JP5563966B2 - Resin modifier - Google Patents

Description

  The present invention relates to a resin modifier, a method for producing a coating film using the resin modifier, and a coating film obtained by the production method.

  Conventionally, resin modifiers have been used in the fields of coating and printing in order to improve film characteristics and surface characteristics.

  The following Patent Documents 1 to 4 describe antistatic agents having a specific structure for the purpose of enhancing the antistatic effect. For example, Patent Document 1 describes an antistatic agent comprising an anion moiety comprising a specific sulfate and a cation moiety comprising a specific amine. Patent Document 2 describes an antistatic agent comprising an anion moiety comprising a nitrate ion or an alkyl sulfonate ion having 1 to 4 carbon atoms in the alkyl group and a cation moiety comprising a specific amine. Patent Document 3 and Patent Document 4 describe a resin composition having a block (b) containing 10 to 100 mol% of a quaternary ammonium salt structural unit. The block (b) is added for the purpose of obtaining an antistatic effect. In addition, the antistatic agent of patent document 1 does not have a polymerizable unsaturated group in a cation part. In the antistatic agent of Patent Document 2, the anion portion is not sulfate. Further, Patent Documents 5 to 6 describe antistatic resin compositions having excellent scratch resistance and the like.

JP 2007-191684 A JP 2004-123924 A Japanese Patent Laid-Open No. 11-60855 Japanese Patent Laid-Open No. 11-60856 JP 2009-263627 A JP 2009-287010 A

  In recent years, with the spread of LCD (Liquid Crystal Display) and the like, a coating film having higher basic performance is required. However, the antistatic agents described in Patent Documents 1 to 4 have room for improvement in that a sufficient antistatic effect is not obtained. In addition to antistatic properties, improvements in basic properties such as water resistance and transparency of the resulting coating film are eagerly desired.

  The present invention relates to a resin modifier capable of obtaining a coating film having good basic properties such as antistatic properties, water resistance, transparency, a method for producing a coating film using the resin modifier, and the production A coating film obtained by the method is provided.

（但し、式中、Ｒ¹は炭素数１〜２２の炭化水素基、ＡＯは炭素数２〜４のアルキレンオキサイド基、ｎはＡＯの平均付加モル数であり、１００以下の正の数、Ｂ^＋は重合性不飽和基を有するアンモニウムイオン（Ｃ）を示す。） The resin modifier of the present invention is a resin modifier represented by the following formula (I).

(In the formula, R ¹ is a hydrocarbon group having 1 to 22 carbon atoms, AO is an alkylene oxide group having 2 to 4 carbon atoms, n is an average added mole number of AO, a positive number of 100 or less, B ⁺ Represents an ammonium ion (C) having a polymerizable unsaturated group.)

  The coating composition of the present invention is a coating composition containing the resin modifier and an organic solvent.

  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 coating composition on the substrate.

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

（但し、式中、Ｒ¹は炭素数１〜２２の炭化水素基、ＡＯは炭素数２〜４のアルキレンオキサイド基、ｎはＡＯの平均付加モル数であり、１００以下の正の数、Ｒ²、Ｒ³、Ｒ⁴はそれぞれ独立して水素原子または炭素数１〜８の炭化水素基、Ｒ^５は炭素数２〜５のアルキレン基、Ｒ^６は水素原子またはメチル基、ＸはＯまたはＮＨを示す。） The coating film of the present invention is also a coating film having a structure represented by the following formula (IV) or the following formula (V) at least partially.

(In the formula, R ¹ is a hydrocarbon group having 1 to 22 carbon atoms, AO is an alkylene oxide group having 2 to 4 carbon atoms, n is an average added mole number of AO, a positive number of 100 or less, R ² , R ³ and R ⁴ are each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ⁵ is an alkylene group having 2 to ⁵ carbon atoms, R ⁶ is a hydrogen atom or methyl group, and X is O or NH is shown.)

