JP3233291B2 - Chlorine-containing resin composition with excellent antistatic properties - Google Patents

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 and, more particularly, to a composition containing an acylated quaternary ammonium salt compound of perchloric acid. And an improved chlorine-containing resin composition.

[0002]

2. Description of the Related Art Chlorine-containing resins such as polyvinyl chloride resins are used as soft products containing a relatively large amount of a plasticizer or so-called semi-hard products containing a relatively small amount of a plasticizer. Widely used for various packaging films or containers, agricultural films, sheets, flooring materials, wall materials and the like.

[0003] These chlorine-containing resins generally have good electrical insulation properties, and are preferable in fields requiring electrical insulation such as electric wire coating materials. However, they accumulate static electricity due to friction. When used as a partition for factories, computer rooms, and the like, a case for transporting and protecting ICs, and a packaging film or sheet for a covering material for electronic communication, a so-called static electricity failure often occurs.

[0004] Also, when a chlorine-containing resin is used as a floor material, there is a disadvantage that dirt is adsorbed by static electricity and the appearance is impaired.

Furthermore, chlorine-containing resins have a poor affinity for water, so that when used in food packaging films or containers, agricultural films, etc., water-drops adhere to the surface, resulting in fogging. It has been desired to prevent charging of the contained resin.

In order to eliminate these drawbacks, for example,
Japanese Patent Publication No. 39-21114 proposes to use an ester of ether alcohol as a plasticizer, but its effect is completely inadequate and not practically satisfactory.

For this reason, various attempts have been made to improve the antistatic properties by adding or applying various antistatic agents to the chlorine-containing resin. In fact, its use has been limited because of its markedly reduced thermal stability.

For example, Japanese Patent Publication No. 40-7366 describes in detail the effect of adding a quaternary ammonium salt type antistatic agent to a vinyl chloride resin containing dioctyl phthalate, a general-purpose plasticizer. And trimethyl dodecylammonium chloride, dimethyl
Quaternary ammonium halide antistatic agents such as hydroxyethyl dodecyl ammonium bromide significantly accelerate the thermal decomposition of vinyl chloride resin, and quaternary ammonium using perchloric acid or organic sulfonic acid anions as anions. Salt-type antistatic agents have a small adverse effect,
Particularly, it is described that a compound using an organic sulfonate anion has a very small adverse effect.

However, the compounds using an organic sulfonate anion described in the above-mentioned publication have a very large change in coloring due to heating of a chlorine-containing resin, have an insufficient antistatic effect, and have a disadvantage in using a perchlorate anion. Even when a quaternary ammonium salt type antistatic agent was used, the decrease in thermal stability was not negligible and was not actually satisfactory.

For this reason, it has been proposed to use a nonionic antistatic agent which does not adversely affect the heat stability. For example, Japanese Patent Publication No. 44-22616 discloses an ester of an ether alcohol and a nonionic antistatic agent. It is described that the antistatic property is further improved by using the antistatic agent in combination, but the effect of improvement is not yet satisfactory. There was concern that bleeding would occur, and improvement was strongly desired.

[0011]

In view of the above situation, the present inventors have intensively studied to obtain a chlorine-containing resin composition having good antistatic properties and thermal stability and excellent bleeding properties. As a result, by using an acylated aliphatic quaternary ammonium salt compound of perchloric acid, not only is the antistatic property and the thermal stability excellent, but also the chlorine-containing resin composition excellent in the bleeding property is obtained. The inventors have found that the present invention can be obtained, and arrived at the present invention.

That is, in the present invention, 100 parts by weight of a chlorine-containing resin is represented by the following general formula (I) of the following [formula 2] (same as [formula 1]).
The present invention provides a chlorine-containing resin composition having excellent antistatic properties, which is obtained by adding 0.01 to 5 parts by weight of an acylated quaternary ammonium salt compound of perchloric acid represented by the formula:

[0013]

Embedded image (Wherein, R ₁ represents a residue obtained by removing all carboxyl groups from a divalent to tetravalent aliphatic or aromatic carboxylic acid having 2 to 20 carbon atoms, and R ₂ and R ₃ each independently represent a carbon atom Number 1
20 alkyl groups or hydroxyalkyl groups,
A ₁ and A ₂ each independently represent an alkylene group having 2 to 4 carbon atoms, m represents an integer of 0 to 20, n represents an integer of 1 to 20, R ₄ represents _{4 to} 22 carbon atoms. An alkyl group, an aralkyl group having 7 to 20 carbon atoms or (R'CONHR "-)
R ′ represents an alkyl or alkenyl group having 1 to 20 carbon atoms, R ″ represents an alkylene group having 1 to 10 carbon atoms, and R ₅ represents an alkyl group having 1 to 20 carbon atoms. A represents an integer of 1 to 4, b represents an integer of 0 to 3, provided that a + b represents a carboxylic acid residue represented by R ₁
Equal to valence . )

Hereinafter, the chlorine-containing resin composition of the present invention having the above gist will be described in detail.

