JPH0791428B2 - 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 resin 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 were included in old times. 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 present inventor, the product was neither satisfactory in antistatic property nor in colorless transparency. 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 is slightly colored. Therefore, it can be seen that the resin is decomposed. Therefore, it has been necessary to develop an antistatic agent having both excellent antistatic properties and colorless transparency.

(Problems to be Solved by the Invention) The present invention prevents thermal decomposition of a chlorine-containing resin and lowers its electrical resistance to further improve both colorless transparency and antistatic property, It is intended to provide a chlorine-containing resin composition which is suitable for use as a static electricity-free skin material and has a small heating loss.

(Means for Solving the Problem) The present inventor has extensively studied various properties of an antistatic agent and a compound similar thereto proposed in Japanese Patent Publication No. 40-7366, and in particular, the properties exhibited to 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 it to a vinyl chloride resin together with a specific perchlorate.
It has been found that a resin composition having good thermal stability, little coloring, and less likely to be charged can be obtained. In addition, this inventor
In the case of imparting the vinyl chloride resin with the antistatic property and the heat resistance in this manner, coexistence of tri-2-ethylhexyl trimellitate as a plasticizer will keep the antistatic property for a long time, which is convenient. Found. Further, the present inventor, as a result of continuing research, prepared a specific ammonium salt not proposed in the above publication and added it to a vinyl chloride resin together with a specific perchlorate and the above plasticizer, It has been found that a resin composition having a small amount of loss on heating and good colorless transparency and good antistatic property can be obtained. The present invention has been completed based on such knowledge.

The gist of the present invention is to add three kinds of compounds to a chlorine-containing resin.

One of the three compounds is an N- (poly) oxyalkylene-N, N, N-trialkylammonium salt, which has the general formula Is a compound represented by. The second is a perchlorate, which is a compound represented by the general formula M (ClO ₄ ) m (formula 2). The remaining third one is a tri-
2-ethylhexyl trimellitate having the formula: Is a compound represented by. Where R ₁ , R ₂ and R ₃ are
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, and R ₄ is 2 carbon atoms.
-4 is an alkylene group, n 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 an integer of 1 or 2.

That is, the present invention comprises (a) an ammonium salt represented by the above formula 1, (b) a perchlorate represented by the above formula 2, and (c) a trimellitic acid ester represented by the above formula 4. And (d) a chlorine-containing resin, which provides a hardly-charged chlorine-containing resin composition.

(Relationship with Prior Art) The ammonium salt represented by the above formula 1 is disclosed in JP-B-40-
Most of them are different, although they partially overlap with the ammonium salt proposed in Japanese Patent No. 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 perhalogenic 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 chlorine 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, in formula 1, the corresponding one is (R ₄ O) nH, R ₄ is an alkylene group having 2-4 carbon atoms, 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, the ammonium salt of the formula 1 in which the present invention is used is mostly different from the ammonium salt proposed in Japanese Patent Publication No. 40-7366.

The present invention also provides that the ammonium salt of formula 1 is used in combination with the perchlorate of formula 2.
This is different from that disclosed in Japanese Examined Patent Publication No. 40-7366. 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 in most cases the resin can be kept colorless and transparent.

The invention also requires the use of tri-2-ethylhexyl trimellitate as a plasticizer. This plasticizer is known as a plasticizer for vinyl chloride resins, but it is not known to use it with ammonium salts and perchlorates which act as antistatic agents.

(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. Because.

(Explanation of Perchlorate) As the perchlorate of the 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 to 1 part of the compound of the formula 1, and the preferable ratio is 0.05 part-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 the amount is 5 parts or more, not only the antistatic effect, which is exhibited in cooperation with the ammonium salt of the formula 1, does not improve in proportion to the increased amount, but also the thermal stability of the resin is impaired and the water resistance decreases. This is because such harmful effects appear.

(Explanation of tri-2-ethylhexyl trimellitate) Tri-2-ethylhexyl trimellitate (hereinafter referred to as TM) is known as a plasticizer for vinyl chloride resin as described above. The product exhibits the properties of a hard resin when added in a small amount to the vinyl chloride resin, but the product exhibits the properties of a soft resin when a large amount of TM is added. When TM is added to the resin together with the ammonium salt of formula 1 and the perchlorate of formula 2, the loss on heating when this is heated is small, and the compatibility of TM with the resin is excellent, so it is difficult to charge for a long time. In addition, a colorless and transparent or slightly colored product can be obtained. The amount of TM added to the resin is 30 to 100 parts with respect to 100 parts 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.

(Effect of Compounding Order) The composition according to the present invention has slightly different properties depending on the order of addition of the compounds to be compounded. The common wisdom about compositions generally 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 this 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. And adding the mixture to TM and vinyl chloride resin,
It is possible to obtain a vinyl oxide resin that is less likely to be charged.
Alternatively, the ammonium salt and the perchlorate may be separately added to TM and mixed well, then the mixtures may be mixed together and then mixed with the resin. Mix well with chlorate, mix under heating (eg 40-100 ° C) for 1-2 hours and cool, then add this to TM and mix well, then add this mixture to resin Then, 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.

