JPH07118571A - Antistatic coating composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in antistatic properties and transparency by mixing a film-forming thermoplastic or thermosetting resin with a specified sulfonate. CONSTITUTION:100 pts.wt. film-forming thermoplastic or thermosetting resin is mixed with 0.1-5 pts.wt., in total, at least one member selected from among sulfonates of formulas I and II [R<1> to R<3> are each 6-20C linear or branched alkyl or alkenyl; m and p are each 2-4; n and q are each 1-100; and M<1> to M<3> are each an alkali (alkaline earth) metal atom or a phosphonium group having four hydrocarbon groups] and optionally 10-60wt.% at least one member selected from among a polyalkylene glycol, a nonionic surfactant and a cationic surfactant to obtain the title composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel antistatic coating composition. More specifically, the present invention relates to an antistatic coating composition having excellent antistatic properties and good transparency.

[0002]

2. Description of the Related Art The main use of paints is to form a thin film on the surface of products for the purpose of aesthetics and protection. The exteriors and interiors of automobiles, building materials, mechanical products, electrical products, general household products,
It is used for ornaments. Various synthetic resins are used for the components of the thin film formed by paint, but since synthetic resins are inherently hydrophobic and have high electrical insulation properties, they tend to be charged due to the accumulation of static electricity, resulting in a poor appearance. It is inevitable that the work efficiency will be deteriorated, and the work efficiency in the processes such as processing, packaging, and printing will be deteriorated, and it will also cause an accident due to spark discharge due to static electricity. Therefore, various antistatic methods for various paints have been studied.

As a method of preventing the static electricity of a coating film, a method of mixing carbon powder or metal powder has been well known in the past. However, although these methods can obtain an antistatic effect,
The transparency of the coating film is impaired.

Various proposals using organic compounds have been made, for example, it has been proposed to use an antistatic agent conventionally used for plastics, fibers, etc. (JP-A-1-252667). This proposal does not mention the transparency of the coating. Generally, in the case of a nonionic surfactant, sufficient antistatic performance cannot be obtained unless it is blended in an amount of 10% by weight or more, which is economically disadvantageous, and in the case of a cationic surfactant, Further, there is a problem in that the surface after coating is tacky and the appearance is damaged, and the anionic surfactant has a deterioration in the transparency of the coating film.

In addition, it has been proposed to use polyalkylene glycol or phosphoric acid ester (JP-A-60-206878, JP-A-1-16871, etc.), but this also has an antistatic property and a coating film. It does not fully satisfy both of the transparency.

[0006]

Under the above circumstances, the present invention provides stable and excellent antistatic performance by adding a predetermined antistatic agent at a low addition amount as compared with conventionally known antistatic agents. The purpose of the present invention is to provide an antistatic coating composition that does not impair the transparency of the coating film.

[0007]

Means for Solving the Problems As a result of intensive studies to develop an antistatic coating composition having the above-mentioned preferable characteristics, the present inventors have found that a film-forming thermoplastic resin or a thermosetting resin. And that the composition containing a combination of a sulfonate having a specific structure or a combination of the resin and the sulfonate and a nonionic surfactant or a cationic surfactant is suitable for the purpose, The present invention has been completed based on this finding.

That is, the present invention relates to (A) 100 parts by weight of the coating film-forming thermoplastic resin or thermosetting resin,
(B) (B-1) General formula (I)

[Chemical 3] And (B-2) general formula (II)

[Chemical 4] (R ¹ , R ² and R ³ in the formula are each 6 to ² carbon atoms.
A linear or branched alkyl group or alkenyl group of 0, which may be the same or different from each other, m and p are each an integer of 2 to 4; n and q are each an integer of 1 to 100, and m
And n and p and q may be the same or different from each other, and M ¹ , M ² and M ³ are each an alkali metal atom, an alkaline earth metal atom or 4 A phosphonium group having a hydrocarbon group, which may be the same or different from each other) at least one selected from the sulfonates represented by 0.1 to 5 Or 100 parts by weight of the above component (A), the component (B) and the component (C) (C-1) polyalkylene glycol, (C-
2) at least one selected from nonionic surfactants and (C-3) cationic surfactants in a total amount of 0.1 to 5 parts by weight, and based on the total amount thereof. The present invention provides an antistatic coating composition containing component (C) in an amount not exceeding 60% by weight.