（但し、式中、Ｒ¹は炭素数１〜２２の炭化水素基、ＡＯは炭素数２〜４のアルキレンオキサイド基、ｎはＡＯの平均付加モル数であり、１００以下の正の数、Ｒ⁸は水素原子または炭素数１〜８の炭化水素基、Ｒ⁹は炭素数１〜８の炭化水素基を示す。）

(In the formula, R ¹ is a hydrocarbon group having 1 to 22 carbon atoms, AO is an alkylene oxide group having 2 to 4 carbon atoms, n is an average added mole number of AO, a positive number of 100 or less, R ⁸ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ⁹ represents a hydrocarbon group having 1 to 8 carbon atoms.)

  According to the resin modifier of the present invention and the method for producing a coating film using the coating composition containing the resin modifier, the coating film having excellent basic performance such as antistatic property, water resistance and transparency Can be obtained. In addition, the coating film of the present invention has excellent basic performance such as antistatic properties, water resistance, and transparency.

[Resin modifier]
The resin modifier of the present invention is a resin modifier represented by the formula (I) (hereinafter also referred to as “compound (I)”).

In the formula (I), from the viewpoints of solubility in an organic solvent and industrial availability, R ¹ is a hydrocarbon group having 1 to 22 carbon atoms, preferably a hydrocarbon group having 1 to 20 carbon atoms, A hydrocarbon group having 8 to 20 carbon atoms is more preferable, a hydrocarbon group having 10 to 18 carbon atoms is more preferable, and a hydrocarbon group having 12 to 18 carbon atoms is still more preferable. From the viewpoint of antistatic properties, AO is an alkylene oxide group having 2 to 4 carbon atoms, (AO) _n is a single addition of ethylene oxide, propylene oxide, and butylene oxide, and a random number of two or more alkylene oxide groups, Although block, random / block addition, etc. are shown, it is preferable to contain ethylene oxide from the viewpoint of antistatic properties and wettability. From the viewpoint of antistatic properties of the compound (I), n represents an average number of added moles, is a positive number of 100 or less, preferably 1 to 80, more preferably 1 to 70, A number of 50 is further preferred, and a number of 1 to 30 is even more preferred.
The ammonium ion (C) has a polymerizable unsaturated group from the viewpoint of water resistance and transparency. Examples of the polymerizable unsaturated group include α, β-unsaturated carbonyl ester or amide group such as (meth) acrylic ester group, (meth) acrylamide group, maleic acid ester, maleimide group, α, β-unsaturated nitrile group. , Allyl group, styryl group, vinyl group, isopropenyl group, etc., from the viewpoint of antistatic property and wettability to the substrate of the coating film containing the resin modifier of the present invention, allyl group or α, A β unsaturated carbonyl group is preferred. By increasing the wettability, irregular reflection of the coating film is suppressed and the anti-fogging effect is improved.

Ｒ²、Ｒ³、Ｒ⁴は、それぞれ独立して水素原子または炭素数１〜８の炭化水素基を示すが、帯電防止性及び工業的入手性の観点から、炭素数１〜８の炭化水素基であることが好ましく、炭素数１又は２の炭化水素基であることがさらに好ましい。Ｒ⁵は炭素数２〜５のアルキレン基を示すが、帯電防止性及び工業的入手性の観点から、炭素数２〜３であることが好ましい。Ｒ^６は水素原子またはメチル基、ＸはＯまたはＮＨを示すが、帯電防止性の観点から、ＮＨであることが好ましい。Ｒ^２、Ｒ^３、Ｒ^４の合計炭素数は帯電防止性と工業的入手性の観点から2〜12が好ましく、より好ましくは３〜９であり、更に好ましくは３〜６である。 The ammonium ion (C) is preferably a compound represented by the following formula (II) from the viewpoint of antistatic properties.

R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, but from the viewpoint of antistatic properties and industrial availability, a hydrocarbon having 1 to 8 carbon atoms. It is preferably a group, more preferably a hydrocarbon group having 1 or 2 carbon atoms. R ⁵ represents an alkylene group having 2 to ⁵ carbon atoms, and preferably 2 to 3 carbon atoms from the viewpoint of antistatic properties and industrial availability. R ⁶ represents a hydrogen atom or a methyl group, and X represents O or NH. From the viewpoint of antistatic properties, NH is preferable. The total carbon number of R ² , R ³ and R ⁴ is preferably 2 to 12 from the viewpoint of antistatic properties and industrial availability, more preferably 3 to 9, and even more preferably 3 to 6.

