JPH0931243A - Antistatic agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antistatic agent, capable of manifesting excellent antistatic effects and strong durability in washing with water and wiping off and having good fast-acting properties and persistence by adding thereof to a synthetic resin. SOLUTION: This antistatic agent comprises a reactional product prepared by reacting a 3-20C dicarboxylic acid, a dicarboxylic acid anhydride, a lower alkyl ester of the dicarboxylic acid or a dicarboxylic acid halide with (a) a 6-30C aliphatic alcohol or a 6-30C aliphatic amide and (b) a polyhydric alcohol or a compound having an oxirane ring.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antistatic agent. More specifically, the present invention relates to an antistatic agent which, when added to a synthetic resin, exhibits excellent durability against washing with water and exhibits an excellent antistatic effect.

[0002]

2. Description of the Related Art Due to its excellent properties, synthetic resins have been used in large quantities in a wide range of fields as molding materials for films, molded products, fibers and the like. Polyolefins, polyvinyl chloride, polystyrene,
There are ABS resin, acrylic resin, polyester, polyamide, polyurethane and the like, and these resins have excellent electrical insulation properties. On the other hand, however, static electricity is easily generated and accumulated due to friction and the like, which may cause various injuries and ignition due to electrification during molding, processing, use and the like. For example, these synthetic resins are apt to be contaminated by adsorbing dust due to electrification during molding, and stains adhere strongly to cause a significant decrease in commercial value. In addition, the discharge spark may ignite and explode when a flammable gas is used. Further, expensive electronic parts and the like housed in a synthetic resin container may be destroyed due to discharge due to accumulated static electricity. Conventionally, a method of blending carbon black into a synthetic resin as an antistatic agent has been performed in order to prevent the synthetic resin from being charged. However, although this compound has a good antistatic property, the color tone of the obtained molded product is black, and therefore it is not suitable when color classification is required. In addition, it cannot be used for applications that dislike dirt caused by carbon black. Therefore,
As a method of imparting an antistatic effect to a synthetic resin, a method of kneading various antistatic agents into a resin at the time of processing, a method of applying various antistatic agents to the surface of a molded article after molding the synthetic resin, and a method of processing the synthetic resin A method of blending a thermoplastic resin with a hydrophilic resin is usually used. Of the above methods, when a method of applying an antistatic agent to a molded product is used, it easily exhibits excellent antistatic properties,
It is extremely weak against washing with water and wiping off, and it requires a step of applying an antistatic agent in addition to the molding step, which is costly. In addition, the method of blending a synthetic resin with a hydrophilic resin has an antistatic effect that lasts for a long time, but in order to obtain a sufficient antistatic effect, a large amount of a hydrophilic resin must be blended. May deteriorate the physical properties of, and is also disadvantageous in terms of cost. Therefore, a method of imparting antistatic properties to a resin by adding various antistatic agents during resin processing is widely used. As a method of imparting antistatic properties to resins by adding various antistatic agents during molding of synthetic resins, many proposals have been made as follows. For example, a method using N, N-bishydroxyethylalkylamine (Japanese Patent Publication No. 48-177).
46), a method using a polyhydric alcohol fatty acid ester (Japanese Patent Publication No. 44-925), a method using an aliphatic alcohol (Japanese Patent Publication No. 46-1253), glycerin monofatty acid ester and organic phosphite. (Japanese Patent Application Laid-Open No. 58-79042), N,
A method using N-bishydroxyethylalkylamine fatty acid ester (Japanese Patent Laid-Open No. 58-191729),
A method in which alkyldiethanolamine is used in combination with a higher alcohol (JP-A-62-1974434), and a method in which alkyldiethanolamine, a higher alcohol and glycerin monofatty acid ester are used in combination (JP-A-62-29)
5936), a method of using diethanolamide and glycerin mixed fatty acid ester in combination (JP-A-2-28).
9634). As an advantage of the method of adding the antistatic agent at the time of molding the synthetic resin, compared with the method of applying the antistatic agent, there is no need for the antistatic agent coating step,
Further, it is known that the effect can be usually exerted with a small amount of addition, so that the physical properties of the synthetic resin are not greatly affected and the cost is advantageous. However, conventional addition type antistatic agents have the shortcomings that they are less fast-acting than the coating type antistatic agents, they are less durable than when a hydrophilic resin is added, and they are weak in washing and wiping. It was

