JP2011184591A - Antistatic agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic composition capable of obtaining a coating membrane equipped simultaneously with static prevention, transparency and waterproof property. <P>SOLUTION: The antistatic composition contains a compound expressed by formula (I) [wherein, R<SP>1</SP>is a 4-20C hydrocarbon; R<SP>2</SP>is H or CH<SB>3</SB>; X is CH<SB>2</SB>or O; AO is 2-4C oxyalkylene; (n)=0 to 30; and M is an alkali metal or ammonium] and a compound expressed by formula (II) [wherein, R<SP>3</SP>, R<SP>4</SP>are each independently H or CH<SB>3</SB>; Y is O or NR<SP>5</SP>; and R<SP>5</SP>is H or a 1-6C hydrocarbon] by (90/10) to (40/60) weight ratio [(the weight of the compound of the formula (I))/(the weight of the compound of the formula (II))]. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an antistatic agent composition, a method for producing a coating film using the antistatic agent composition, and a coating film obtained by the producing method.

  Conventionally, various types of antistatic agents exist (see, for example, Patent Document 1). However, a coating film formed by adding an antistatic agent is often inferior in transparency.

  Therefore, as a conventional antistatic agent for the purpose of preventing a decrease in the transparency of the coating film, a specific anionic antistatic agent (for example, see Patent Document 2) or a polymer type quaternary ammonium salt (for example, Patent Document 3) is disclosed.

JP 63-205384 A JP 2007-191684 A International Publication No. 2007/032170

  However, the antistatic agents described in Patent Document 2 and Patent Document 3 have a problem that when washed with water, the antistatic performance decreases and the water resistance is poor.

  The present invention relates to an antistatic agent composition capable of obtaining a coating film having antistatic properties, transparency and water resistance, a method for producing a coating film using the antistatic agent composition, and the production A coating film obtained by the method is provided.

（但し、式中、Ｒ^１は炭素数４〜２０の炭化水素基、Ｒ^２は水素又はＣＨ_３、ＸはＣＨ_２又はＯ、ＡＯは炭素数２〜４のオキシアルキレン基、ｎ＝０〜３０、Ｍはアルカリ金属又はアンモニウムを示す。）

（但し、式中、Ｒ^３、Ｒ^４はそれぞれ独立して水素又はＣＨ_３、ＹはＯ又はＮＲ^５、Ｒ^５は水素または炭素数1〜６の炭化水素基を示す。） The antistatic composition of the present invention comprises a compound of the following formula (I) and a compound of the following formula (II) in a weight ratio ((weight of the compound of the following formula (I)) / (of the following formula (II) It is an antistatic agent composition comprising a compound weight)) in a ratio of 90/10 to 40/60.

(In the formula, R ¹ is a hydrocarbon group having 4 to 20 carbon atoms, R ² is hydrogen or CH ₃ , X is CH ₂ or O, AO is an oxyalkylene group having 2 to 4 carbon atoms, and n = 0 to 0. 30, M represents an alkali metal or ammonium.)

(In the formula, R ³ and R ⁴ each independently represent hydrogen or CH ₃ , Y represents O or NR ⁵ , and R ⁵ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms.)

  The method for producing a coating film of the present invention is a method for producing a coating film in which a coating film is formed on the substrate by irradiating active energy rays after coating the antistatic agent composition on the substrate.

  The coating film of this invention is a coating film obtained by the said manufacturing method.

  According to the antistatic agent composition of the present invention and the coating film manufacturing method using the antistatic agent composition, a coating film having antistatic properties, transparency, and water resistance can be obtained. . Moreover, according to the coating film of this invention, it has the outstanding antistatic property, transparency, and water resistance.

[Antistatic agent composition]
The antistatic agent composition of the present invention comprises a compound of the formula (I) (hereinafter also referred to as “compound (I)”) and a compound of the formula (II) (hereinafter also referred to as “compound (II)”). In a ratio of 90/10 to 40/60 by weight ratio ((weight of the compound of the formula (I)) / (weight of the compound of the formula (II))) is there.

