JPH0717802B2 - Antistatic chlorine-containing resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention relates to a chlorine-containing resin composition having low electrostatic properties.

(Prior Art) Generally, since synthetic resin has high electric insulation, it is easily charged with static electricity. When the synthetic resin is charged with static electricity, it becomes easy to adsorb dust and causes various harmful effects. For example, in the processing step of the synthetic resin, dust is adsorbed and the quality of the product is deteriorated. After the product is made, the dust is adsorbed and the surface is soiled, which lowers the value of the product. Therefore, it is important to prevent the synthetic resin from being charged in order to increase the value of the synthetic resin product. An antistatic agent is generally added to prevent the synthetic fiber from being charged.

Chlorine-containing resins, especially vinyl chloride resins, have good weather resistance and good dimensional stability, and can be made into hard or soft resins and have the property of being flame-retardant. Widely used. The chlorine-containing resin is the same as other synthetic resins in that it is easily charged. In addition, the chlorine-containing resin has a drawback that it is easily decomposed when it is heated for molding.
If decomposition occurs, the product will not be colored and transparent. Moreover, the property of being easily decomposed is often promoted also by mixing various materials, for example, mixing an antistatic agent. Therefore, it has been particularly difficult to make the chlorine-containing resin difficult to be charged.

In order to make the synthetic resin less likely to be charged, carbon black and metal powder have been blended for a long time. However, if carbon black or metal powder is blended, the product becomes opaque, and it is not possible to develop any beautiful color. Therefore, it has been demanded to make the vinyl chloride resin less likely to be charged and to provide a colorless and transparent product.

In order to meet this demand, an antistatic agent made of an organic compound has been used. Various types of compounds have already been proposed as antistatic agents. For example, Japanese Patent Publication No. 40-7366
Japanese Patent Laid-Open No. The quaternary ammonium salt represented by is proposed. Here, R ₁ is an alkyl group having 8 to 22 carbon atoms, an alkenyl group,
An alkylamidoethyl group or an alkylamidopropyl group, R ₂ , R ₃ and R ₄ represent an alkyl group or a hydroxyalkyl group having 1 to ₄ carbon atoms, and X is a perhalogen acid, a benzene-based sulfonic acid, or an alkylbenzene. It is said to represent the anion of the sulfonic acid series.

According to the proposal of this publication, it is possible to obtain a resin product which is unlikely to be charged and which is less colored than conventional products. However, as a result of additional tests by the inventor, the product was not sufficiently satisfactory in terms of antistatic property and colorless and transparent property. This is because when the electrical resistance of the obtained resin product is measured, the value as described in this publication cannot be obtained, and when the degree of coloring is measured, it is not completely colorless and transparent, and some coloring is seen. Therefore, the resin appears to be decomposed. Therefore, it has been necessary to develop an antistatic agent having excellent antistatic properties and good colorless and transparent properties.

(Problems to be Solved by the Invention) The present invention provides a chlorine-containing resin composition which is excellent in colorless transparency and which is excellent in antistatic property, while reducing the electric resistance thereof and preventing thermal decomposition of the chlorine-containing resin. Is what you are trying to do.

(Means for Solving the Problem) The present invention has extensively studied various characteristics of an antistatic agent proposed in Japanese Patent Publication No. 40-7366 and compounds similar thereto, particularly the properties exhibited by a vinyl chloride resin. . As a result, according to the present invention, when a specific quaternary ammonium compound is selected from the antistatic agents proposed in the above publications and added to a vinyl chloride resin together with a specific perchlorate,
It has been found that a resin composition which is difficult to be charged and which is relatively less colored can be obtained. Further, the present invention, in the case of imparting the vinyl chloride resin with the hardly-charged property and the thermal stability in this way,
It was found that the use of an ester having an ether bond in the molecule as a plasticizer further enhances the antistatic property. Furthermore, as a result of continuing the research, the present invention shows that when a specific ammonium salt not proposed in the above-mentioned publication is prepared and added to a vinyl chloride resin together with a specific perchlorate, almost no ammonium salt is obtained. It has been found that a colorless transparent resin composition having poor chargeability can be obtained. The present invention has been completed based on such knowledge.

