JPH062856B2 - 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 process of processing a synthetic resin, dust is adsorbed and the quality of the product is deteriorated. After the product is produced, 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 fibers 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. 40-7
No. 366 discloses a general formula as an antistatic agent. 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, and R ₂ , R _3, and R ₄ are alkyl groups having 1 to ₄ carbon atoms or a hydroxy group. It represents an alkyl group, and X represents an anion of perhalogen acid, benzene-based sulfonic acid, or alkylbenzene-based sulfonic acid.

According to the proposal of this publication, it is possible to obtain a resin product that is hard to be charged and is less colored than the conventional ones. However, as a result of additional tests by the inventor, the product is colorless and transparent and has a poor electrostatic property. The sex was not satisfactory either. 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, but some coloring is observed. This is because the resin seems to be decomposed. Therefore, it has been necessary to develop an antistatic agent that has both good antistatic properties and colorless transparency.

(Problems to be Solved by the Invention) The present invention prevents the thermal decomposition of a chlorine-containing resin and lowers its electrical resistance to provide a chlorine-containing resin which is more excellent in both colorless transparency and antistatic property. It is intended to provide a resin composition.

(Means for Solving the Problem) The present inventor has extensively studied various properties 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. did.
As a result, the present inventor selects a specific quaternary ammonium compound from the antistatic agents proposed in the above publications, and adds this together with a specific perchlorate to a vinyl chloride resin to improve thermal stability. It has been found that a resin composition that is well colored and less likely to be charged can be obtained. That is, when the above-mentioned specific ammonium compound is used together with a perchlorate, a phase retention effect appears and, unlike the case where the ammonium compound is used alone, both thermal stability and antistatic property are remarkably improved. Found. Furthermore, this inventor
As a result of continuing research, when a specific ammonium salt not proposed in the above publication was prepared and added to a vinyl chloride resin together with a specific perchlorate, a colorless and transparent resin composition with poor electrostatic property was obtained. I found that I could get things. The present invention has been completed based on such knowledge.

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

That is, the present invention comprises (a) 0.5 to 5 parts by weight 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. A non-chargeable chlorine-containing resin composition comprising 0.02 to 0.5 part by weight of 1 part by weight of an ammonium salt represented by (a) and (c) a chlorine-containing resin. Is.

(Relationship with Prior Art) The ammonium salt represented by the above formula 1 is disclosed in
Most of them are different from each other, although they partially overlap with the ammonium salt proposed in JP-A-7366. More specifically, 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 perhalogen acid, benzene-based sulfonic acid, or alkylbenzene-based sulfonic acid, both are 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. Moreover, in Formula 3, R ₄ has 1 carbon atom.
-4 hydroxyalkyl group, while having the formula 1
Then, the equivalent of this is (R ₄ O) nH, and R ₄
Is an alkylene group having 2-4 carbon atoms, and n is an integer of 1-15.
Is only one part when n is 1. That is, when n is an integer of 2 or more, the ammonium salt of formula 1 has formula 3
It is completely different from the ammonium salt of. others,
All of R ₁ , R ₂ and R ₃ only partially overlap. Therefore, most of the ammonium salt of formula 1 used in the present invention is different from the ammonium salt proposed in Japanese Patent Publication No. 40-7366.

Further, the present invention uses the ammonium salt of the formula 1 together with the perchlorate of the formula 2 in Japanese Patent Publication No. 40-7.
This is different from what is disclosed in Japanese Patent No. 366. 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, the present invention is completely novel because the perchlorate is allowed to coexist with the ammonium salt of the formula 1 to enhance the antistatic effect and to keep the resin colorless and transparent.

(Explanation of Ammonium Salt) In the ammonium salt of the formula 1 used in the present invention, as described above, any one of R ₁ , R ₂ and R ₃ has a carbon number of 5-.
It is necessary to have 24 alkyl groups, of which the most commonly used are those having 8-18 carbon atoms. Further, the remaining _{two of} R ₁ , R ₂ and R ₃ need to be alkyl groups having 1 to 5 carbon atoms, of which one commonly used is one having 1 carbon atoms.
-2 is an alkyl group. Further, R ₆ needs to be an alkylene group having 2 to 4 carbon atoms, of which the alkylene group having 2 to 36 carbon atoms is commonly used. n needs to be an integer from 1-15,
Commonly used are 1-5. Further, X is usually an anion of hydrochloric acid or perchloric acid.