Ｒ⁷、Ｒ⁸はそれぞれ独立して水素原子または炭素数１〜８の炭化水素基を示すが、帯電防止性及び工業的入手性の観点から、炭素数１〜８の炭化水素基であることが好ましく、炭素数１〜6の炭化水素基であることがより好ましく、炭素数１〜３の炭化水素基であることがさらに好ましい。また、Ｒ⁷が好ましくはアリル基であって、Ｒ⁸が好ましくは水素原子または炭素数１〜８の炭化水素基、より好ましくは炭素数１〜6の炭化水素基、更に好ましくは炭素数１〜３の炭化水素基であることも好ましい。具体的には、メチル基、エチル基、プロピル基（ｎ-プロピル基、ｉ−プロピル基）、ブチル基（ｎ-ブチル基、ｉ−ブチル基、ｔ-ブチル基）、アリル基、ペンチル基、ヘキシル基、オクチル基、２−エチルヘキシル基等が挙げられる。
Ｒ⁹は炭素数１〜８の炭化水素基を示すが、帯電防止性及び工業的入手性の観点から、炭素数１〜６の炭化水素基であることが好ましく、炭素数１〜２の炭化水素基であることがより好ましい。具体的には、メチル基、エチル基、プロピル基（ｎ-プロピル基、ｉ−プロピル基）、ブチル基（ｎ-ブチル基、ｉ−ブチル基、ｔ-ブチル基）、ペンチル基、ヘキシル基、オクチル基、２−エチルヘキシル基等が挙げられる。
Ｒ⁷、Ｒ^８、Ｒ^９の合計炭素数は帯電防止性と工業的入手性の観点から２〜１５が好ましく、より好ましくは２〜１２であり、更に好ましくは２〜９である。 The ammonium ion (C) is preferably a compound represented by the following formula (III) from the viewpoint of antistatic properties and wettability.

R ⁷ and R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, but from the viewpoint of antistatic properties and industrial availability, it should be a hydrocarbon group having 1 to 8 carbon atoms. Is more preferable, it is a C1-C6 hydrocarbon group, and it is still more preferable that it is a C1-C3 hydrocarbon group. R ⁷ is preferably an allyl group, and R ⁸ is preferably a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms, still more preferably 1 carbon atom. It is also preferable that it is ~ 3 hydrocarbon group. Specifically, methyl group, ethyl group, propyl group (n-propyl group, i-propyl group), butyl group (n-butyl group, i-butyl group, t-butyl group), allyl group, pentyl group, A hexyl group, an octyl group, 2-ethylhexyl group, etc. are mentioned.
R ⁹ represents a hydrocarbon group having 1 to 8 carbon atoms, but from the viewpoint of antistatic properties and industrial availability, a hydrocarbon group having 1 to 6 carbon atoms is preferable, and a carbon group having 1 to 2 carbon atoms. More preferably, it is a hydrogen group. Specifically, methyl group, ethyl group, propyl group (n-propyl group, i-propyl group), butyl group (n-butyl group, i-butyl group, t-butyl group), pentyl group, hexyl group, An octyl group, 2-ethylhexyl group, etc. are mentioned.
The total carbon number of R ⁷ , R ⁸ and R ⁹ is preferably 2 to 15 from the viewpoint of antistatic properties and industrial availability, more preferably 2 to 12 and even more preferably 2 to 9.

  Compound (I) preferably has active energy ray curability. The active energy ray curability means a property that cures by irradiation with active energy such as ultraviolet rays, electron beams, radiation, X-rays, or in combination with an initiator.

  Examples of groups that are cured (reacted) by active energy rays include α, β unsaturated carbonyl groups, allyl groups, α, β-unsaturated nitrile groups, styryl groups, vinyl groups, and isopropenyl groups. As the active energy ray, ultraviolet rays are preferable from the practical viewpoint.