The gist of the present invention is to add a predetermined amount of three kinds of compounds to a chlorine-containing resin. One of the three compounds is N- (poly) oxyalkylene-
An N, N, N-trialkylammonium salt of the general formula It is a compound represented by the following formula, and is mixed in an amount of 0.5 to 5 parts with respect to 100 parts by weight of the chlorine-containing resin. The other one is a perchlorate, which is a compound represented by the general formula M (ClO ₄ ) m (formula 2), and is compounded in an amount of 0.02 to 0.5 part with respect to 1 part by weight of the ammonium salt. . Where R ₁ , R ₂ and R
₃ , one of them is an alkyl group having 5 to 24 carbon atoms, the other two are alkyl groups having 1 to 5 carbon atoms, R ₄ is an alkylene group having 2 to ₄ carbon atoms, and n is Is an integer of 1-15, X is an anion of hydrochloric acid, chloric acid or perchloric acid, M is a metal ion or ammonium ion NH ₄ ⁺ belonging to 1A or 2A in the periodic table, and m is 1 or It is an integer of 2.

The remaining third is an ester compound having an ether bond in the molecule, which is 30 per 100 parts by weight of the chlorine-containing resin.
~ 100 parts are included.

That is, the present invention provides (a) 0.5 to 5 parts of the ammonium salt represented by the above formula 1 with respect to 100 parts by weight of the chlorine-containing resin, and (b) the perchlorate represented by the above formula 2 in the above (a).
To 0.02 to 0.5 part, and (c) an ester having an ether bond is a chlorine-containing resin.
The present invention provides a hardly-charged chlorine-containing resin composition containing 30 to 100 parts by weight of 100 parts by weight and (d) a chlorine-containing resin.

(Relationship with Prior Art) The ammonium salt represented by the above formula 1 is disclosed in JP-B-40-
Most of them are different from each other, only partially overlapping with the ammonium salt proposed in 7366. In detail,
The ammonium salt proposed in the above publication has the general formula as described above. At first glance, it is similar to the compound of formula 1 used in the present invention. However, in Equation 1,
Since X is limited to the anions of hydrochloric acid, chloric acid, or perchloric acid, while in Formula 3, X is limited to the anions of perhalogenic acid, benzene-based sulfonic acid, or alkylbenzene-based sulfonic acid, both The same thing is
Only if an anion of perchloric acid is used as X. That is, in Formula 1, when X is an anion of hydrochloric acid and chloric acid, the compound of Formula 1 is completely different from that of Formula 3. In addition, in the formula 3, R ₄ is a carbon number 1-
4 is a hydroxyalkyl group, on the other hand, the corresponding one in formula 1 is (R ₄ O) nH, R ₄ is a C 2-4 alkylene group, and n is an integer of 1-15. Therefore, these match only in a part when n in Expression 3 is 1. That is, when n is an integer of 2 or more, the ammonium salt of formula 1 is completely different from the ammonium salt of formula 3. In addition, R ₁ , R ₂ and R ₃ are
All of them only partially overlap. Therefore, most of the ammonium salt of formula 1 used in this invention is
It is different from the ammonium salt proposed in 40-7366.

The present invention also uses the ammonium salt of the formula 1 together with the perchlorate of the formula 2 in Japanese Examined Patent Publication No. 40-7366.
This is different from what is disclosed in the publication. That is, the above-mentioned publication makes the ammonium salt represented by Formula 3 act as an antistatic agent alone, and does not teach that it works in cooperation with other compounds. However,
According to the present invention, the perchlorate is allowed to coexist with the ammonium salt of the formula 1 and the specific ester to enhance the antistatic action, and the resin can be kept almost colorless and transparent.
It's totally new.

(Explanation of Ammonium Salt) As described above, the ammonium salt of formula 1 used in the present invention requires that any one of R ₁ , R ₂ and R ₃ is an alkyl group having 5 to 24 carbon atoms. Among them, the most commonly used one is an alkyl group having 8-18 carbon atoms. The remaining _{two of} R ₁ , R ₂ and R ₃ need to be alkyl groups having 1 to 5 carbon atoms, among which one commonly used is 1 to 5 carbon atoms. 2 is an alkyl group. Further, R ₄ is required to be an alkylene group having 2 to ₄ carbon atoms, of which an alkylene group having 2 to 3 carbon atoms is commonly used. n is required to be an integer of 1-15, but one commonly used is 1-5. Further, X is usually an anion of hydrochloric acid or perchloric acid.