In the formula (I), R ¹ represents a hydrocarbon group having 4 to 20 carbon atoms from the viewpoint of solubility of the compound (I) in an organic solvent, industrial availability, and transparency of the coating film. A hydrocarbon group having 6 to 16 carbon atoms is preferable, a hydrocarbon group having 6 to 14 carbon atoms is more preferable, and a hydrocarbon group having 8 to 12 carbon atoms is further preferable. From the same point of view, R ² is hydrogen or CH ₃ , preferably hydrogen. Further, X is CH ₂ or O from the viewpoint of solubility of the compound (I) in an organic solvent, industrial availability, and transparency of the coating film, but CH ₂ is preferable. From the viewpoint of antistatic ability and solubility of the compound (I) in an organic solvent, AO is an oxyalkylene group having 2 to 4 carbon atoms, preferably an oxyalkylene group having 2 carbon atoms. From the viewpoint of antistatic ability, n is 0 to 30, preferably 1 to 20, more preferably 3 to 15, still more preferably 5 to 15, and still more preferably 7 to 15. From the viewpoints of solubility of the compound (I) in an organic solvent, industrial availability, and transparency of the coating film, M is an alkali metal or ammonium, but is preferably ammonium.

In the formula (II), from the viewpoint of water resistance of the coating film, R ³ and R ⁴ are each independently hydrogen or CH ₃ , but hydrogen is preferable. From the viewpoint of the water resistance of the coating film, Y is O or NR ⁵ but O is preferred. From the viewpoint of antistatic ability, R ⁵ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, preferably hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, and hydrogen or a hydrocarbon group having 1 to 2 carbon atoms. Is more preferable.

  From the viewpoint of water resistance of the coating film, the weight ratio is 90/10 to 40/60, preferably 90/10 to 50/50, and more preferably 85/15 to 50/50. When the weight ratio exceeds 90/10, that is, when the content of the compound of the formula (I) increases, transparency and water resistance decrease, and when the weight ratio becomes less than 40/60, When the content of the compound of the formula (II) is increased, the antistatic property is lowered. The said weight ratio of this invention is calculated | required from this viewpoint.

  The antistatic agent composition preferably has active energy ray curability. The active energy ray curability means a property in which hardening is caused by irradiation with active energy such as ultraviolet rays, electron beams, radiation, X-rays, or in combination with an auxiliary agent.

  In the present invention, the antistatic agent composition may contain other antistatic agents having a structure different from that of the compound (I) and the compound (II) and having antistatic properties, transparency, water resistance and the like. . However, from the viewpoint of antistatic properties and transparency, the total amount of the compound (I) and the compound (II) is preferably 50% by weight or more, more preferably 70% by weight or more based on the total amount of the antistatic agent composition. It is more preferably 90% by weight or more, still more preferably 95% by weight or more, and still more preferably substantially 100% by weight.

  The antistatic agent composition may contain an organic solvent, if necessary. Examples of the organic solvent include, but are not limited to, aliphatic hydrocarbons such as hexane, alcohols such as methanol, ethanol, isopropyl alcohol, methoxyethanol, ethoxyethanol, methoxycarbitol, and benzyl alcohol, acetone, methyl ethyl ketone, and methyl isobutyl. Ketones such as ketones, halogen solvents such as methylene chloride and chloroform, ethers such as diethyl ether, aromatics such as toluene and xylene, esters such as n-butyl acetate and n-ethyl acetate, methylpyrrolidone, dimethylsulfate Examples thereof include foxides, but polar solvents such as ketones and esters are preferred from the viewpoints of solubility of compound (I) and compound (II) in an organic solvent and transparency of a coating film. In addition, when the other component (for example, resin monomer) described later is in a liquid state and is mutually dissolved with compound (I) and compound (II), the resin monomer is used as an organic solvent. Also good.

The antistatic agent composition preferably contains a resin or a resin monomer from the viewpoint of the transparency and hardness of the coating film. The resin or resin monomer is not particularly limited as long as it is a resin or resin monomer suitable for use in coating on a substrate after being made into a solution with an organic solvent. Resin or resin monomer. Among these, from the viewpoint of maintaining transparency, an acrylic resin or a monomer thereof is preferable. From the viewpoint of improving the transparency and hardness of the coating film, the resin or monomer is preferably a resin or resin monomer having two or more polymerizable functional groups. Examples when both are taken into account include di (meth) acrylates such as ethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol di (meth) acrylate monoalkyl ester, Tri (meth) acrylates such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol EO adduct And polyfunctional (meth) acrylates such as penta (meth) acrylate and resins formed by polymerization of these monomers.
As the content of the resin or resin monomer, the total content of the compound (I) and the compound (II) in the antistatic agent composition is based on 100 parts by weight of the resin or resin monomer. The amount of 1 to 40 parts by weight is preferred, the amount of 5 to 40 parts by weight is more preferred, the amount of 10 to 30 parts by weight is more preferred, and the amount of 15 to 30 parts by weight is even more preferred.
The resin or resin monomer that can react by irradiation of active energy rays causes a curing reaction directly by irradiation of active energy such as ultraviolet rays or electron beams or indirectly by the action of an initiator. A resin or resin monomer having a functional group is shown.