[0003]

The present invention, when added to a synthetic resin, exerts an excellent antistatic effect, has good fast-acting property and durability, and has a strong durability against washing and wiping. The purpose of the present invention is to provide an antistatic agent that exhibits excellent properties.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have made a specific dicarboxylic acid react with an aliphatic alcohol or an aliphatic amine, and a polyhydric alcohol. It was found that the product obtained thereby gives good antistatic properties when added to a synthetic resin and exhibits excellent durability,
Based on this finding, the present invention has been completed. That is, the present invention provides a dicarboxylic acid having 3 to 20 carbon atoms, a dicarboxylic acid anhydride, a lower alkyl ester of dicarboxylic acid or a dicarboxylic acid halide, and (a) having 6 to 3 carbon atoms.
An antistatic agent containing a reaction product obtained by reacting an aliphatic alcohol having 0 or an aliphatic amine having 6 to 30 carbon atoms with (b) a polyhydric alcohol or a compound having an oxirane ring is provided. is there.

The dicarboxylic acid having 3 to 20 carbon atoms used in the present invention is an organic compound having two carboxyl groups in the molecule, and examples thereof include aliphatic saturated dicarboxylic acid, aliphatic unsaturated dicarboxylic acid and aromatic dicarboxylic acid. And so on. Examples of the saturated aliphatic dicarboxylic acid include linear dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, methylmalonic acid, methylsuccinic acid, ethylsuccinic acid. Examples thereof include acid, octylsuccinic acid, dicarboxylic acid having a side chain such as methylglutaric acid, cyclohexanedicarboxylic acid, and alicyclic dicarboxylic acid such as camphoric acid. Examples of the aliphatic unsaturated dicarboxylic acid include maleic acid, fumaric acid, linear dicarboxylic acids such as glutaconic acid, citraconic acid, mesaconic acid, and dicarboxylic acids having a side chain such as methylglutaconic acid. it can. Aromatic dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, 2,
Examples thereof include 6-naphthalenedicarboxylic acid, ubitic acid, and methylterephthalic acid. In the present invention, among the above-mentioned dicarboxylic acids, dicarboxylic acid anhydrides can be used for those forming a dicarboxylic acid anhydride. The dicarboxylic acid anhydride is ring-opened by reaction with an aliphatic alcohol, a polyhydric alcohol or an aliphatic amine to form a monoester or monoamide having one free carboxyl group. In the present invention,
The lower alkyl esters of the above dicarboxylic acids can be used. Examples of the lower alkyl ester of dicarboxylic acid include monomethyl ester, dimethyl ester, monoethyl ester, diethyl ester and the like. Lower alkyl esters of dicarboxylic acids react with aliphatic alcohols, polyhydric alcohols or aliphatic amines to liberate lower alcohols and form ester or amide bonds. In the present invention, the acid halide of the above dicarboxylic acid can be used. Examples of the acid halide of dicarboxylic acid include monochloride, dichloride, monobromide, dibromide and the like. Acid halides of dicarboxylic acids react with aliphatic alcohols, polyhydric alcohols or aliphatic amines to liberate hydrogen halides and form ester or amide bonds.

