JPH0564675B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to an antistatic agent containing a quaternary ammonium salt of carboxymethyl cellulose (hereinafter abbreviated as CMC), which has a high degree of substitution of carboxymethyl groups per anhydroglucose unit. (Prior art and problems) Various quaternary ammonium salts and hydroxybetaine compounds have been used for antistatic treatment of plastics and synthetic fiber materials (Japanese Patent Application Laid-open No. 137099/1983).
and water-soluble acrylic resin (Special Publication No. 60-52188)
Antistatic agents such as these are applied to the surfaces of plastics and synthetic fiber materials. However, many conventional antistatic agents are relatively low-molecular or water-soluble, and can be eluted by water or peel off due to their low affinity with the surfaces of plastics and synthetic fiber materials, resulting in the antistatic effect being lost. There were flaws that were lost. This invention was made to solve these drawbacks, and by forming an antistatic coating of quaternary ammonium salt of CMC that is poorly soluble or insoluble in water, it has a high antistatic effect that is water resistant and durable. It's something you get. Regarding this CMC quaternary ammonium salt, only the following is known, and its use as an antistatic agent of the present invention is not disclosed. Namely, West German Patent No. 1103336 discloses dimethyl laurylcetylammonium salt of CMC, U.S. Patent No. 2881074 discloses CMC trimethyloctadecylammonium salt,
-Deutsche Apotheker-
Zeitung), Vol. 106, No. 35, pp. 1206-1208,
In 1966, CMC dodecyldimethyl (3,4-dichlorobenzyl) ammonium salt, Pharmaceutical Industry (Pharm.Ind.), No. 37
Volume, No. 2, Page 100, 1975 discloses CMC cetyltrimethylammonium salt. However, CMC, which is the raw material for these CMC quaternary ammonium salts, has a carboxymethyl group substitution degree (hereinafter abbreviated as DS) per anhydroglucose unit.
Since there is no specific description regarding this, it is assumed that the DS of the commercially available product is less than 1.0. Since the quaternary ammonium group is bonded to the carboxymethyl group of CMC at a molecular ratio of 1:1,
The number of quaternary ammonium groups that can be introduced is less than 1.0 molecule per glucose unit, and the properties of a larger amount of quaternary ammonium groups cannot be utilized. In addition, these conventional CMC quaternary ammonium salts are generally water-soluble (insoluble in organic solvents) when the molecular weight of the quaternary ammonium group is small, but become water-insoluble when the molecular weight of the quaternary ammonium group becomes large. It also does not dissolve well in polar solvents such as alcohol and acetone, or in non-polar solvents such as toluene. Therefore, it is difficult to use it as a solution in an organic solvent. (Means for Solving the Problems) Conventional CMC quaternary ammonium salts using CMC with low DS are difficult to use as solutions in organic solvents as described above, but the inventors of the present invention is a quaternary ammonium salt of CMC with a high DS of 1.5 to 3.0, and depending on the type of quaternary ammonium group, it is particularly difficult to dissolve in water or insoluble in water but soluble in organic solvents. He came up with an invention. Thus, this invention has the following formula: [In the formula, R is a hydrogen atom or a quaternary ammonium salt of a carboxymethyl group, and n is 10 to 1000. However, the degree of substitution of carboxymethyl group per anhydroglucose unit is 1.5 to 3.0, and the quaternary ammonium salt of carboxymethyl group has the sub-formula: (In the formula, R ¹ to ^{R 4} are each a C _1-20 linear or branched saturated or unsaturated aliphatic hydrocarbon group, or three of R ¹ to ^{R 4} are the above-mentioned hydrocarbon groups. and one is an aralkyl group or a trialkylammonium alkyl group, or two of R ¹ to ^{R 4} are the above hydrocarbon groups and the remaining two are an aralkyl and dialkyphenoxy (or alkylphenoxy) alkyleneoxyalkyl group. or one or two of R ¹ to R ⁴ are the above-mentioned hydrocarbon groups and the remaining two or three form a ring together with the nitrogen atom)], in particular a carboxy group that is sparingly soluble or insoluble in water. This is an antistatic agent characterized by containing methylcellulose quaternary ammonium salt. The CMC quaternary ammonium salt used in the present invention is prepared by mixing a solution of carboxymethyl cellulose or a salt thereof having a degree of substitution by carboxymethyl groups per anhydroglucose unit of 1.5 to 3.0 with a corresponding quaternary ammonium compound or a solution thereof. The carboxymethylcellulose quaternary ammonium salt produced is separated and purified. CMC used as a raw material for the CMC quaternary ammonium salt used in this invention has a DS1.5 from the viewpoint of solubility of the quaternary ammonium salt in organic solvents.
Must be ~3.0. Such a high degree of substitution
As CMC, for example, one produced by the multistage etherification method described in Japanese Patent Application Laid-open No. 176202/1984 can be used. CMC is usually a sodium salt,
Alkali metal salts such as potassium salts are used.
alkaline earth metal salts and acid forms, such as calcium salts;
The sodium salt is most preferred, although the partially acid form can also be used. On the other hand, the quaternary ammonium compound must have bactericidal properties, but it must also have DS1.5~
When a quaternary ammonium salt of CMC of 3.0 is formed, a salt that is soluble in an organic solvent or an aqueous solution of at least about 50% organic solvent is selected from the viewpoint of film-forming properties and water resistance. From these viewpoints, suitable quaternary ammonium compounds with relatively large molecular weights include lauryltrimethylammonium salt, cetyltrimethylammonium salt, tetradecyldimethylbenzylammonium salt, stearyltrimethylammonium salt, and trioctylmethylammonium salt. , dimethyldistearylammonium salt, dimethyloleyllinolyl ammonium salt,
Trimethylmonobhenylammonium salt, methyltrilauryl ammonium salt, laurylpyridinium salt, cetylpyridinium salt, benzethonium salt, methylbenzethonium salt, laurylphenoxyethyldimethylammonium salt, laurylisoquinolinium salt, laurylnicotinium salt, laurylquinal Examples include deinium salts, and suitable anions constituting these include halogen ions such as chlorine, bromine, and fluorine, sulfate ions, nitrate ions, and phosphate ions. In this invention, CMC quaternary ammonium salts having a quaternary ammonium group of the above-mentioned quaternary ammonium compounds can be used, including lauryltrimethylammonium salt, tetradecylzylthylbenzylammonium salt, cetyltrimethylammonium salt of CMC. , stearyltrimethylammonium salt, laurylpyridinium salt, cetylpyridinium salt, benzethonium salt, methylbenzethonium salt, laurylphenoxyethyldimethylammonium salt, laurylisoquinolinium salt, and the like are preferred. The method of the present invention uses a CMC quaternary ammonium salt which is sparingly soluble or insoluble in water as described above, for example.
A solution dissolved in a lower alkyl alcohol such as ethanol, methanol, or isopropanol, or an organic solvent such as acetone or toluene is applied or sprayed onto the surface of plastics or synthetic fiber materials, and the solvent is removed by a normal method such as vacuum drying. This is done by forming a film of CMC quaternary ammonium salt on the surface. The content of the quaternary ammonium salt solution depends on the antistatic property and thickness of the film, but is usually about 0.01 to 30%. Depending on the type of quaternary ammonium salt, a mixture of an organic solvent and a small amount of water may be used as the solvent. (Examples) The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. CMC quaternary ammonium salt production example 200g of 1% aqueous solution of the following CMC sodium salt
To the mixture, equivalent amounts of aqueous solutions of various quaternary ammonium compounds listed below were added and stirred. The generated precipitate was filtered, thoroughly washed with water, and then dried under vacuum at room temperature to obtain each CMC.
A quaternary ammonium salt was obtained. The solubility of these products is shown in Table 1. Both were insoluble in water but soluble in lower alcohols. 1 CMC sodium salt DS used Polymerization degree 1% aqueous solution viscosity (cps) 2.41 700 610 2 Quaternary ammonium compound used Benzethonium chloride Methylbenzethonium chloride Cetylpyridium chloride Examples 1 to 3, comparative examples Shown in the above production example DS2.4, manufactured by method
CMC benzethonium salt with a degree of polymerization of 700,