The coating film-forming thermoplastic resin or thermosetting resin of the component (A) in the antistatic coating composition of the present invention is particularly preferably a thermoplastic resin or thermosetting resin capable of forming a coating film. There is no limitation, and thermoplastic resins or thermosetting resins used in general paints, preferably transparent paints are included. Examples of such a thermoplastic resin include acrylic resin, vinyl resin, urethane resin, polyester resin,
Hydrocarbon resins and the like, and thermosetting resins include, for example, phenolic resins, unsaturated polyester resins, and epoxy resins, as well as thermosetting acrylic resins, urethane resins, alkyd resins, and maleic acid resins.

The component (B) comprises one or both of the component (B-1) represented by the general formula (I) and the component (B-2) represented by the general formula (II). R ¹ , R ² and R ³ in the formula each have 6 carbon atoms.
To 20 alkyl or alkenyl groups, which may be linear or branched, and R ¹ , R ² and R ³ are the same. Or may be different. As such, for example, hexyl group, octyl group, decyl group,
Examples thereof include dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, hexadecenyl group, octadecyl group, octadecenyl group and the like. R ¹ and R ²
If R ³ has less than 6 carbon atoms, the compatibility with the resin may be poor and transparency may be impaired. If it exceeds 20, antistatic performance may be deteriorated.

Further, (CH ₂ ) _m and (CH ₂ ) _p are an alkylene group having 2 to 4 carbon atoms, that is, an ethylene group, a propylene group and a butylene group, and are any one of these. Or may be a combination of two or more kinds, and may be the same or different from each other, preferably one or both of the alkylene groups of each of these components. It is preferable that at least 70% or more of the total number of the alkylene groups of 1 are ethylene groups. If the number of ethylene groups is too small, the antistatic property tends to decrease. Further, q and s are 1 to 100, preferably 3 to 80, more preferably 6 to 50, and most preferably 9 to 40, and when these exceed 100, the antistatic property is lowered and they are blended. If the physical properties of the resin are impaired, and if the resin is relatively small, some problems may occur in transparency and heat resistance depending on the type and amount of other compounding ingredients.

The sulfonates of the components (B-1) and (B-2) are alkali metal salts, alkaline earth metal salts or phosphonium salts having four hydrocarbon groups of the corresponding sulfonic acids. And the general formula (I) and (I
M ¹ , M ² and M ^{3 in} I) may be the same or different from each other. The alkali metal salt is preferably sodium salt, potassium salt, lithium salt or the like, and the alkaline earth metal salt is preferably magnesium salt, calcium salt or the like.

Examples of the salt residue of the phosphonium salt include those represented by the general formula (III)

[Chemical 5] (In the formula, R ⁴ , R ⁵ , R ⁶ and R ⁷ are an optionally substituted linear or branched alkyl group having 1 to 18 carbon atoms or a phenyl group) Examples of the substituent include a hydroxyl group, a halogen atom and an amino group. As such, for example, tetramethylphosphonium group, tetraethylphosphonium group, tetrabutylphosphonium group, trimethylstearylphosphonium group, trimethyldodecylphosphonium group, trimethylphenylphosphonium group, triphenylmethylphosphonium group, tetraphenylphosphonium group, di ( Examples thereof include 2-hydroxyethyl) dibutylphosphonium group and p-hydroxyphenyltriethylphosphonium group. The phosphonium salt is particularly effective as a compounding ingredient in the high heat resistant resin.

The components (B-1) and (B-2) may be used alone or in combination of two or more.

In the antistatic coating composition of the present invention, when the components (B-1) and (B-2) are used in combination, only the component (B-1) or the component (B-2) is added. Compared with the case where it is used alone, the antistatic property, in particular, the stability of the performance over time and the transparency are improved, which is advantageous. (B
When the component (-1) and the component (B-2) are used in combination, the blending weight ratio of the two components is preferably 9: 1 to 1: 9, more preferably 8: 2 to 2: 8. Be done. If this ratio is higher than 9: 1, the antistatic property tends to deteriorate, and if it is lower than 1: 9, the transparency tends to deteriorate.