In the present invention, as component (a), an aliphatic alcohol having 6 to 30 carbon atoms or an aliphatic amine having 6 to 30 carbon atoms is used. When the aliphatic alcohol or the aliphatic amine is a mixture of compounds having different carbon numbers, an aliphatic alcohol or an aliphatic amine having an average carbon number of 6 to 30 can be used. As the (a) aliphatic alcohol having 6 to 30 carbon atoms, a saturated aliphatic alcohol can be used, and an unsaturated aliphatic alcohol can be used. Further, as the aliphatic alcohol having 6 to 30 carbon atoms, a linear, cyclic, or side chain aliphatic alcohol can be used.
Examples of such aliphatic alcohols include hexyl alcohol, octyl alcohol, isooctyl alcohol, capryl alcohol, caproyl alcohol, lauryl alcohol, myristyl alcohol, myristrail alcohol, heptadecyl alcohol, palmityl alcohol, isopalmityl. Examples thereof include alcohol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, aralkyl alcohol, ricinoleyl alcohol, linoleyl alcohol, behenyl alcohol, oleyl alcohol and lignoceyl alcohol. (A) C6 used in the present invention
As the aliphatic amine of ~ 30, a saturated aliphatic amine can be used, and an unsaturated aliphatic amine can be used. As the aliphatic amine having 6 to 30 carbon atoms, a linear, cyclic, or side chain aliphatic amine can be used. Further, the aliphatic amine having 6 to 30 carbon atoms is preferably a primary aliphatic amine or a secondary aliphatic amine. Examples of such aliphatic amines include hexylamine, octylamine,
Isooctylamine, caprylamine, caproylamine, laurylamine, myristylamine, myristrailamine, heptadecylamine, palmitylamine,
Isopalmitylamine, palmitoleylamine, stearylamine, isostearylamine, aralkylamine,
Primary aliphatic amines such as ricinoleylamine, linoleylamine, behenylamine, oleylamine, lignoceylamine, N, N-dibutylamine, N, N-dioctylamine, N, N-dicaprylamine, N, N Examples thereof include secondary aliphatic amines such as dicaproylamine, N, N-dilaurylamine and N, N-dimyristylamine.

In the present invention, the component (a) has 6 to 6 carbon atoms.
The aliphatic alcohol of 30 or the aliphatic amine having 6 to 30 carbon atoms may be used alone or in combination of two or more kinds of aliphatic alcohol or two or more kinds of aliphatic amine. Further, one or more kinds of aliphatic alcohols and one or more kinds of aliphatic amines can be mixed and used. In the present invention, when the aliphatic alcohol or the aliphatic amine has less than 6 carbon atoms, the amount of the antistatic agent transferred to the surface of the synthetic resin molded product is large and the appearance is impaired.
Moreover, durability against washing with water may be insufficient.
When the carbon number of the aliphatic alcohol or the aliphatic amine exceeds 30, the antistatic effect may be insufficient. In the present invention, a dicarboxylic acid having 3 to 20 carbon atoms, a dicarboxylic acid anhydride, a lower alkyl ester of dicarboxylic acid or a dicarboxylic acid halide and (a) a carbon number of 6 to 3
The reaction ratio of the aliphatic alcohol or the aliphatic amine of 0 is not particularly limited, but the amount of the aliphatic alcohol or the aliphatic amine is 0 per mol of the dicarboxylic acid or the derivative thereof.
The reaction is preferably 8 to 1.2 mol, and more preferably 0.9 to 1.1 mol with an aliphatic alcohol or an aliphatic amine.