The ammonium salt of formula 1 is 0.5 per 100 parts by weight of resin.
Used at a rate of -5 parts. Of these, preferred is 3 parts or less. The reason is that the ammonium salt is 0.5
When it is less than the number of parts, the effect does not appear sufficiently,
On the other hand, when the amount is more than 5 parts, the ammonium salt is not compatible with the resin and is leached to the surface of the product, which not only deteriorates the appearance of the product but also reduces heat resistance and water resistance.

(Explanation of Perchlorate) As the perchlorate of formula 2, M in the general formula is required to be a metal ion or ammonium group belonging to 1A and 2A of the periodic table. That is, M is, for example, lithium, sodium, potassium, rubidium, beryllium,
Magnesium, calcium, strontium, barium and ammonium.

Of these, preferred are lithium, barium, magnesium and ammonium.

The addition amount of the perchlorate of formula 2 is determined based on the amount of the ammonium salt of formula 1. That is, the compound of the formula 2 is 0.02-0.5 part by weight with respect to 1 part of the compound part of the formula 1, and the preferable ratio is 0.05-0.3 part. The reason is that when the perchlorate of formula 1 is 0.02 or less,
This is because a sufficient antistatic effect cannot be obtained, and conversely 0.
When it is 5 parts or more, not only the antistatic effect exhibited in cooperation with the ammonium salt of the formula 1 does not improve to the extent that it increases, but also the thermal stability of the resin is impaired and the water resistance decreases. This is because the harmful effect of appears.

(Description of ester having ether bond) An ester having an ether bond in the molecule generally has higher antistatic property than an ester having no ether bond known as a general-purpose plasticizer.

Examples of the ester used in the present invention include esters of aliphatic or aromatic mono-, di-, tricarboxylic acids and phosphoric acids with alkoxyl alkyl alcohols or polyoxyalkylene monoalkyl ethers (polyalkylene glycol monoalkyl ethers), and Examples thereof include diesters of polyalkylene glycol and fatty acids.

Specific examples of the aliphatic monocarboxylic acid include butyric acid, octylic acid (including 2-ethylhexylic acid), lauric acid, palmitic acid, oleic acid and the like, and aliphatic di-carboxylic acids include glutaric acid and adipic acid. , Azelaic acid, sebacic acid, etc., aromatic mono-, di-, tri-, carboxylic acid as carboxylic acid, phthalic acid (including phthalic anhydride), trimellitic acid (including trimellitic anhydride),
Etc. An ester obtained from trimellitic acid is particularly preferable because it has a small volatilization loss.

Further, as the polyoxyalkylene-monoalkyl ether, ethylene glycol monobutyl ether, di-ethylene glycol monobutyl ether, triethylene glycol monomethyl ether, di-ethylene glycol monohexyl ether, propylene glycol monobutyl ether, di-propylene glycol monoethyl ether. Ether and the like, and examples of the polyalkylene glycol include di-ethylene glycol, tri-ethylene glycol, hexaethylene glycol, di-propylene glycol, butylene glycol, and the like.

These esters can be easily synthesized under usual esterification conditions of acid and alcohol. The amount of addition to the resin is 30 to 100 parts by weight, preferably 40 to 70 parts by weight, based on 100 parts by weight of the resin.

(Other Compounds) Various other chlorine-containing resins, especially vinyl chloride resins, are added when the products are processed into vinyl chloride resins. For example, stabilizers, fillers, dyes and pigments, etc. are added. The composition according to the present invention may be added with various additives generally added in the processing of the resin.

(Examples) Hereinafter, the reason why the composition according to the present invention is excellent will be specifically described with reference to Examples and Comparative Examples. In the following, simply "parts" means "parts by weight". The physical properties of the product obtained there were measured as follows.

Tensile test: 20 ℃, dumbbell No.3, tensile speed: 200mm / min Compatibility: 50 ℃, presence / absence of bleed after 120 hours under 95% relative humidity Electrical resistance: (1) Surface resistance: 30 ℃ OH under 50% relative humidity (2) Volume resistivity: 30 ℃, ohm under 50% relative humidity-cm Volatility loss: Weight loss rate after heating at 100 ℃ for 6 hours.

