JPH05186764A - Liquid antistatic composition and antistatic polar polymer composition - Google Patents

Abstract

PURPOSE:To obtain liq. antistatic compsn. which gives a polar polymer consistent antistatic properties by mixing a specific polyester with a perchlorate in a specified wt. ratio. CONSTITUTION:100 pts.wt. polyester of formula I (wherein R1 is 1-6C alkylene; R2 is 2-8C alkylene, alkenylene, or phenylene; R3 is H or methyl; R4 is 2-3C alkylene; R5 is 1-8C alkyl; m1 is 1-4; and n1 is 2-8) is mixed with 1-8 pts.wt. perchlorate of formula II (wherein one of R6, R7, and R8 is 8-24C alkyl and the rest are 1-5C alkyl; R9 is 2-3C alkylene; and m2 is 1-5) (e.g. N-dioxyethylene- N,N,N-monooctyldimethylammonium perchlorate) to give a liq. antistatic compsn.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic liquid composition (hereinafter abbreviated as liquid composition) for antistatic a polar polymer, and an antistatic polar composition containing the liquid composition. It relates to a polymer composition.

[0002]

2. Description of the Related Art Generally, a film or sheet made of a polar polymer such as polyvinyl chloride is easily charged.
Therefore, when the film or sheet is used as a curtain in a clean room, dust is attached due to the electrification of the film or sheet. Further, when an IC product is packaged using these films or sheets as a packaging material, the packaged IC product may be inconvenient due to the charging of these packaging materials. Therefore, in the electronics industry including the IC industry in recent years, it has been desired to impart antistatic performance to polar polymers such as polyvinyl chloride.

As a conventional method for preventing the charge of the polar polymer, (a) a method of applying a surfactant-based antistatic agent to the surface of the polar polymer (coating method), (b)
A method of kneading an antistatic agent into a polar polymer (kneading method), (c) a method of adding a conductive filler of metal powder or carbon to the polar polymer (filler addition method), and the like are adopted.

[0004]

However, the above-mentioned coating method (a) has a problem that the antistatic effect is significantly reduced over time, and the kneading method (b) usually involves an antistatic agent and a polar polymer. Bleed of the antistatic agent occurs due to its low compatibility with, and further deterioration of the transparency of the molded product becomes a problem. In addition, the above-mentioned method (c) of adding a filler has a problem that a transparent molded product cannot be obtained and coloring (color printing) of the molded product cannot be performed. Therefore, the present invention addresses the above-mentioned conventional demands and solves the above-mentioned conventional problems.

That is, the first object of the present invention is a composition to be contained in a polar polymer, which maintains stable antistatic property of the polar polymer for a long period of time, and has good transparency when formed into a molded product. It is to provide a liquid composition that can be formed and also has excellent water resistance, heat resistance and bleeding resistance.

A second object of the present invention is to maintain a stable antistatic property for a long period of time, and to obtain a molded product with good transparency, and to obtain water resistance, heat resistance and bleed resistance. It is an object of the present invention to provide a polar polymer composition capable of achieving excellent properties.

[0007]

The invention according to claim 1 for achieving the above-mentioned first object is a general formula (hereinafter, referred to as
Also called a formula. ) (I)

[Chemical 6] And the general formula (II)

[Chemical 7] A liquid composition containing a perchlorate compound represented by the formula (1) and blending it with a polar polymer to make the polar polymer antistatic. This composition is based on 100 parts by weight of the polyester (hereinafter, simply referred to as "parts").
The perchlorate compound is contained in a ratio of 1 to 8 parts.

A second aspect of the present invention for attaining the first object.
The invention related to

[Chemical 8] And the general formula (II)

[Chemical 9] A perchlorate compound represented by and general formula (III)

[Chemical 10] And a liquid composition containing the dibasic acid ether represented by the formula (1) and blending it with a polar polymer to make the polar polymer antistatic. This composition is characterized in that it is contained in a ratio of 1 to 8 parts of the perchlorate compound and 20 to 900 parts of the dibasic acid ester with respect to 100 parts of the polyester.

The polar polymer composition of the invention according to claim 3 for achieving the above-mentioned second object is 20 to 100 parts of the antistatic liquid composition according to claim 1 with respect to 100 parts of the polar polymer. It is characterized by being mixed in parts.

Furthermore, the polar polymer composition of the invention according to claim 4 for attaining the above-mentioned second object comprises 20 parts of the antistatic liquid composition according to claim 2 per 100 parts of the polar polymer. It is characterized by being mixed up to 100 parts.