In the above general formula (I), the carboxylic acid giving the residue represented by R ₁ includes oxalic acid, succinic acid, adipic acid, suberic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, triphthalic acid Examples include melitic acid, pyromellitic acid, glutaric acid, azelaic acid, tartaric acid, citric acid, butanetricarboxylic acid, and butanetetracarboxylic acid.

The alkyl group having ₄ to 22 carbon atoms represented by R ₄ includes butyl, sec-butyl, tert-butyl, isobutyl, amyl, tert-amyl, hexyl, heptyl, Octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, tertiary nonyl, decyl, isodecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, etc. The aralkyl group having 7 to 20 carbon atoms includes a benzyl group, a diphenylmethyl group, a cinnamyl group, a phenethyl group, a styryl group and the like.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ₂ or R ₃ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a secondary butyl group, a tertiary butyl group and an isobutyl group. , Amyl, tertiary amyl, hexyl, heptyl, octyl, isooctyl, 2
-Ethylhexyl group, tertiary octyl group, nonyl group, tertiary nonyl group, decyl group, isodecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group and the like, and represented by R ₂ or R ₃ Examples of the hydroxyalkyl group include a hydroxyalkyl group corresponding to the above alkyl group. Examples of the alkyl group having 1 to 20 carbon atoms represented by R ′ include the same alkyl group as the alkyl group represented by R ₂ or R ₃ , and the alkenyl group represented by R ′ includes a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-heptenyl group, 2-heptenyl group, 1
-Nonenyl group, 3-nonenyl group, 8-nonenyl group, 1-
Undecenyl group, 2-undecenyl group, 3-undecenyl group, 4-undecenyl group, 10-undecenyl group, 3
-Tridecenyl group, 4-tridecenyl group, 8-tridecenyl group, 1-pentadecenyl group, 6-pentadecenyl group, 8-pentadecenyl group, 5-heptadecenyl group, 8
A heptadecenyl group, a 10-nonadecanyl group, an 8-heneicosenyl group, a 10-heneicosenyl group, and the like. Examples of the alkylene group having 1 to 10 carbon atoms represented by R "include an ethylene group, a propylene group, a trimethylene group, a butylene group, an isobutylene group, a tetramethylene group,
Examples include a pentamethylene group and a hexamethylene group.
Examples of the alkylene group having 2 to 4 carbon atoms represented by A ₁ or A ₂ include an ethylene group, a 1,2-propylene group, and a 1,3-
Examples include a propylene group, a butylene group, and an isobutylene group. Examples of the alkyl group having 1 to 20 carbon atoms represented by R ₅ include the same alkyl groups as the alkyl groups represented by R _{2 and} R ₃ .

Accordingly, the acylated quaternary ammonium salt of perchloric acid represented by the above general formula (I) includes:
For example, the following compounds [compounds 3] to [formula 10] (compounds 1 to 8) can be mentioned.

[0019]

Embedded image Compound 1

[0020]

Embedded image Compound 2

[0021]

Embedded image Compound 3

[0022]

Embedded image Compound 4

[0023]

Embedded image Compound 5

[0024]

Embedded image Compound 6

[0025]

Embedded image Compound 7

[0026]

Embedded image Compound 8

The compounded amount of the acylated quaternary ammonium salt of perchloric acid is 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the chlorine-containing resin.
Parts by weight.

The acylated quaternary ammonium salt of perchloric acid represented by the general formula (I) is, for example, a quaternary ammonium salt type compound of perchloric acid having a hydroxyl group and the carboxylic acid or carboxylic acid. It can be easily synthesized by an esterification reaction or a transesterification reaction with a partial ester.

The following [Synthesis Example] specifically shows a method for producing the compound represented by the above general formula (I), but the present invention is not limited by this Synthesis Example.

(Synthesis Example) Synthesis of Compound 3 (Compound 5) 60.3 g (0.2 mol) of dimethyl n-octyl-β-hydroxyethylammonium perchlorate
55.6 g (0.2 mol) of dibutyl phthalate and 0.03 g (0.03%) of tetraisopropoxytitanium are placed in a flask, and stirred at a reaction temperature of 180 to 200 ° C. and a reduced pressure of 50 to 100 torr. A transesterification reaction was carried out for one hour, and a theoretical amount (about 15 g) of butanol was distilled off to obtain 101 g of a yellow viscous liquid product.