The components (B-1) and (B-2) are, for example, those represented by the general formula (IV)

[Chemical 6] (In the formula, R ⁸ is a linear or branched alkyl group or alkenyl group having 6 to 20 carbon atoms, R ⁹ is a hydrogen atom or an alkyl group, and M is a hydrogen atom or the above salt residue.) in the compound represented by the general formula _{(V) HO - {(CH} 2) r O} s -H ... (V) ( an integer of r in the formula 2~4, (CH _{2) r} alkylene group May be one kind or may be a combination of two or more kinds, y is 1 to 100,
The polyalkyleneoxy group in {(CH ₂ ) _r O} _s may be one kind or may be a combination of two or more kinds), or may be reacted with a glycol represented by the general formula ( A lower alkyl ester of the compound of IV) is transesterified with a glycol of general formula (V), and when M is a hydrogen atom, the sulfonic acid of these reaction products is subjected to a predetermined salt-forming reaction. It can be manufactured.

The compound of the general formula (IV) and the general formula (V)
The glycol is used in a molar ratio of 0.5: 1 to 2:
A range of 1 is preferred. In this case, these reaction products contain the component (B-1), the component (B-2), and optionally the glycol of the component (C-1) described later, and the antistatic coating composition of the present invention as it is. It is advantageous because it has a suitable composition of matter.

Regarding the reaction conditions for obtaining the above reaction product, in the case of dehydration esterification reaction, under normal pressure or reduced pressure,
Reaction temperature 50 to 150 ° C, preferably 80 to 120 ° C
The reaction time is 30 minutes to 20 hours, preferably 2 to 12 hours. In the case of transesterification reaction, the reaction temperature is 50 to 150 ° C., preferably 80 at atmospheric pressure or reduced pressure.
A reaction time of 10 minutes to 20 hours, preferably 30 minutes to 6 hours at ˜120 ° C. is suitable.

These reactions are carried out without solvent or in a solvent such as carbon tetrachloride or xylene. The reaction temperature and the reaction time are appropriately selected depending on the molar ratio, the degree of reduced pressure and the like. In the transesterification reaction, a commonly used catalyst such as an acid catalyst such as p-toluenesulfonic acid or sulfuric acid or a base catalyst such as sodium hydroxide, potassium hydroxide or sodium hydrogen carbonate is used. When the starting material is an unneutralized material, it is not necessary to add an acid catalyst.

The salt formation reaction method is not particularly limited, and a conventionally known method can be used. For example, by reacting the sulfonic acid of the above reaction product with a hydroxide, carbonate, hydrogen carbonate or the like of an alkali metal or an alkaline earth metal, an alkali metal salt or an alkaline earth metal salt of the sulfonic acid is obtained. To be The phosphonium salt can be obtained by allowing a halogen salt of a phosphonium compound to act on the alkali metal salt of sulfonic acid to cause metathesis, or by causing a phosphonium hydroxide compound to act directly.

In the antistatic coating composition containing the component (A) and the component (B) of the present invention, the component (A) 100
It is necessary to add 0.1 to 5 parts by weight, preferably 0.15 to 4 parts by weight, of the component (B) with respect to parts by weight. If the compounding amount of the component (B) is too small, the desired effect cannot be obtained sufficiently, and if it is too large, the effect is not improved for the amount, and the physical properties of the coating film are likely to be impaired.

Next, in the antistatic coating composition of the present invention, for the purpose of further improving the antistatic property and / or the transparency, in addition to the components (A) and (B), (C) is further added. The components can be added in an amount not exceeding 60% by weight based on the total amount of the components (B) and (C).

The component (C) is at least one selected from the group consisting of (C-1) polyalkylene glycol, (C-2) nonionic surfactant and (C-3) cationic surfactant. Is.