The above-mentioned compound of the formula (I) is directly esterified with a dibasic acid and glycols or transesterified with a dicarboxylic acid ester and glycols,
Or a condensation reaction of dicarboxylic acid chloride and a diol,
Can be synthesized by various polyester synthesis reactions and esterification reaction with a monohydric alcohol for sealing.

[0012] For example, as the dibasic acid for the direct esterification reaction, maleic anhydride, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, etc., or a mixture thereof is used. The glycols that can be used include ethylene glycol,
Propylene glycol, butylene glycol, hexamethylene glycol, etc. or mixtures thereof may be used.

Examples of the monohydric alcohol for sealing include alkyl alcohols having an alkoxy group such as ethoxy, propoxy, butoxy, pentyloxy, and hexyloxy in which carbon atoms are increased by 1 from methoxy having 1 carbon atom. , Diethylene glycol monomethyl ether,
Alcohol supplied from diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, etc. or mixtures thereof can be used.

The perchlorate compound represented by the formula (II) can improve the antistatic ability when used in combination with the polyester of the formula (I). Examples of the perchlorate compound of the formula (II) include N-dioxyethylene-N, N, N
-Monooctyldimethylammonium perchlorate, N-
Dioxyethylene-N, N, N-monododecyldimethylammonium perchlorate, N-dioxypropylene-
N, N, N-monostearyldimethylammonium perchlorate, N-trioxyethylene-N, N, N-monolauryldimethylammonium perchlorate and the like can be used.

In the invention of claim 1, it is preferable that the perchlorate compound is contained in a ratio of 1 to 8 parts per 100 parts of the polyester. When the amount of the perchlorate compound is less than 1 part, sufficient antistatic effect cannot be obtained, and when it exceeds 8 parts, bleeding occurs in the polar polymer composition and thermal stability is deteriorated.

In the above formula (III), m ₃ is 0.
Represents an integer of 4 and, when m ₃ is 0, R ₁₁ has 6 carbon atoms.
When an alkyl group having to 13, m ₃ is 1 to 4 R ₁₁ represents an alkyl group having 1 to 8 carbon atoms. Further, the carbon number of R _{10 11} and the integer of m ₃ may be different.

The compound of formula (III) can be synthesized by an esterification reaction of an aliphatic or aromatic dibasic acid with a monoalkyl ether of ethylene or propylene glycol, or an alcohol having 6 to 13 carbon atoms.

As the dibasic acid, maleic anhydride,
Fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, etc., or a mixture thereof can be used, and as the glycol monoalkyl ether, ethylene glycol monomethyl ether,
Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, propylene glycol mono-2-ethylhexyl ether, diethylene glycol monoethyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, tripropylene glycol monobutyl ether, etc. Alcohol supplied from a mixture of As the alcohol having 6 to 13 carbon atoms, 2-ethylhexyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecanol, tridecanol or the like or a mixture thereof can be used.

In the second aspect of the invention, it is preferable to add 1 to 8 parts of the perchlorate compound and 20 to 900 parts of the dibasic acid ester to 100 parts of the polyester. If the amount of the perchlorate compound is less than 1 part, a sufficient antistatic effect cannot be obtained, and if it exceeds 8 parts, bleeding occurs in a molded product of the polar polymer composition and thermal stability is deteriorated.

In the inventions of claims 1 and 2, the polar polymer means, for example, polyvinyl chloride, polyvinylidene chloride, vinyl chloride or a copolymer of vinylidene chloride and vinyl acetate or other vinyl compound. .. Moreover, in the liquid composition according to the first and second aspects, if necessary, an additive such as an antioxidant can be mixed with the polar polymer together with the filler and used.

In the third aspect of the invention, it is preferable to add 20 to 100 parts of the liquid composition to 100 parts of the polar polymer. If the liquid composition is less than 20 parts, good antistatic ability cannot be obtained, and if it is more than 100 parts, not only the water resistance and oil resistance of the polar polymer molded product deteriorate but also the flexibility becomes too large to be practical. ..

Similarly, in the invention of claim 4, it is preferable to add 20 to 100 parts of the liquid composition to 100 parts of the polar polymer. When the amount of the liquid composition is less than 20 parts, good antistatic ability cannot be obtained, and when it is more than 100 parts, not only the water resistance and oil resistance of the polar polymer molded article are deteriorated but also the flexibility becomes too large, which is practical. No longer.

[0023]

The polyester of formula (I) has an ether group, which is a strongly hydrophilic group, and a carbonyl group having a high affinity for polar polymers in the molecule. The dibasic acid ester of the formula (III) has an ether group, which is a strongly hydrophilic group, or a lipophilic alkyl group having 6 to 13 carbon atoms, and a carbonyl group having a high affinity for polar polymers in the molecule. ing. Therefore, when the polyester and / or the dibasic acid ester is blended with a polar polymer, excellent antistatic performance and plasticity are exhibited. The perchlorate compound of the formula (II) has a function of greatly improving the antistatic performance in the above-mentioned polyester, or in the blend with the polyester and the dibasic acid ester.