Colorability: Coloring is judged by the naked eye and divided into 6 levels. Colorlessness is 1
The yellow coloring was evaluated as 6.

Example 1 In this example, an ammonium salt of formula 1 wherein R ₁ is an octyl group, R ₂ and R ₃ are both ethyl groups, R ₄ is an ethylene group and n is 6, Polyoxyethylene-N, N, N-octyl, diethylammonium perchlorate was used. Further, as the perchlorate of the formula 2, lithium perchlorate in which M is lithium was used.

Ammonium perchlorate 2 to 100 parts of vinyl chloride resin
Parts, 0.2 parts of lithium perchlorate, 50 parts of diethoxyethyl phthalate, 2.5 parts of barium-zinc-based stabilizer (Nissan Fuero, LTL-272), and epoxy-based stabilizer (Adeka Argus, D -178) 2 parts. This compound was kneaded with a roll at 160 ° C. for 6 minutes and then pressed at 170 ° C. for 7 minutes to obtain a resin sheet.

The physical properties of this sheet were measured. As the physical properties, a tensile test, compatibility, electric resistance, coloring degree, and volatilization loss were measured. As a result, the elongation in the tensile test was 325.
%, Tensile strength 2.50 kg / mm ² , compatibility test showed no bleed, surface resistance 2.7 × 10 ⁸ ohm, volume resistivity
It was 4.5 × 10 ⁸ ohm-cm, the coloring property was very slightly colored, and was evaluated as 2. The loss on volatilization was 0.39%. Therefore,
As a whole, it was recognized as a soft vinyl chloride resin sheet which is hard to be charged, is colorless and transparent, and is good.

Example 2 In this example, as the ammonium salt of formula 1, Was used. Further, lithium perchlorate was used as the perchlorate of Formula 2.

To 100 parts of vinyl chloride resin, 4 parts of the above ammonium chloride, 0.4 part of lithium perchlorate, and 45 parts of butoxyethyl phosphate as a plasticizer were added, and the same amount of stabilizer as in Example 1 was added. A sheet was obtained in exactly the same manner as in Example 1.

When the physical properties of this sheet were measured, the elongation rate in the tensile test was 300%, the tensile strength was 2.45 kg / mm ² , bleeding was not recognized in the compatibility test at all, and the electrical resistance was the surface resistance.
1.5 × 10 ⁸ ohm, volume resistivity 1.9 × 10 ⁸ ohm-cm
Then, the coloring property was evaluated as 3, the volatilization loss was 0.28%, and it was recognized that charging was extremely difficult and transparency was not a problem in practical use.

Example 3 In this example, as the ammonium salt of Formula 1, And magnesium perchlorate was used as the perchlorate of Formula 2.

More specifically, 100 parts of vinyl chloride resin, 2 parts of the above ammonium salt, 1.0 part of magnesium perchlorate, and tetraethylene glycol-di-2 ethylhexoate (4GO) 60.
Parts, and the same amount of the same stabilizer used in Example 1 was blended. Thereafter, this composition was treated in exactly the same manner as in Example 1 to obtain a sheet.

When the physical properties of this sheet were measured, the elongation rate in the tensile test was 315%, the tensile strength was 2.50 kg / mm ² , bleeding was not observed in the compatibility test, and the electrical resistance was a surface resistance of 9.0 × 10 ⁷ ohms, volume specific Resistance is 3.0 × 10 ⁸ ohm-cm, coloring degree is 3
The loss on volatilization was 0.33. Therefore, it was confirmed that the sheet is extremely unlikely to be charged and that the transparency has no practical problem.

Example 4 In this example, as the ammonium salt of Formula 1, And barium perchlorate was used as the perchlorate of Formula 2.

More specifically, 4 parts of the above ammonium salt, 0.5 part of barium perchlorate and 65 parts of trimethoxyethyl trimellitate were added to 100 parts of vinyl chloride resin, and the same stabilizer as used in Example 1 was added. The same amount was blended. Thereafter, this composition was treated in exactly the same manner as in Example 1 to obtain a sheet.