In the present invention, a polyhydric alcohol or a compound having an oxirane ring is used as the component (b). Examples of the polyhydric alcohol (b) include alkane polyols, partial dehydration condensation products of polyols, and alkylene oxide adducts thereof. Examples of such polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-propanediol, glycerin, diglycerin, triglycerin, tetraglycerin, sorbitan, sorbitol,
Erythritol, pentaerythritol, dipentaerythritol, dipropylene glycol, mannitol,
Alkane polyols such as glucose, butylene glycol, 1,4-butanediol, 1,2,4-butanetriol, trimethylolpropane and heptanediol,
Alternatively, these (poly) alkylene oxide adducts and the like can be mentioned. Examples of the compound (b) having an oxirane ring used in the present invention include ethylene oxide, propylene oxide, butylene oxide and glycidol. The oxirane ring reacts with the carboxyl group of the dicarboxylic acid to form one ester bond and one free hydroxyl group, thus
One oxirane ring corresponds to two hydroxyl groups.
In the present invention, the polyhydric alcohol or the compound having an oxirane ring of the component (b) may be used alone, or two or more polyhydric alcohols or a compound having two or more oxirane rings may be mixed. Further, one or more polyhydric alcohols and one or more compounds having an oxirane ring can be mixed and used. In the present invention, the reaction ratio of the dicarboxylic acid having 3 to 20 carbon atoms, the dicarboxylic acid anhydride, the lower alkyl ester of the dicarboxylic acid or the dicarboxylic acid halide and the compound (b) having a polyhydric alcohol or an oxirane ring is not particularly limited. However, it is preferable to react 0.8 to 1.2 mol of a compound having a polyhydric alcohol or an oxirane ring with respect to 1 mol of a dicarboxylic acid or its derivative, and 0.9 to a compound having a polyhydric alcohol or an oxirane ring. More preferably, the reaction is 1.1 mol.

In the present invention, a dicarboxylic acid having 3 to 20 carbon atoms, a dicarboxylic acid anhydride, a lower alkyl ester of dicarboxylic acid or a dicarboxylic acid halide,
The order of reacting (a) the aliphatic alcohol or aliphatic amine having 6 to 30 carbon atoms with (b) the polyhydric alcohol or the compound having an oxirane ring is not particularly limited, and the order of the reaction is appropriately determined depending on the reaction mode. You can choose.
For example, a dicarboxylic acid or its derivative can be reacted with an aliphatic alcohol or an aliphatic amine, and then with a polyhydric alcohol or a compound having an oxirane ring. When the reaction is possible, the dicarboxylic acid or its derivative can be reacted with a polyhydric alcohol or a compound having an oxirane ring, and then with an aliphatic alcohol or an aliphatic amine. Alternatively, an aliphatic alcohol or an aliphatic amine and a polyhydric alcohol or a compound having an oxirane ring can be simultaneously added to and reacted with a dicarboxylic acid or a derivative thereof. The mode of the reaction will be described below with reference to specific examples.
When a compound having a dicarboxylic acid anhydride, (a) an aliphatic alcohol and (b) an oxirane ring is used as a raw material, the dicarboxylic acid anhydride and the aliphatic alcohol are mixed at a molar ratio of about 1: 1 to obtain about 80%. The reaction product is reacted with the compound having an oxirane ring at a molar ratio of about 1: 1 at about 70 to 90 ° C for 3 to 3 hours.
The desired compound can be obtained by reacting for 8 hours. Also, lower alkyl ester of dicarboxylic acid,
When (a) an aliphatic amine and (b) a polyhydric alcohol are used as raw materials, a lower alkyl ester of dicarboxylic acid and an aliphatic amine are mixed at a molar ratio of about 1: 1 and the pressure is gradually reduced, and the reaction is performed. About 120 ~ while raising the temperature
220 ℃, 10 ^-5 ~10 ^-2 and 1-5 hours at elevated temperature under reduced pressure conditions, such as Pa, further the reaction product with a polyhydric alcohol mole to about 1: 1, about 120 to 220 ° C., 10 ^{- 5} ~
The target compound can be obtained by reacting under a high temperature and reduced pressure condition such as 10 ⁻² Pa for 3 to 8 hours.