Further, the polyester of the formula (I) is non-migratory due to the polycondensation product, and the polar polymer composition is water resistant,
Bleed resistance. The liquid composition according to the invention of claim 1 or 2 has a good storage stability, although two or three of the polyester, the perchlorate compound and the dibasic acid ester are premixed in an effective predetermined ratio. According to the third or fourth aspect of the invention, the physical properties are excellent in transparency and coloring and have high antistatic properties.

[0025]

【Example】

(Test Example) First, a test example according to the present invention will be described. Polyvinyl chloride (polar polymer) 100 with a degree of polymerization of 1000
2 parts of barium / zinc-based stabilizer, and the respective predetermined amounts of the polyester, dibasic acid ester, and perchlorate compound shown in Table 1 were blended to each of Test Examples 1 to 7 and Comparative Examples 1 to 5. A polar polymer composition was prepared and its physical properties relating to antistatic property were investigated.

The polyesters listed in Table 1 were those obtained by polycondensation reaction of glycol and dibasic acid.
In Table 1, the numerical value at the lower right of the bracket in each polyester item indicates the degree of polymerization. The unit of numerical value of the compounding amount is part. Also,
Each compound in Table 1 is shown by an abbreviation for convenience of description. The abbreviations for each compound are as follows.

[0027]

[Table 1]

That is, the abbreviations relating to glycol are:
1,3BG = 1,3 butylene glycol, PG = propylene glycol, and the abbreviations of dibasic acids are AA = adipic acid, SA = sebacic acid, PA = phthalic anhydride, M
A = maleic anhydride, the abbreviation of ether is EGB
E = ethylene glycol monobutyl ether, DEGE
E = diethylene glycol monoethyl ether, DEG
BE = diethylene glycol monobutyl ether, EG
EE = ethylene glycol monoethyl ether. And the abbreviation of dibasic acid ester is DOP = di-
2-ethylhexyl phthalate, DIDP = di-isodecyl phthalate, DBGA = dibutyl glycol adipate, DBDGA = dibutyl diglycol adipate, D
BGP = dibutyl glycol phthalate, and the abbreviations for perchlorate compounds are: A = N-dioxyethylene-N, N, N-monooctyldimethylammonium perchlorate, B = N-dioxyethylene-N , N, N-monostearyldimethylammonium perchlorate C = N-dioxypropylene-N, N, N-monolauryldimethylammonium perchlorate.

Each of the test and comparative formulations was tested at 155 ° C.
The mixture was kneaded for 10 minutes, and press-molded at 170 ° C. for 6.5 minutes to produce a molded product of a soft vinyl chloride resin sheet having a thickness of 1 mm. The obtained sheet (molded product) had good transparency, and the measurement results of physical properties such as surface resistivity, volume resistivity, water resistance, heat resistance and bleed resistance were as shown in Tables 2 and 3. It was (Table 2 shows the measurement results of Test Examples 1 to 7, and Table 3 shows the measurement results of Comparative Examples 1 to 5.)

[0030]

[Table 2]

[0031]

[Table 3]

The methods for measuring the physical properties shown in Tables 2 and 3 are as follows. Surface resistivity is JIS
According to K6911, the volume resistivity was measured according to JIS K6723. However, the test was performed after leaving it for 1 day in an atmosphere of 23 ° C. and 60% RH. Water resistance is 15 ℃
Each sheet was immersed in the water for 24 hours, the weight loss% of the sheet before and after the immersion was measured, and the value was evaluated. Regarding the heat resistance, each sheet was heated at 170 ° C. for 3 hours, and the weight loss% of the sheet before and after the heating was measured.

Also, each sheet small piece (2 cm × 6 cm) is 17
Heat resistance was also investigated by heating to 0 ° C. and measuring the time (every 15 minutes) required for each piece of sheet to blacken. The burrit resistance of each sheet is 40 ° C and 100% RH.
After leaving it in the atmosphere for 1 week, apply a certain amount of ink evenly on the sheet, and leave it in the atmosphere at 23 ° C, 60% RH for 1 day, and then visually check the degree of the ink peeling. It was judged by. The result of the judgment is displayed as "good", "somewhat bleed", and "very bleed". The transparency was determined by macroscopic observation (sensory evaluation) through each sheet. The results of the observation are: ○ good transparency,
△ Slightly cloudy, × cloudy, and displayed.