The ammonium salt of Formula 1 is based on 100 parts by weight of resin.
Used at a rate of 0.5-5 parts. Of these, preferred is 3 parts or less. The reason is that ammonium salt
If the amount is less than 0.5 part, the effect is not sufficiently exhibited. On the contrary, if 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. It is because heat resistance and water resistance are lowered.

(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, perylium, 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 to 1 part by weight of the compound 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.

(Other Compounds) A chlorine-containing resin, especially a vinyl chloride resin, is usually added with a plasticizer not only when it is used as a soft resin but also when it is used as a hard resin. In addition, stabilizers, fillers, 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.

(Effect of Compounding Order) The composition according to the present invention has slightly different properties depending on the order of addition of compounds to be compounded. The common wisdom about compositions is that the formulation for making the composition does not change much in the properties of the resulting product, no matter which order it is added. However, in the composition of the present invention, when the addition order of the composition is changed, the electrical resistance of the obtained composition, that is, the antistatic property, is slightly changed. In that respect, the composition feels very strange.

For example, rather than adding the ammonium salt of formula 1 and the perchlorate salt of formula 2 separately to the vinyl chloride resin, the ammonium salt of formula 1 and the perchlorate salt of formula 2 are mixed well in advance. Then, by adding the mixture to the vinyl chloride resin, the vinyl chloride resin which is less likely to be charged can be obtained. When a plasticizer is used, the ammonium salt and perchlorate may be separately added to the plasticizer and mixed well, then the mixture may be mixed, and then mixed with the resin. First, an ammonium salt and a perchlorate are mixed well at first, and especially when heated (for example, 40-100 ° C.).
After mixing for 2 hours and cooling, this is added to a plasticizer and mixed well, and when this mixture is added to a resin, a vinyl chloride resin that is less likely to be charged can be obtained. In addition to the poor charge resistance, thermal stability and water resistance are further improved.

(Influence of Plasticizer) Further, when the composition of the present invention is blended with the plasticizer, it is also influenced by the type of the plasticizer. As the plasticizer, fatty acid ester, phthalic acid ester, adipic acid ester, trimellitic acid ester and the like can be used. Such a plasticizer may be used in an amount of 30-100 parts, preferably 40-70 parts, based on 100 parts by weight of the resin.

(Effects of the Invention) The composition according to the present invention comprises 0.5 to 5 parts by weight of the ammonium salt of the formula 1 with respect to 100 parts by weight of the chlorine-containing resin, and the formula 2
Since _0.02 to _0.5 parts by weight of the perchlorate of 1 to 1 part by weight of the ammonium salt represented by (a) and a chlorine-containing resin are contained, it is difficult to be charged as a composition. Since it is difficult to adsorb dust, it is possible to process this to obtain a chlorine-containing resin product with excellent quality. Further, since the resin product thus obtained is less likely to be charged, it does not adsorb dust, and therefore the surface can be kept in the configuration. From this, it becomes clear to measure the electrical resistance of the product. That is, in the case of the present invention, the electric resistance value is 1 digit or more in ohm unit, and usually 2 digits to 4 digits, as compared with the conventional one.
It is clear from the fact that the digits are getting smaller. Further, the composition according to the present invention is supposed to contain the above-mentioned ammonium salt and perchlorate salt, but gives a colorless and transparent product with little coloring. Thus, according to the present invention, a colorless and transparent chlorine-containing resin product which is difficult to be charged can be obtained, so that the practical effect is great.

(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 ° C, Damper No. 3, Tensile speed 200mm / min Compatibility: 120 ° C at 50 ° C, 95% relative humidity Judgment of bleeding after placement Electric resistance: (1) Surface resistance: Ohms at 30 ° C and 50% relative humidity (2) Volume resistivity: Ohms at 30 ° C and 50% relative humidity-cm Volatile loss: Weight loss rate after heating at 100 ° C for 6 hours (weight% ).