When the physical properties of this sheet were measured, the elongation rate in the tensile test was 350%, the tensile strength was 2.7 kg / mm ² , bleeding was not observed in the compatibility test at all, and the electrical resistance was 8.0 × 10 ⁸
It had an ohm and a volume resistivity of 3.5 × 10 ⁹ ohm-cm, was colorless and transparent, and was evaluated to have a coloring degree of 1. The volatilization loss was 0.07. Therefore, the sheet is hard to be charged, is colorless and transparent,
Since the loss on heating was small, it was recognized as a good quality product that can retain its properties for a long time.

Comparative Example 1 This comparative example is an example in which only an ammonium salt was added as an antistatic agent without using a perchlorate. As an antistatic agent, Was used. Dioctyl phthalate was used as the plasticizer.

To 100 parts of vinyl chloride, 5 parts of the above antistatic agent and 50 parts of a plasticizer were added, and the same amount of the same stabilizer as in Example 1 was added thereto. After that, a sheet was obtained in exactly the same manner as in Example 1.

When the physical properties of this sheet were measured, the elongation rate in the tensile test was 330%, the tensile strength was 2.50 kg / mm ² , no bleed was observed in the compatibility test, the electrical resistance was 6.0 × 10 ⁹ ohms, and the volume resistivity was 1.0. × 10 ¹¹ ohm-cm, colorability was considerably colored, and a rating of 4 was obtained, with a volatilization loss of 0.46%. Therefore, as a whole, it was relatively easily charged and was considerably colored, so it was recognized as a defect.

Comparative Example 2 This comparative example is an example in which only a general-purpose plasticizer was added to a vinyl chloride resin and no antistatic agent was used.

50 parts of dioctyl phthalate as a plasticizer was added to 100 parts of vinyl chloride resin, and the same amount of the same stabilizer as in Example 1 was added thereto. After that, a sheet was obtained in exactly the same manner as in Example 1.

When the physical properties of this sheet were measured, the elongation rate in the tensile test was 310, the tensile strength was 2.55 kg / mm ² , bleeding was not observed at all in the compatibility test, and the electrical resistance was 10 × 10 ¹²
The ohm and volume resistivity were 9.0 × 10 ¹² ohm-cm, the coloring property was colorless and transparent, and was evaluated as 1. The loss on volatilization was 0.77%. Therefore, it was confirmed that the colorless transparency was good although it had a drawback that it was easily charged as a whole.

(Effects of the Invention) The composition according to the present invention comprises the ammonium salt of formula 1
The perchlorate, the ester having an ether bond, and the chlorine-containing resin are contained in a predetermined amount, so that the composition is less likely to be charged, and therefore it is difficult to adsorb dust. A resin product containing can be obtained. Further, since the resin product thus obtained is difficult to be charged, it does not adsorb dust, and therefore the surface can be kept beautiful. This becomes apparent when the electrical resistance of the product is measured. Moreover, it is speculated that the composition according to the present invention contains the above-mentioned ammonium salt and perchlorate, but it is possible to provide a product with little coloring and colorless transparency, which poses no practical problem. In this way, according to the present invention, a chlorine-containing resin product that is not easily charged and has good transparency can be obtained, so that the practical effect is great.

Claims (1)

[Claims] 1. (a) General formula 0.5 to 5 parts by weight of the ammonium salt represented by the above with respect to 100 parts by weight of the chlorine-containing resin, and (b) the perchlorate represented by the general formula M (ClO ₄ ) m 0.02 to 0.5 part per 1 part by weight of salt, (c) 30 to 100 parts of ester having an ether bond in the molecule per 100 parts by weight of chlorine-containing resin, and (d) chlorine-containing resin are included. A chlorine-containing resin composition having a low electrostatic property, which is characterized in that (However, _one of R ₁ , R ₂ and R ₃ is an alkyl group having 5 to 24 carbon atoms, the other is an alkyl group having 1 to 5 carbon atoms, R ₄ is an alkylene group having 2 to ₄ carbon atoms, n is an integer of 1-15, X is an anion of hydrochloric acid, chloric acid or perchloric acid, and M is 1A in the periodic table.
Or a metal ion or ammonium ion belonging to 2A, m
Is 1 or 2. )