(Effect of the invention) Since the composition according to the present invention contains the ammonium salt of formula 1, the perchlorate of formula 2, and the chlorine-containing resin,
The composition is less likely to be charged, and thus does not adsorb dust in the processing step, so that this can be processed to obtain a chloride-containing resin product with excellent quality. Further, the resin product thus obtained does not adsorb dust because it is difficult to be charged, and therefore the surface can be kept beautiful. This is evident when measuring the electrical resistance of the product. That is, according to the present invention, it is apparent that the electric resistance value is smaller by one digit or more in ohm unit, usually by two to three digits than that of the conventional one. Further, the composition according to the present invention is supposed to contain the above-mentioned ammonium salt and perchlorate, but it gives a colorless and transparent product with little coloring. Further, since the composition according to the present invention contains tri-2-ethylhexyl trimellitate, when the content is low, the composition exhibits the properties of a hard resin, and conversely when the content is high, The composition exhibits the properties of a soft resin, the properties of the product can be widely changed, and a colorless and transparent product can be obtained. Moreover, since tri-2-ethylhexyl trimellitate is contained, the volatile content from the composition is reduced, and therefore, the property of being difficult to be charged can be maintained for a long time. Since the present invention retains the heat resistance and the antistatic property for a long time as described above, it has a great practical effect.

For example, in the case of automobile interior materials, when the light transmittance of the windshield decreases due to the presence of a plasticizer in the interior materials, the safety of the automobile decreases, so the resin composition of the present invention is It is extremely suitable for use as a material.

(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 ℃ , Ohm under 50% relative humidity (2) Volume resistivity: 30 ° C, Ohm under 50% relative humidity-cm Volatilization loss: Weight loss rate after heating at 100 ° C for 6 hours (% by weight) ... heating loss Also say.

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, ammonium salt of formula 1 wherein R ₁ octyl group, R ₂ and R ₃ are both methyl groups, R ₄ is ethylene group and n is 2 That is, Was used. Further, as the perchlorate of formula 2, magnesium perchlorate Mg (ClO ₄ ) in which M is magnesium
₂ was used.

100 parts of vinyl chloride resin to the above ammonium perchlorate salt 2
Parts, 0.5 parts of magnesium perchlorate, and TM70,
Further, 2.5 parts of a barium-zinc-based stabilizer (LTL-272, manufactured by Nissan Fuero Co., Ltd.) and 2 parts of an epoxy-based stabilizer (D-178, manufactured by Adeka Agas Co., Ltd.) were added as stabilizers. The mixture was roll milled at 160 ° C for 6 minutes and then at 170 ° C for 7 minutes.
The resin sheet was obtained by pressing for a minute.

The physical properties of this sheet were measured. As the physical properties, tensile strength, compatibility, electric resistance, coloring degree, and volatilization increase were measured. As a result, the elongation rate in the tensile test was 370%, the tensile strength was 2.75 Kg / mm ² , no bleed was observed in the compatibility test, the surface resistance was 3.1 × 10 ⁹ ohms, and the volume resistivity was 1.8 × 1
It was 0 ¹⁰ ohm-cm, completely colorless and transparent, and the coloring degree was evaluated to be 1, and the volatilization loss was 0.03%. From this, it was confirmed that this sheet is hard to be charged, is colorless and transparent, and retains its properties for a long time.

Example 2 In this example, ammonium salt of formula 1 wherein R ₁ is an octyl group, R ₂ and R ₃ are ethyl groups, R ₄ is an ethylene group and n is 2 , Ie The compound represented by the structural formula of was used. As the perchlorate of Formula 2, barium perchlorate Ba (ClO ₄ ) _{2 in} which M is barium was used.

Specifically, 100 parts of vinyl chloride resin, 1 part of ammonium perchlorate, 0.6 part of barium perchlorate, and TM7
0 part was added, and the same stabilizer as that used in Example 1 was further mixed in the same amount. 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 340%, the tensile strength was 2.50 Kg / mm ² , bleeding was not observed in the compatibility test at all, and the electrical resistance had a surface resistance of 3.
0 × 10 ⁹ ohms, volume resistivity 9.5 × 10 ⁹ ohms-cm, colorless and transparent, and evaluated to have a coloring degree of 1, loss on heating of 0.05
%Met. Therefore, it was confirmed that this sheet is not easily charged, is colorless and transparent, and has a small weight loss upon heating, and thus can retain its properties for a long time.

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

More specifically, 100 parts of vinyl chloride resin was added with 3 parts of the upper ammonium salt, 0.3 part of barium perchlorate and 60 parts of TM, and the same amount of the stabilizer used in Example 1 was further added.

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 290%, the tensile strength was 2.65 Kg / mm ² , bleeding was not recognized at all in the compatibility test, and the electrical resistance was 1.0 × 1
0 ⁹ ohm, a volume resistivity of 6.0 × 10 ⁹ ohm -cm, coloring degree was colorless and transparent is evaluated as 1, the heating loss was 0.055. Therefore, it was recognized that the sheet is not likely to be charged, is colorless and transparent, and has a small heat loss, so that it can maintain its characteristics for a long time.