Colorability: Coloring was visually evaluated and divided into 6 levels. Colorlessness was evaluated as 1 and yellow coloring was evaluated as 6.

Example 1 In this example, the ammonium salt of Formula 1 is an N-polyene such that R ₁ is a decyl group, R ₂ and R ₃ are both methyl groups, R ₄ is an ethylene group and n is 3. Oxyethylene-N, N, N-decyl, dimethylammonium perchlorate was used. Further, as the perchlorate of Formula 2, magnesium perchlorate in which M is magnesium was used.

To 100 parts of vinyl chloride resin, 3 parts of the above ammonium perchlorate, 0.7 part of magnesium perchlorate, 50 parts of dioctyl phthalate, and 2.5 parts of a palladium-zinc-based stabilizer (Nissan Fuero LTL-272), 2 parts of an epoxy-based stabilizer (D-178 manufactured by ADEKA ARGUS CORPORATION) was blended. This compound was roll-kneaded at 160 ° C. for 6 minutes and then pressed at 170 ° C. for 7 minutes to form 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 percentage in the tensile test was 345.
%, Expansion force 2.55 kg / mm ² , bleeding was not observed at all in the compatibility test, surface resistance was 8.0 × 10 ³ ohms, volume resistivity was 4.3 × 10 ⁹ ohm-cm, coloring was 1 and it was colorless and transparent. The volatilization loss was 0.45%. Therefore, it was confirmed that this sheet is a soft vinyl chloride resin sheet which is hard to be charged, is colorless and transparent, and is good.

Example 2 In this example, no plasticizer was used. As the ammonium salt of formula 1, R ₁ is a decyl group and R _{2 is}
And R ₃ are both methyl groups, R ₄ is an ethylene group and n
Is N-polyoxyethylene-N, N,
N-decyl and dimethylammonium perchlorate were used. This ammonium salt differs from the ammonium salt of Example 1 only in the value of n. Further, as the perchlorate of the formula 2, lithium perchlorate in which M is magnesium was used.

To 100 parts of vinyl chloride resin, 4.8 parts of the above ammonium salt, 0.8 part of lithium perchlorate, 3 parts of epoxidized soybean oil as a stabilizer, 1 part of octyl-tin mercaptide, and 1 part of barium-zinc stabilizer were added. After thoroughly mixing the product at room temperature, it was kneaded with a roll at 175 to 185 ° C for 6 minutes and then pressed at 180 ° C for 7 minutes to obtain a resin sheet.

When the physical properties of this sheet were measured, no bleeding was observed in the compatibility test, and the surface electric resistance was 4 × 10.
¹⁰ ohm, volume resistivity 7 × 10 ¹⁰ ohm-cm,
The degree of coloration was colorless and transparent, and was evaluated to be 1. It was recognized that the product was hard to be charged and was colorless and transparent to give a good product.

Example 3 In this example, as the ammonium salt of formula 1, Was used. In addition, barium perchlorate was used as the perchlorate of Formula 2.

To 100 parts of vinyl chloride resin, 1 part of the above ammonium chloride, 0.4 part of barium perchlorate, and 40 parts of digisyl adipate 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 2.60 kg / mm ² , bleeding was not recognized in the compatibility test, and the electrical resistance was a surface resistance of 4.5 × 10 ⁸ ohms and a volume. The specific resistance was 2.0 × 10 ⁹ ohm-cm, the coloring property was colorless and transparent, and was evaluated to be 1. The volatilization loss was 0.15%, which was recognized to be colorless and transparent because it was difficult to be charged. It was

Example 4 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, 0.3 part of lithium perchlorate, which is 3 parts of the above ammonium salt, and 45 parts of dibutyl phthalate 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 percentage in the tensile test was 290%, the resistance force was 2.30 kg / mm ² ,
No bleeding was found in the compatibility test, and the electrical resistance was 4.0 × 10 ⁸ ohms surface resistance and 2.1 × 10 ⁹ volume resistivity.
Ohm-cm, colorability is colorless and transparent, and is evaluated as 2,
The volatilization loss was 2.55%. Therefore, as a whole, it was recognized that the product was hard to be charged, was colorless and transparent, and was good.

