Ltd.). A 3 mm film was obtained. The obtained film was visually observed and yellowed.

Claims (6)

  (A) polyvinyl chloride resin 50 to 90% by weight, (b) antistatic plasticizer 1 to 50% by weight, (c) quaternary ammonium salt compound 0.5 to 7% by weight and (d) anhydrous hydrotal An antistatic film containing 0.05 to 6% by weight of a site compound.   (C) The antistatic film according to claim 1, wherein the content of the quaternary ammonium salt compound is 1 to 5% by weight.   (D) Content of anhydrous hydrotalcite type compound is 0.1 to 3 weight%, The antistatic film of Claim 1 or 2 characterized by the above-mentioned. The antistatic film according to claim 1, wherein the antibacterial plasticizer has a volume resistivity of less than 10 ¹¹ Ωcm.   (B) The antistatic plasticizer is an aliphatic dibasic acid diester and / or a phthalic acid diester. The antistatic film according to any one of claims 1 to 4. The antistatic film according to claim 1, wherein the film has a surface resistivity of less than 10 ¹⁰ Ω.