The polyalkylene glycol of the component (C-1) has a general formula (VI) HO {(CH ₂ ) _t O} _u H (VI) (wherein t is an integer of 2 to 4 and u is 2). ˜100). In this compound, t is preferably 2
Or 3 and the alkylene group of (CH ₂ ) _t may be one type, or may be a combination of two or more types. Further, u is preferably selected in the range of 3 to 80, more preferably 6 to 50, and most preferably 9 to 40,
The polyoxyalkylene group of {(CH ₂ ) _t O} _u may be one type or a combination of two or more types. Examples of such a compound include polyethylene glycol, polypropylene glycol, and ethylene glycol-propylene glycol copolymer.

Examples of the nonionic surfactant as the component (C-2) include octylic acid monoglyceride, decanoic acid monoglyceride, lauric acid monoglyceride, lauric acid diglyceride, lauric acid triglyceride, myristic acid monoglyceride, myristic acid diglyceride, myristic acid. Triglyceride, palmitic acid monoglyceride,
Palmitic acid diglyceride, palmitic acid triglyceride, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, pentaerythritol monostearate ester, pentaerythritol distearic acid ester, pentaerythritol monolaurate ester, pentaerythritol dilaurate ester, stearyl alcohol, lauryl ester. Examples thereof include alcohol, octyl alcohol, glycerin monostearate succinate, lauryl diethanolamine, palmityl diethanolamine, stearyl diethanolamine, lauric acid diethanolamide, palmitic acid diethanolamide, and stearic acid diethanolamide.

Among these, particularly those having 6 to 14 carbon atoms
Fatty acid glyceride having a fatty acid monoglyceride content of 70% by weight or more, a fatty acid diethanolamide derived from a fatty acid having 6 to 14 carbon atoms, and an alkyl group or an alkenyl group having 6 to 14 carbon atoms N-substituted diethanolamine is preferable. If the number of these carbon atoms is too small, volatility becomes high and problems such as volatilization during coating film formation easily occur. Is difficult to obtain. As the fatty acid glyceride, a fatty acid monoglyceride or a mixture thereof with a fatty acid diglyceride or a fatty acid triglyceride is used. When the content of the fatty acid monoglyceride is less than 70% by weight, it becomes difficult to obtain the immediate effect of the antistatic performance. These (C-2) components may be used alone or in combination of two or more.

Examples of the cationic surfactant as the component (C-3) include trimethylstearyl ammonium chloride, trimethylbenzyl ammonium chloride, dimethyldilauryl ammonium chloride, dimethyl distearyl ammonium chloride, dimethyl dibenzyl ammonium chloride, etc. Can be mentioned. These may be used alone or in combination of two or more.

The components (A), (B) and (C) of the present invention
In the antistatic coating composition containing components,
With respect to 100 parts by weight of the component (A), the total amount of the component (B) and the component (C) is 0.1 to 5 parts by weight, preferably 0.15 to 4 parts by weight, and the total amount of these components. Against (C)
It is necessary to mix the components in amounts not exceeding 60% by weight. If the blending amounts of the components (B) and (C) are too small, the desired effects cannot be obtained sufficiently, and if they are too large, the effects are not improved relative to the amounts, and the physical properties of the coating film are improved. It will be easier to get there. Further, if the blending amount of the (C) component with respect to the total amount of the (B) component and the (C) component is less than 10% by weight, the effect of addition is not sufficiently exerted, and if it exceeds 60% by weight, the desired effect is not obtained. The effect cannot be obtained sufficiently.

In the antistatic coating composition of the present invention, if necessary, as a secondary component, for example, ethylene glycol stearic acid ester, polyethylene glycol stearic acid ester, and the like, as long as the object of the present invention is not impaired.
A leveling agent, a defoaming agent, an ultraviolet absorber, a flame retardant, a colorant and the like can be added depending on polyethylene glycol lauric acid ester and the like, improvement of coating workability, quality required for a coating film and the like.

The antistatic coating composition of the present invention can be applied to a coating film-forming resin without impairing its original physical properties.
Antistatic property can be imparted.