Example 5 This example considers the order of addition.

In this example, as the ammonium salt of Formula 1, Was used. Further, lithium perchlorate was used as the perchlorate of Formula 2. Diisonyl phthalate was used as the plasticizer.

The order of addition was as follows. That is, to 100 g of diisononyl phthalate, 5 g of the above ammonium salt and 0.4 g of lithium perchlorate were added, and this mixture was stirred at 60 ° C. for 1 hour.
Mix well for time and cool to get a clear solution. 55 parts of the above solution was added to 100 parts of vinyl chloride resin, and then the same stabilizer as used in Example 1 was added in exactly the same proportion as in Example 1.

After that, a sheet having a thickness of 1 mm was obtained in exactly the same manner as in Example 1, and the physical properties of this sheet were measured. As a result, the elongation percentage in the tensile test was 310%, and the resistance force was 2.4.
kg / mm ² , no bleeding was observed in the compatibility test, and the electrical resistance was 4.8 × 10 ⁸ ohms in surface resistance, 9.5 × 10 ⁸ ohms-cm in specific volume resistance, and the coloring property was very slight. It was evaluated as 2, and the volatilization loss was 0.35%.
Therefore, it was recognized that the product as a whole was difficult to be charged, was colorless and transparent, and was good.

Example 6 This example is an example in which the same materials as in Example 5 were used and added simultaneously without considering the order of addition.

First, 100 parts of vinyl chloride resin, 52.5 parts of diisononyl phthalate, and 2.5 parts of the ammonium salt used in Example 5 were used.
Parts and 0.2 parts of lithium perchlorate were added simultaneously, and the same stabilizer was added in the same proportion.

After that, a sheet having a thickness of 1 mm was obtained in exactly the same manner as in Example 1, and the physical properties of this sheet were measured. As a result, the elongation rate in the tensile test is 300% and the resistance force is 2.5.
kg / mm ² , no bleeding was found in the compatibility test, and the electrical resistance was 7.5 × 10 ⁸ ohms, and the volume resistivity was
The coloring property was 2.0 × 10 ⁹ ohm-cm, and the coloring property was very slightly colored, and was evaluated as 2. The loss on volatilization was 0.40%. Therefore, it was recognized as a soft vinyl chloride resin sheet which is hard to be charged as a whole and is colorless and transparent.

Comparing Example 6 with Example 5, since Example 5 has a smaller electric resistance value, Example 5 is superior in antistatic property. This is considered to be due to the addition method.

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.

5 parts of the above antistatic agent and 50 parts of plasticizer in 100 parts of vinyl chloride
And the same amount of the same stabilizer as in Example 1 were added. 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 a tensile test was 330%, the tensile strength was 2.50 kg / mm ² , bleeding was not recognized at all in a compatibility test, and the electrical resistance was a surface resistance of 6.0 × 10 ^9. Ohm, volume resistivity 1.0 × 10
¹¹ ohm-cm, colorability is considerably colored and rated 4;
The volatilization loss was 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 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 in the compatibility test at all, and the electrical resistance had a surface resistance of 1.
0 × 10 ¹² ohms, volume resistivity 9.0 × 10 ¹² ohm-cm, colorless and transparent, and evaluated as 1.
It was 77%. Therefore, it was confirmed that the colorless transparency was good although it had a drawback that it was easily charged as a whole.

Claims (1)

[Claims] 1. (a) General formula 0.5 to 5 parts by weight with respect to 100 parts by weight of a chlorine-containing resin, (b) a perchlorate represented by the general formula M (ClO ₄ ) m, and an ammonium salt represented by (a) 1 0.02 to 0.5 parts by weight with respect to parts by weight, (c) characterized by containing a chlorine-containing resin,
An antistatic chlorine-containing resin composition. However, R ₁ , R ₂ and R
1 is an alkyl group having a carbon number of 5-24 of the _three, the other is an alkyl group having 1-5 carbon atoms, _{R 4} is an alkylene group having 2-4 carbon atoms, n represents 1-15 integer, X is hydrochloride , An anion of chloric acid or perchloric acid, M is a metal ion or ammonium ion belonging to 1A or 2A in the periodic table, and m is 1 or 2.