The hydroxyl value of the obtained product was 9, and as a result of infrared spectroscopy, the absorption due to the hydroxyl group at 3500 cm ^-1 was almost disappeared, confirming that the product was the desired product.

As the chlorine-containing resin in the present invention, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-acrylate copolymer, Blends of chlorine resins with ABS resins, MBS resins, NBR and the like can be mentioned.

The chlorine-containing resin composition having excellent antistatic properties of the present invention is particularly effective for use as a semi-hard or soft product containing a plasticizer. As the above plasticizer,
For example, phthalate plasticizers (dibutyl phthalate, di-2-ethylhexyl phthalate, bis (butoxyethoxyethyl) phthalate, di-n-octyl phthalate, dinonyl phthalate, didecyl phthalate, diundecyl phthalate, n- Octyl-n-decyl phthalate, butylbenzyl phthalate, etc.), phosphate plasticizers (tricresyl phosphate, tri-2-ethylhexyl phosphate, tris (butoxyethoxyethyl) phosphate, triphenyl phosphate, 2-phenyl
Ethylhexyl diphenyl phosphate, etc.), adipate plasticizer (di-2-ethylhexyl adipate, bis (butoxyethoxyethyl) adipate, diisodecyl adipate, etc.), sebacate ester plasticizer
(Dibutyl sebacate, di-2-ethylhexyl sebacate, etc.), azelaic acid ester plasticizers (di-2-ethylhexyl azelate, etc.), trimellitic acid ester plasticizers (tributyl trimellitate, tri-2-ethylhexyl trimellitate) And epoxidized soybean oil, epoxidized linseed oil and the like, chlorinated paraffin, chlorinated fatty acid esters, and the like.

In the chlorine-containing resin composition of the present invention, other additives such as Ca, B
a, Mg, Zn, Cd, Sn, Pb carboxylates, phenolates, organic acid salts such as organic phosphate salts, oxides, hydroxides, carbonates, silicates, phosphates, and salts of the above metals Inorganic metal compounds such as phosphates, aluminates or double salts thereof, general-purpose heat stabilizers such as organic tin compounds, epoxy compounds such as epoxy resins, organic phosphite compounds, ultraviolet absorbers, light stabilizers, pigments , A dye, a filler, a foaming agent, a lubricant, a flame retardant, a β-diketone compound, a phenol compound, and the like.

[0035]

EXAMPLES Hereinafter, the chlorine-containing resin composition of the present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples.

Example 1 [Blending] Parts by weight Vinyl chloride resin 100 Di-2-ethylhexyl phthalate 20 Adekastab AC-216 (Ba / Zn-based liquid stabilizer manufactured by Asahi Denka Kogyo KK) 2.8 Adekizer O- 130P (epoxidized soybean oil manufactured by Asahi Denka Kogyo Co., Ltd.) 2.0 Antistatic agent (see Table 1) The composition obtained by the above [Blending] is kneaded in a roll at 180 ° C for 5 minutes, and then at 160 ° C and 200 kg. Pressing was performed for 5 minutes under the condition of / cm ² to prepare a sheet having a thickness of 1 mm.

Using the prepared sheet, the volume resistivity (Ωcm) and the surface resistivity (Ω) were measured at 30 ° C. and a relative humidity of 60%. Further, using this sheet, transparency, bleeding property and thermal stability (minute) in a gear oven at 175 ° C. were measured.

The transparency was measured by a 10-point method. Good 1 ← ──── → 10 Bad Bleedability was measured at room temperature and 70 ° C (100% relative humidity).
%), The surface condition was observed and evaluated after standing for 6 months and 1 month, respectively. ◎: Surface glossy ○: Slight glossy △: Cloudy ×: Scratch

The results are shown in Table 1 below. In Table 1, Compounds 1 to 8 are the above-mentioned exemplary compounds (see [Chemical Formula 3] to [Chemical Formula 10]), and Comparative Compound I used in Comparative Examples is the following [Chemical Formula 11]. Compound and Comparative Compound II is sorbitan monopalmitate.

[0040]

Embedded image Comparative compound I

[0041]

[Table 1]

Example 2 [Blending] Parts by weight Vinyl chloride resin 100 Di-2-ethylhexyl phthalate 50 Adekastab AC-212 (Ba / Zn liquid stabilizer manufactured by Asahi Denka Kogyo KK) 2.5 Adekizer O- 130P (epoxidized soybean oil manufactured by Asahi Denka Kogyo Co., Ltd.) 3.0 Antistatic agent (see [Table 2])

In order to see the effect of the soft blending, the blend according to the above [blending] was roll-kneaded at 170 ° C. for 5 minutes and then pressed at 160 ° C. and 200 kg / cm ² for 5 minutes to obtain a 1 mm thick layer. Created a sheet. The prepared sheet was subjected to a test for volume resistivity, surface resistivity, transparency, thermal stability, and bleedability in the same manner as in Example 1.