In addition to the above components, the antistatic agent composition includes commonly used initiators, curing agents such as diisocyanate compounds, pigments / dyes, or beads such as glass beads, polymer beads, inorganic beads, calcium carbonate, talc. Additives such as inorganic fillers such as, surface conditioners such as leveling agents, stabilizers, UV absorbers, and dispersants can be blended.
The antistatic agent composition preferably contains an initiator such as a UV initiator or a photocationic initiator from the viewpoint of curing acceleration. For example, acetophenones, genzophenones, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkylcion compounds, disulfide compounds, thiuram compounds, fluoroamine compounds and the like are used. More specifically, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzyldimethylketone, 1- (4-dodecylphenyl) -2 -Hydroxy-2-methylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzophenone and the like can be mentioned.

[Production Method of Antistatic Agent Composition]
The antistatic agent composition can be obtained by dissolving the compound (I) and the compound (II) in an organic solvent and adding the resin or resin monomer or the additive as necessary.

Compound (I) is a method in which the following hydroxyl group-containing compound is sulfated with SO ₃ gas or chlorosulfuric acid and then neutralized with a neutralizing agent, and the following hydroxyl group-containing compound is directly sulfated with amidosulfuric acid or sodium methylsulfate. And a method in which the obtained sulfate is further subjected to salt exchange. Specific examples of the hydroxyl group-containing compound include poly (0-30) oxyethylene-1- (allyloxymethyl) -2-lauryloxyethyl ether, poly (0-30) oxyethylene-1- (isopropenyloxymethyl). ) -2-lauryloxyethyl ether, poly (0-30) oxyethylene-1- (allyloxymethyl) -2-octyloxyethyl ether, poly (0-30) oxyethylene-1- (allyloxymethyl)- 2-stearyloxyethyl ether, poly (0-30) oxyethylene-1- (allyloxymethyl) -2-oleyloxyethyl ether, poly (0-30) oxyethylene-1- (allyloxymethyl) -2- Behenyloxyethyl ether, poly (0-30) oxyethylene-1- (allyloxymethyl) ) Undecyl ether, poly (0-30) oxyethylene-1- (allyloxymethyl) lauryl ether, poly (0-30) can be mentioned oxyethylene-1- (allyloxymethyl) tridecyl ether.
Examples of M of the compound (I) include alkali metals such as Na, K, and Li, and ammonium such as NH ₄ , triethanolammonium, monomethylammonium, dimethylammonium, trimethylammonium, and tetramethylammonium.

Specific examples of the compound (II) include maleic anhydride, citraconic anhydride, 2-3-dimethylmaleic anhydride, 2-propylmaleic anhydride, maleimide, N-methylmaleimide, N-ethylmaleimide, N- Examples include hexylmaleimide, 2-methyl-N-methylmaleimide, 2-3-dimethylmaleimide, and the like. These can be obtained by butane oxidation or microbial fermentation.
Moreover, a commercial item can be used for compound (I) and compound (II).

[Method for producing coating film]
The coating film of the present invention can be obtained by coating the base material with the antistatic agent composition of the present invention described above, drying it as necessary, and then irradiating with active energy rays. In addition, it is preferable to use what dissolved compound (I) and compound (II) in the organic solvent from a viewpoint of handleability as an antistatic agent composition. Moreover, it is preferable to contain the resin or resin monomer which can react by irradiation of an active energy ray from a viewpoint of the antistatic property of a coating film, transparency, water resistance, hardness, and cost.