The antistatic agent of the present invention is preferably used in a proportion of 0.3 to 5 parts by weight based on 100 parts by weight of the synthetic resin. If the amount of the antistatic agent added is less than 0.3 parts by weight per 100 parts by weight of the synthetic resin, a good antistatic effect may not be obtained, and the durability against washing may be insufficient. If the amount of the antistatic agent added is more than 5 parts by weight per 100 parts by weight of the synthetic resin, the amount of the synthetic resin molded product transferred to the surface is large and the appearance may be impaired. The antistatic agent of the present invention can be added alone to the synthetic resin, or two or more kinds can be mixed and added to the synthetic resin. The synthetic resin to be used for the antistatic agent of the present invention is not particularly limited, and examples thereof include polyethylene, polypropylene, polyvinyl chloride, polystyrene,
Examples thereof include ABS resin, butadiene-styrene copolymer (SBR resin), polycarbonate, polyamide, phenol resin, polyacetal, polyphenylene oxide resin, polysulfone, polyether sulfone, polyphenylene sulfide and the like. The antistatic agent of the present invention includes other additives usually added to synthetic resins, for example, lubricants, stabilizers, ultraviolet absorbers, plasticizers,
It can be used in combination with dyes and pigments.

[0011]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In the examples and comparative examples, the antistatic agent was evaluated by the following methods. (1) Surface resistivity MCP-TESTER HIRESTA MODEL
HT-210 [manufactured by Mitsubishi Petrochemical Co., Ltd.] was used for measurement under the following conditions. (A) After molding, 24 at 20 ° C and 50% relative humidity
It was measured after adjusting the time condition (surface resistivity on the first day after molding). (B) After molding, it was immersed in running water for 10 minutes to remove surface water, and conditioned for 24 hours under conditions of 20 ° C. and 50% relative humidity and then measured (surface resistivity after washing with water). (C) After molding, 15 at 20 ° C and 50% relative humidity
After standing for 0 days, measurement was performed (surface resistivity 150 days after molding). (2) Appearance The appearance of the molded product used for surface resistivity measurement was evaluated according to the following criteria. ◯: Good Δ: Haze generated ×: Poor gloss Synthetic Example 1 A 500 ml flask equipped with a thermometer, a reflux condenser and a stirrer was charged with 148 g (1 mol) of phthalic anhydride and 130 g (1 mol) of octyl alcohol, and 90 3 at ℃
After reacting for a time, monooctyl phthalate ester was obtained. The capacity of the obtained monooctyl phthalate ester is 3,000 m.
Then, 122 g (1 mol) of erythritol was added thereto, the pressure was gradually reduced and the temperature was raised, and while water produced was distilled off, 10 ^-4 Pa, 220
The temperature was adjusted to 0 ° C. to obtain the desired slightly viscous pale yellow liquid material (antistatic agent 1). Synthesis Example 2 A 500 ml flask equipped with a thermometer, a reflux condenser and a stirrer was charged with 98 g (1 mol) of maleic anhydride and 186 g (1 mol) of lauryl alcohol, and the mixture was heated at 90 ° C. for 3 days.
After reacting for a time, maleic acid monolauryl ester was obtained.
Furthermore, 74 g (1 mol) of glycidol is added, and the temperature is 80 ° C.
And reacted for 5 hours to obtain a compound of formula [1] (antistatic agent 2).

Embedded image Synthesis Examples 3 to 16 In the same manner as in Synthesis Example 1 or Synthesis Example 2, antistatic agents 3 to 16 shown in Table 1 were obtained. The conventional antistatic agents used in Comparative Examples 4 to 5 are also shown in Table 1.

[0012]

[Table 1]