As is clear from Tables 2 and 3, the test examples 1 to 7 have good antistatic properties because the surface resistivity and the volume resistivity are smaller than those of the comparative examples 1 to 5. Is recognized. Further, it is recognized that the test examples 1 to 7 have the same or higher transparency as the comparative examples 1 to 5 and are excellent in water resistance and heat resistance.

Next, examples of the present invention will be described. Example 1 50 parts of the polyester of Test Example 1 in Table 1 and 3 parts of the perchlorate compound were mixed and mixed to prepare 53 parts of a polar polymer antistatic liquid composition. This composition was stable for a long period of time, such as 90 days, in a sealed storage at room temperature.

Then, 53 parts of the above-mentioned liquid composition after storage was mixed with 100 parts of polyvinyl chloride (polar polymer) having a polymerization degree of 1000. This formulation contains the respective amounts of polyester and perchlorate compounds which make polyvinyl chloride antistatic. Then, the blend was kneaded at 155 ° C. for 10 minutes and press-molded at 170 ° C. for 6.5 minutes to give a thickness of 1 as in the case of the above-mentioned test example.
A molded product of a soft vinyl chloride resin sheet of mm was obtained.

This sheet had good transparency, and the surface resistivity, volume resistivity, water resistance, heat resistance and bleeding resistance were almost the same as those of Test Example 1 (see Table 2). When this sheet was colored with printing ink, the colorability was good.

Example 2 50 parts of the polyester of Test Example 6 in Table 1 above, 10 parts of a dibasic acid ester and 3 parts of a perchlorate compound were blended and mixed to prevent the polar polymer from being charged. 63 parts of a liquid composition of This composition was stable for a long period of time, such as 90 days, in a sealed storage at room temperature.

Then, 63 parts of the above-mentioned liquid composition after storage was mixed with 100 parts of polyvinyl chloride (polar polymer) having a polymerization degree of 1000. This formulation contains the respective amounts of polyester, dibasic acid ester and perchlorate compound, which makes polyvinyl chloride antistatic. Next, the blend was kneaded at 155 ° C. for 10 minutes and press-molded at 170 ° C. for 6.5 minutes to obtain a molded product of a soft vinyl chloride resin sheet having a thickness of 1 mm as in the case of the above-mentioned test example. ..

The sheet had good transparency, and the surface resistivity, volume resistivity, water resistance, heat resistance and bleeding resistance were almost the same as those of Test Example 6 (see Table 2). When this sheet was colored with printing ink, the colorability was good.

[0041]

EFFECTS OF THE INVENTION A molded product produced by using an appropriate amount of the liquid composition of the invention of claim 1 or the invention of claim 2 in a polar polymer has a long-term stable excellent antistatic property and excellent water resistance. In addition to exhibiting excellent heat resistance and heat resistance and bleeding resistance, it also has good transparency and enables coloring. Particularly, the invention of claim 2 further improves the antistatic property and plasticity of the liquid composition of the invention of claim 1 by including the above-mentioned specific dibasic acid ester. A molded article obtained from the polar polymer composition having an antistatic property according to claims 3 and 4 has stable long-term antistatic property, water resistance, heat resistance, bleeding resistance, and transparency. Coloring is possible because of good properties. Therefore, according to the third or fourth aspect of the present invention, molded articles such as long-term stable antistatic curtains and packaging sheets can be obtained. Therefore, the present invention is particularly preferable in the electronics industry field.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Shumei Hashimoto 19-18 Sakurada-cho, Atsuta-ku, Nagoya-shi, Aichi Toho Rika Kogyo Co., Ltd.

Claims (4)

[Claims] 1. A compound represented by the general formula (I) is: And a polyester represented by the general formula (II): A liquid composition containing a perchlorate compound represented by the formula (1) and blending it with a polar polymer to make the polar polymer antistatic, wherein the perchlorate compound is added to 100 parts by weight of the polyester. An antistatic liquid composition, characterized in that it is contained in a proportion of 1 to 8 parts by weight. 2. A compound represented by the general formula (I) is: And a polyester represented by the general formula (II): A perchlorate compound represented by the general formula (III) A liquid composition containing a dibasic acid ester represented by the formula (1) and blending it with a polar polymer to make the polar polymer antistatic, wherein 1 part by weight of the perchlorate compound is 1 part by weight of the polyester. ~ 8 parts by weight and the dibasic acid ester 20-90
An antistatic liquid composition, characterized in that it is contained in an amount of 0 part by weight. 3. A polar polymer composition comprising 20 to 100 parts by weight of the antistatic liquid composition according to claim 1 with respect to 100 parts by weight of the polar polymer. 4. A polar polymer composition comprising 20 to 100 parts by weight of the antistatic liquid composition according to claim 2 with respect to 100 parts by weight of the polar polymer.