The results are shown in the following [Table 2]. In Table 2, Compounds 2 to 7 are the above-described exemplary compounds (see Chemical Formulas 4 to 9), and Comparative Compound I was
A compound represented by the above formula [11], and a comparative compound
II is sorbitan monopalmitate.

[0045]

[Table 2] Example 3 [Blending] Parts by weight Vinyl chloride resin 100 Di-2-ethylhexyl phthalate 50 Adekastab AC-212 (Ba / Zn liquid stabilizer manufactured by Asahi Denka Kogyo Co., Ltd.) 2.5 Adekizer O-130P (Asahi Epoxidized soybean oil manufactured by Denka Kogyo Co., Ltd. 2.0 Antistatic agent (see [Table 3])

To see the effect of the amount of the antistatic agent,
A sheet was prepared from the composition according to the above [formulation] in the same manner as in Example 1, and a volume resistivity, a surface resistivity,
Transparency, thermal stability and bleedability tests were performed.

The results are shown in Table 3 below. In Table 3, compound 4 is the above-mentioned exemplified compound (see [Chem. 6]).
And Comparative Compound I is a compound shown in the above [Chemical Formula 11].

[0048]

[Table 3] Example 4 [Blending] Parts by weight Vinyl chloride resin 100 ADK STAB AC-169 (Ba / Zn-based liquid stabilizer manufactured by Asahi Denka Kogyo Co., Ltd.) 2.5 Adecaizer O-130P (Epoxy conversion manufactured by Asahi Denka Kogyo Co., Ltd.) Soybean oil) 3.0 Compound 4 (see [Chem. 6]) 1 Plasticizer (see [Table 4]) 50

In order to examine the effect of the type of plasticizer, the composition according to the above [Blending] is roll-kneaded at 170 ° C. for 5 minutes, and then pressed at 160 ° C. and 200 kg / cm ² for 5 minutes to obtain a thickness. A 1 mm long sheet was made. The prepared sheet was subjected to a test for volume resistivity, surface resistivity, transparency, thermal stability, and bleedability in the same manner as in Example 1.

The results are shown in Table 4 below. In Table 4, compound 4 is the above-mentioned exemplified compound (see [Chem. 6]).
Wherein Comparative Compound I is the compound shown in the above [Chemical Formula 11], and Comparative Compound II is sorbitan monopalmitate.

[Table 4]

From the results of each of the above Examples, the chlorine-containing resin composition of the present invention, which contains an acylated quaternary ammonium salt compound of perchloric acid, has an antistatic ability (volume resistivity and surface resistivity). ) Is remarkably improved, and the heat stability does not decrease even when a large amount of an antistatic agent is blended.
Moreover, it is understood that the bleeding property is small. On the other hand, the quaternary ammonium perchlorate type antistatic agent conventionally used remarkably lowers the thermal stability of the chlorine-containing resin, and cannot be blended in a large amount due to large bleed.

[0052]

Industrial Applicability The chlorine-containing resin composition of the present invention has improved antistatic properties and excellent thermal stability and bleeding properties.

Claims (1)

(57) [Claims] 1. A quaternary ammonium salt compound of an acylated perchloric acid represented by the following general formula (I): 0.01 to 5 parts by weight per 100 parts by weight of a chlorine-containing resin. And a chlorine-containing resin composition having excellent antistatic properties. Embedded image (Wherein, R ₁ represents a residue obtained by removing all carboxyl groups from a divalent to tetravalent aliphatic or aromatic carboxylic acid having 2 to 20 carbon atoms, and R ₂ and R ₃ each independently represent a carbon atom Number 1
20 alkyl groups or hydroxyalkyl groups,
A ₁ and A ₂ each independently represent an alkylene group having 2 to 4 carbon atoms, m represents an integer of 0 to 20, n represents an integer of 1 to 20, R ₄ represents _{4 to} 22 carbon atoms. An alkyl group, an aralkyl group having 7 to 20 carbon atoms or (R'CONHR "-)
R ′ represents an alkyl group or alkenyl group having 1 to 20 carbon atoms, R ″ represents an alkylene group having 1 to 10 carbon atoms, and R ₅ represents an alkyl group having 1 to 20 carbon atoms. A represents an integer of 1 to 4 and b represents an integer of 0 to 3, provided that a + b represents a carboxylic acid residue represented by R ₁
Equal to valence . )