Example 4 This example examines the effect of the order of addition of antistatic agents.

In this example, as the ammonium salt of Formula 1, Was used. As the perchlorate of Formula 2, magnesium perchlorate Mg (ClO ₄ ) ₂ was used.

The order of addition was as follows. First, 3 g of the above ammonium salt and 0.1 g of magnesium perchlorate were added to 100 g of TM, and this was well mixed at 50 ° C. for 2 hours to form a mixture. 70 parts of this mixture was mixed with 100 parts of vinyl chloride resin, and then the same amount of the stabilizer used in Example 1 was added and well mixed at room temperature. Then, this mixture was kneaded with a roll at 170 ° C. for 6 minutes, and then 170 A resin sheet having a thickness of 1 mm was obtained by pressing at 7 ° C. for 7 minutes.

When the physical properties of this sheet were measured, the elongation rate in the tensile test was 360%, the tensile strength was 2.6 kg / mm ² , bleeding was not observed in the compatibility test at all, and the electrical resistance was 2.0 × 10 ⁹
The ohm and volume resistivity were 4.9 × 10 ⁹ ohm-cm, the coloring degree was evaluated to be 1, and the weight loss upon heating was 0.03. Therefore, this sheet was recognized as being good in that it is difficult to be charged, is colorless and transparent, and has a small loss on heating, and therefore can retain its properties for a long time.

Example 5 This example is an example in which the same materials as in Example 4 were used and the addition was simultaneously performed.

To 68 parts of vinyl chloride resin, 68 parts of TM as a plasticizer, 2.1 parts of the same ammonium salt used in Example 4 and 0.07 part of magnesium perchlorate were added at the same time.
The same amount of the stabilizer used in the step 1 was added and mixed well at room temperature. Thereafter, the same treatment as in Example 4 was carried out to obtain a sheet.

When the physical properties of this sheet were measured, the elongation rate in the tensile test was 355%, the tensile strength was 2.7 kg / mm ² , no bleeding was observed in the compatibility test, and the electrical resistance was 5.5% in surface resistance.
X10 ⁹ ohms, volume resistivity 1.8 x 10 ¹⁰ ohm-cm,
The degree of coloring was evaluated as 1, and the weight loss on heating was 0.035. Therefore, this sheet was recognized as a good one that retains its properties for a long time because it is difficult to be charged, is colorless and transparent, and has a small loss on heating.

Compared with the electrical resistance of Example 4, the electrical resistance of Example 5 has a smaller resistance value. Therefore, it is considered that the antistatic property of Example 4 is superior. To be 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.

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 , bleeding was not observed in the compatibility test at all, and the electrical resistance was 6.0 × 1
0 ⁹ ohm, a volume resistivity of 1.0 × 10 ¹¹ ohm -cm, coloring is evaluated as 4 correspond colored, volatility 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 In this comparative example, only a plasticizer was added to vinyl chloride resin,
In this example, 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. Then, 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 was 1.0 x 1
It was evaluated to be 0 ¹² ohm, volume resistivity 9.0 × 10 ¹² ohm-cm, and colorless and transparent, and the volatility loss 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.

Comparative Example 3 This comparative example does not use the perchlorate of Formula 2. As an antistatic agent Was used. TM was used as the plasticizer.

100 parts of vinyl chloride resin, 1 part of the above antistatic agent, TM70
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 the tensile test was 340%, the tensile strength was 2.6 kg / mm ² , bleeding was not recognized in the compatibility test, and the electrical resistance was 8 × 10 5.
^{It was 10} ohms, the volume resistivity was 8 × 10 ¹¹ ohm-cm, the colorability was colorless and transparent, and was evaluated as 1. The loss on volatilization was 0.03%. Therefore, it was recognized as defective because it was easily charged as a whole.

Comparative Example 4 This comparative example is an example in which the ammonium salt of Formula 1 was not used as the antistatic agent, and only the perchlorate of Formula 2 was used. Magnesium perchlorate was used as the perchlorate.

To 100 parts of vinyl chloride resin, 1.3 parts of magnesium perchlorate and 45 parts of TM were added, and the same stabilizer as in Example 1 was added thereto in the same amount. After that, the same treatment as in Example 1 was performed to obtain a sheet.

When the physical properties of this sheet were measured, the elongation rate in a tensile test was 240%, the tensile strength was 2.90 Kg / mm ² , bleeding was not recognized in a compatibility test, and the electrical resistance was a surface resistance of 5.0.
× 10 ¹² ohms, volume resistivity is 2 × 10 ¹³ ohm-cm, coloring is slightly evaluated and evaluated as 2, and volatilization loss is
It was 0.02%. Therefore, it was recognized as defective because it was easily charged as a whole.

Claims (1)

[Claims] 1. (a) General formula An ammonium salt represented by: (b) a perchlorate represented by the general formula M (ClO ₄ ) m, (c) tri-2-ethylhexyl trimellitate, and (d) a chlorine-containing resin. An antistatic chlorine-containing resin composition, characterized in that However, R ₁ , R ₂ and R ₃
Among them, one 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 to 15, X is hydrochloric acid, 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.