The substrate on which the antistatic agent composition is applied is not particularly limited. For example, glass, cellulose resin such as triacetate cellulose (TAC) diacetyl cellulose, acetate butyrate cellulose, polyester resin such as polyethylene terephthalate (PET), acrylic resin, polyurethane resin, polycarbonate resin, polysulfone resin, polyether resin, polyolefin Resins, nitrile resins, polyether ketone resins, polyamide resins and the like can be mentioned.
The coating method is not particularly limited, and examples thereof include a bar coating method, a roll coater method, a screen method, a flexo method, a spin coating method, a dip method, a spray method, and a slide coating method. Moreover, as drying conditions after coating, for example, the drying temperature is 50 to 150 ° C., and the drying time is 0.5 to 5 minutes.

  The irradiation amount of the active energy ray is 10 to 500 mJ when ultraviolet rays are used as the active energy ray from the viewpoint of suppressing damage to the base material (for example, resin base material) on which the antistatic agent composition is applied. It is preferable that

The surface specific resistance value of the coating film of the present invention is preferably 5 × 10 ¹² Ω or less, more preferably 1 × 10 ¹² Ω or less, from the viewpoint of maintaining the antistatic property of the coating film. The surface resistivity can be measured according to the method described in the examples.

Further, the surface specific resistance value after washing of the coating film of the present invention is preferably 5 × 10 ¹² Ω or less, more preferably 1 × 10 ¹² Ω or less, from the viewpoint of maintaining the water resistance of the coating film. .

  The haze value of the coating film of the present invention is preferably 1% or less from the viewpoint of transparency. The haze value can be measured according to the method described in the examples.

  Examples and the like specifically showing the present invention will be described below. In addition, the evaluation item in an Example etc. measured as follows.

[Production of Compound (I)]
<Production of poly (10) oxyethylene-1- (allyloxymethyl) -2-lauryloxyethyl ether sulfate ammonium salt>
2077 g of aliphatic alcohol having 12 carbon atoms (Calcoal 2098 manufactured by Kao Co., Ltd.) was charged into a 5 L four-necked flask with a cock, and stirred at 30 ° C. while purging with nitrogen. 1.6 g of diethyl ether complex of boron trifluoride (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added, and 255 g of allyl glycidyl ether was added dropwise over 2.5 hours. Then, it stirred at 30 degreeC for 4 hours. After adding 500 g of 4% sodium hydroxide aqueous solution and stirring for 10 minutes, only the aqueous layer was removed from the bottom cock, and further washed with 1 kg of ion-exchanged water 3 times (total 3 kg). The obtained sample was transferred to a 5 L four-necked flask and unreacted alcohol was removed at 50 Pas over 5 hours while heating in a silicon bath at 130 ° C. to give 1-allyloxymethyl 2-lauryloxyethanol. 503 g of composition was obtained.
238 g of the obtained 1-allyloxymethyl-2-lauryloxyethanol composition and 0.22 g of KOH were charged into an autoclave equipped with a stirrer, a temperature controller, and an automatic introduction device, and dehydrated at 110 ° C. and 13 hPa for 30 minutes. Reaction was performed. After dehydration, nitrogen substitution was performed, and after raising the temperature to 120 ° C., 339 g of ethylene oxide (EO) was charged. After addition reaction and ripening at 120 ° C. for 4 hours, the mixture was cooled to 80 ° C., and unreacted EO was removed at 40 hPa for 30 minutes. After removing unreacted EO, 0.23 g of acetic acid was added to the autoclave, and the mixture was stirred for 30 minutes at 80 ° C., and then extracted to obtain an alkoxylate composition having an average EO addition mole number of 10 moles.
100 g of the obtained alkoxylate composition was charged into a 300 ml four-necked flask equipped with a stirrer, and heated to 100 ° C. in a silicon bath under a nitrogen stream. Add 0.6 g of urea (Wako Pure Chemical Industries) and 17 g of amidosulfuric acid (reagent manufactured by Wako Pure Chemical Industries, Ltd.), react at 100 ° C. for 5 hours, and filter to obtain the desired poly (10) oxyethylene. 113 g of -1- (allyloxymethyl) -2-lauryloxyethyl ether sulfate ammonium salt was obtained.
[Preparation of antistatic agent composition]
Acrylic resin (Daicel Cytec, DPHA [dipentaerythritol hexaacrylate]) as a resin that can react with active energy rays, a curing agent (Ciba Specialty Chemicals, Irgacure 184), and an organic solvent Methyl ethyl ketone, compound (I) shown in Table 1 and compound (II) were mixed to prepare antistatic agent compositions of Examples 1 to 7 and Comparative Examples 1 to 4. Each blending amount was as shown in Table 1. In addition, each compounding quantity shown in Table 1 shows each weight part number when the total weight of resin, hardening | curing agent, compound (I), and compound (II) which can react with an active energy ray is 100 weight part.