The antistatic coating composition of the present invention may contain a solvent for diluting the above-mentioned components. The solvent is not particularly limited as long as it is a solvent used for general paints, for example, isopropyl alcohol, isobutanol, alcohols such as butyl alcohol, dimethyl ketone, ketones such as methyl ethyl ketone, esters such as ethyl acetate, Aromatic hydrocarbons such as toluene and xylene, turpentine oil, butyl cellosolve, ethers such as carbitol, and water are used. The amount of such a solvent to be used may be in a wide range, but is usually 10 to 500% by weight, preferably 30 to 20% by weight based on the total amount of the resin component (A) component and the other antistatic agent component.
It is selected in the range of 0% by weight.

The method for preparing the antistatic coating composition of the present invention is not particularly limited. For example, a method in which a predetermined resin component is previously dissolved in a solvent and a predetermined antistatic agent component is added and mixed, , A method of simultaneously mixing a predetermined resin component, a predetermined antistatic agent component, and a solvent. The antistatic coating composition of the present invention thus prepared is applied to the surface to be coated of various products by a conventionally known coating method, for example, spray coating, brush coating or screen printing.

[0033]

EFFECT OF THE INVENTION The antistatic coating composition of the present invention has the remarkable effect of being excellent in antistatic property and also having good transparency, and is used for automobile exteriors and interiors, building materials, mechanical products, electric products, general products. It is suitable for painting household items and ornaments.

[0034]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Examples 1 to 18 and Comparative Examples 1 to 7 Acrylic paint [DIANAL LR-469 (trade name, manufactured by Mitsubishi Rayon Co., acrylic resin (Tg = 77 ° C.)) 36
To a solution prepared by dissolving 47% by weight of isopropanol in 17% by weight of methyl ethyl ketone], and an antistatic agent component (indicated by the antistatic agent component No.) having a composition of the blending weight ratio shown in Table 1 is added, Each antistatic coating was prepared by stirring and dissolving. At this time, the solubility of the antistatic agent component component in the acrylic resin solution was visually determined. Next, each antistatic paint was applied to an acrylic plate and dried to form a coating film having a film thickness of 100 μm.
After holding this coating film under the conditions of 20 ° C. and 65% RH for 1 day, its surface resistance was measured by Hiresta manufactured by Mitsubishi Petrochemical Co., Ltd., and the transparency and appearance of the coating film were visually evaluated.
The results are shown in Table 2.

[0036]

[Table 1] R ¹ , R ² and R ³ in the table are represented by C _k (k is the number of carbon atoms) depending on the number of carbon atoms of the alkyl group. The components (C) indicated by abbreviations in the table are as follows. PEG (9): Polyethylene glycol having an average degree of polymerization of 9 SMG: monoglyceride stearate LMG: monoglyceride lauric acid LDA: lauryl diethanolamine TSA: trimethylstearyl ammonium chloride

[0037]

[Table 2]

From these results, the paints of the respective Examples had good solubility of the blended components in the resin solution at the time of their preparation and were easy to handle, and the coating films all had a surface resistance of 1 × 10 ^12.
It has a small value of less than Ω and is excellent in antistatic property as well as having good transparency and appearance, whereas the paint of Comparative Example has solubility of antistatic agent content, or antistatic property, transparency or appearance of the coating film. There was a problem with at least one of them.

Claims (2)

[Claims] 1. To 100 parts by weight of (A) a coating film-forming thermoplastic resin or thermosetting resin, (B) (B-1) a general formula: And (B-2) general formula: (R ¹ , R ² and R ³ in the formula are each 6 to ² carbon atoms.
A linear or branched alkyl group or alkenyl group of 0, which may be the same or different from each other, m and p are each an integer of 2 to 4; n and q are each an integer of 1 to 100, and m
And n and p and q may be the same or different from each other, and M ¹ , M ² and M ³ are each an alkali metal atom, an alkaline earth metal atom or 4 A phosphonium group having a hydrocarbon group, which may be the same or different from each other) at least one selected from the sulfonates represented by 0.1 to 5 An antistatic coating composition, characterized by containing parts by weight. 2. The component (B), the component (C) (C-1) polyalkylene glycol, the component (C-2) nonionic surfactant and the component (C-3) relative to 100 parts by weight of the component (A). ) 0.1-5 parts by weight of the total amount of at least one selected from the cationic surfactants, and (C) component in an amount not exceeding 60% by weight based on the total amount thereof. The antistatic coating composition according to claim 1, which contains.