Example 1 To 100 parts by weight of a polypropylene resin, 1.0 part by weight of the antistatic agent 1 obtained in Synthesis Example 1 was added, and mixed and stirred for 1 minute with a Henschel mixer. The mixture of resin and antistatic agent was extruded using a single-screw extruder equipped with a T-die with the cylinder temperature and the T-die temperature set to 170 ° C., and molded into a sheet having a thickness of 1.0 mm. The surface resistivity of this sheet on the first day after molding was 1.6 × 10 ¹¹ Ω, and the appearance was good. Surface resistivity after washing with water is 6.1 x 10
^{It was 11} Ω, and the increase in surface resistivity due to washing with water was slight. The surface resistivity 150 days after molding is 2.1 × 10 ¹¹
Ω, and the surface resistivity hardly changed with time. Also, the appearance on the 150th day after molding was almost the same as the appearance on the 1st day after molding and was good. Examples 2 to 15 In the same manner as in Example 1, the types and amounts of the antistatic agents shown in Table 2 were added to prepare sheets, and the appearance was observed and the surface resistivity was measured. The results are shown in Table 2. Comparative Example 1 In the same manner as in Example 1, 1.0 part by weight of the antistatic agent 14 was added to prepare a sheet. The sheet on the first day after molding is
The surface resistivity was 5.7 × 10 ¹⁰ Ω, which was a sufficiently low value, but clouding occurred due to migration of the antistatic agent. However, when this sheet was washed with water, the surface resistivity became 10 ¹⁴ Ω or more, and the antistatic agent was washed off almost completely by washing with water. Also, on the 150th day after molding,
The surface resistivity was still as low as 3.4 × 10 ¹¹ Ω, but the gloss of the sheet was completely lost. Comparative Examples 2 to 5 In the same manner as in Example 1, the types and amounts of the antistatic agents shown in Table 2 were added to prepare sheets, and the appearance was observed and the surface resistivity was measured. The results are shown in Table 2. Comparative Example 6 A sheet was prepared by repeating exactly the same operation as in Example 1 except that the antistatic agent was not added, and the appearance was observed and the surface resistivity was measured. The results are shown in Table 2.

[0014]

[Table 2]

Examples 1 to 1 containing the antistatic agent of the present invention
The polypropylene sheet of No. 15 has a good appearance on the first day after molding and has a low surface resistivity. In addition, the surface resistivity is slightly increased by washing the sheet with water, which shows that the antistatic agent of the present invention has excellent water resistance. Furthermore, the appearance and surface resistivity on the 150th day after molding are almost the same as the appearance and surface resistivity on the 1st day after molding, which shows that the antistatic agent of the present invention has excellent durability. On the other hand, the sheet of Comparative Example 1 in which the antistatic agent 14 having a small number of carbon atoms in the aliphatic alcohol (a) is added,
The first day after molding, clouding occurs due to migration of the antistatic agent, and when the sheet is washed with water, the antistatic agent is almost completely washed off. Further, the appearance of the sheet is further deteriorated 150 days after the molding. The sheet of Comparative Example 2 in which the aliphatic amine having a large number of carbon atoms of the component (a) 15 is added and the antistatic agent 16 having a large number of carbon atoms of the dicarboxylic acid 16
The sheet of Comparative Example 3 to which was added did not exhibit any antistatic property on the first day after molding, and the surface resistivity did not sufficiently decrease even after 150 days after molding. The sheets of Comparative Examples 4 and 5 to which the conventional antistatic agent was added had a surface resistivity on the order of 10 ¹³ Ω on the 1st and 150th days after molding, which was insufficient in antistatic property, and the surface resistance after washing with water. The rate is 10 ¹⁴ Ω
That is all. The film of Comparative Example 6 to which no antistatic agent is added does not show any antistatic property.

[0016]

Effects of the Invention By adding the antistatic agent of the present invention to a synthetic resin, the surface of the molded product can be rapidly made to exhibit the antistatic property without impairing the appearance of the molded product, and the antistatic property can be maintained for a long period of time. It can be maintained for a long time, and has excellent durability against washing and wiping.

Claims (1)

[Claims] 1. A dicarboxylic acid having 3 to 20 carbon atoms, a dicarboxylic acid anhydride, a lower alkyl ester of dicarboxylic acid or a dicarboxylic acid halide, and (a) having 6 to 30 carbon atoms.
An antistatic agent containing the reaction product obtained by reacting the aliphatic alcohol or aliphatic amine having 6 to 30 carbon atoms with (b) a polyhydric alcohol or a compound having an oxirane ring.