[Table] Note ×: Insoluble, △: Partially soluble gel, ○: Soluble

[Table] Or methylbenzethonium salt or cetylpyridium salt was dissolved in a mixed solvent of methanol and ethanol (1:1) to prepare dopes with a concentration of 10%. These dopes are coated with a 100μm coater to a thickness of
100μm PET resin sheet (Diafu Oil Co., Ltd.)
Coated on the surface of Diaph Oil 100) and heated to 50°C.
After drying for 60 minutes, the mixture was left under reduced pressure overnight.
After standing for 4 hours at 23℃ and 40%RH,
Under this environment, the surface resistivity of each surface was measured using Kawaguchi Electric Seisakusho's super megohmmeter (VE-30) and room temperature measurement box (P-
601). For comparison, the surface resistivity of an untreated PET resin sheet was measured under the same conditions. The results are shown in Table 2.

Claims (1)

[Claims] 1. The following formula: [In the formula, R is a hydrogen atom or a quaternary ammonium salt of a carboxymethyl group, and n is 10 to 1000. However, the degree of substitution of carboxymethyl group per anhydroglucose unit is 1.5 to 3.0, and the quaternary ammonium salt of carboxymethyl group has the sub-formula: (In the formula, R ¹ to ^{R 4} are each a C _1-20 linear or branched saturated or unsaturated aliphatic hydrocarbon group, or three of R ¹ to ^{R 4} are the above-mentioned hydrocarbon groups. and one is an aralkyl group or a trialkylammonium alkyl group, or two of R ¹ to ^{R 4} are the above-mentioned hydrocarbon groups and the remaining two are aralkyl and dialkylphenoxy (or alkylphenoxy) alkyleneoxyalkyl groups. or one or two of R ¹ to R ⁴ are the above-mentioned hydrocarbon groups and the remaining two or three form a ring together with the nitrogen atom)], in particular a carboxy group that is sparingly soluble or insoluble in water. An antistatic agent characterized by containing methylcellulose quaternary ammonium salt.