[Production of coating film]
Each antistatic agent composition obtained was applied to a cellulose triacetate (TAC) film (width 10 cm × length 12 cm × thickness 80 μm) so that the coating film after UV irradiation had a thickness of 4 μm (gap: 9 to 13 μm) was applied to almost one surface and dried under the drying conditions shown in Table 1. The dried film was irradiated with ultraviolet rays (200 mJ) in a nitrogen stream with a UV irradiation device (HTE-505HA manufactured by Hitec Co., Ltd., an ultraviolet lamp is USH-500 MB) to obtain a coating film (thickness 4 μm). In addition, the coating thickness measured 1 point on the center line of the width | variety of the coating surface, and 2 points | pieces which took the width | variety to the left and right from the center line, and used the average value of the 3 points | pieces.

[Antistatic property (surface resistivity of coating film) test]
The coating films (Examples 1 to 7 and Comparative Examples 1 to 4) were subjected to the A-4329 type high resistance meter (manufactured by Yokogawa YHP) in a room adjusted to a temperature of 25 ° C. and a relative humidity of 50%. The surface specific resistance value at the center of each was measured. The surface specific resistance value indicates that the smaller the value, the better the antistatic property.
The results are shown in Table 1.

[Water resistance (surface resistivity after washing coating film) test]
The coating films (Examples 1 to 7 and Comparative Examples 1 to 4) were washed with water, and then the surface resistivity was measured. The water washing conditions were as follows: tap water was run from a tap with an inner diameter of 14 mm at a flow rate of 10 L / min, and the test film was placed vertically 10 cm below the tap so that the tap water hits vertically, and coated for 30 seconds. It was carried out while moving so as to apply evenly. Thereafter, the moisture on the coated surface was removed with a hyper dry paper towel manufactured by Nippon Paper Crecia Co., Ltd., and air-dried for 3 minutes at a temperature of 25 ° C. and a relative humidity of 50%, and it was confirmed that there were no water droplets. In addition, a surface specific resistance value shows that water resistance is excellent, so that a numerical value is small.
The results are shown in Table 1.

[Transparency (coating film haze value) test]
For coating films (Examples 1 to 7 and Comparative Examples 1 to 4), in accordance with JIS K 7105 Plastic Optical Properties Test Method (5.5 and 6.4), Haze Meter HM-150 manufactured by Murakami Color Research Laboratory. The haze value was obtained. Specifically, the diffuse transmittance and the total light transmittance were measured based on JIS K7105 using an integrating sphere light transmittance measuring device, and expressed by the ratio. In addition, a haze value shows that it is transparent, so that a numerical value is small.
The results are shown in Table 1.

Claims (5)

The weight ratio ((weight of the compound of the following formula (I)) / (weight of the compound of the following formula (II)) of the compound of the following formula (I) and the compound of the following formula (II) is 90 / 10-10. An antistatic agent composition comprising 40/60.

(In the formula, R ¹ is a hydrocarbon group having 4 to 20 carbon atoms, R ² is hydrogen or CH ₃ , X is CH ₂ or O, AO is an oxyalkylene group having 2 to 4 carbon atoms, and n = 0 to 0. 30, M represents an alkali metal or ammonium.)

(In the formula, R ³ and R ⁴ are each independently hydrogen or CH ₃ , Y is O or NR ⁵ , and R ⁵ is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms.)   The antistatic agent composition according to claim 1, wherein the antistatic agent composition further comprises a resin or a resin monomer that can react by irradiation with active energy rays.   A method for producing a coating film, comprising coating a base material with the antistatic agent composition according to claim 1 and then irradiating an active energy ray to form a coating film on the base material.   The manufacturing method of the coating film of Claim 3 in which the said antistatic agent composition contains resin or resin monomer which can further react by irradiation of an active energy ray.   The coating film obtained by the manufacturing method of Claim 3 or 4.