Compound (I) is preferably a resin modifier having antistatic properties, that is, an antistatic agent. Examples of the antistatic agent include those having a surface specific resistance value of 5 × 10 ¹² Ω or less of a coating film produced using the antistatic agent.

  In the present invention, the compound (I) may be used alone as a resin modifier, and is mixed with another antistatic resin modifier having antistatic properties, water resistance, transparency and the like. May be used. However, from the viewpoint of water resistance and transparency, the compound (I) is preferably 50 parts by weight or more, more preferably 70 parts by weight or more, with respect to 100 parts by weight of the total amount of the resin modifier. More preferably, it is at least part by weight.

[Production Method of Compound (I)]
Compound (I) is obtained by subjecting R ¹ —O— (AO) _n —SO ₃ ^— and an alkali metal salt to salt exchange with a salt of ammonium having a polymerizable unsaturated group and halogen, R ¹ It can be obtained by a method of neutralizing —O— (AO) _n —SO ₃ H with an amine having a polymerizable unsaturated group or ammonium hydroxide having a polymerizable unsaturated group. When water-containing raw materials are used, when water is used during synthesis, or when water is included in the product, dehydration and dissolution in an organic solvent or addition of an organic solvent followed by dehydration As a result, a resin modifier solution containing compound (I) can be obtained. However, when all the substituents of the ammonium group of the ammonium ion (C) are not hydrogen, it is preferable to obtain by the above salt exchange method from the viewpoint of industrial availability, handleability and the like. Further, when at least one of the substituents of the ammonium group of the ammonium ion (C) is hydrogen, it is preferable to obtain by a method of neutralizing with the amine from the viewpoint of simplification of the process such as omitting the dehydration process. .

Examples of the salt of R ¹ —O— (AO) _n —SO ₃ ^— and an alkali metal include R ¹ as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, and nonyl groups. Decyl group, undecyl group, lauryl group, myristyl group, cecil group, stearyl group, oleyl group, behenyl group, nonylphenyl group, and the like. (AO) _n can be a polyoxyethylene group, a polyoxypropylene group , A polyoxybutene group, a polyoxyethylene polyoxypropylene group, and the like. Examples of the alkali metal include lithium, sodium, and potassium. Specifically, lithium salt, sodium salt, potassium salt of polyoxyethylene methyl ether sulfate, lithium salt of polyoxyethylene lauryl ether sulfate, sodium salt, potassium salt, lithium salt of sodium polyoxyethylene oleyl ether sulfate, sodium salt, Mention may be made of potassium salts.
Further, the salt of ammonium having a polymerizable unsaturated group and halogen is preferably a salt of halogen with those corresponding to the chemical formulas (II) and (III), and chloride is preferred from the viewpoint of industrial availability. Regarding R ² , R ³ , and R ⁴ , R ² , R ³ , and R ⁴ are all methyl groups, two are methyl groups, and one is an ethyl group, and two are methyl groups In which one is a benzyl group, two are ethyl groups, and one is a methyl group, and the portion excluding R ² , R ³ , R ⁴ and N ⁺ in the chemical formula (II) 2- (meth) acryloxyethyl group, 3- (meth) acryloxypropyl group, 4- (meth) acryloxybutyl group, 5- (meth) acryloxypentyl group, 6- (meth) acryloxyhexyl group, 8- (meth) acryloxyoctyl group, 4- (meth) acrylamide butyl group, 5- (meth) acrylamide pentyl group, 6- (meth) acrylamide hexyl group, 8- (meth) acrylamide group Examples include a octyl group, a 2- (meth) acrylamidoethyl group, and a 3- (meth) acrylamidopropyl group. Specific examples of the salt of the halogen salt with the compound corresponding to the chemical formula (II) include (3- (meth) acrylamidopropyl) trimethylammonium chloride. In addition, as R ⁷ , R ⁸ , and R ⁹ , R ⁷ , R ⁸ , and R ⁹ are all methyl groups, all are ethyl groups, and all are propyl groups. , Two are methyl groups and one is an ethyl group, two are methyl groups and one is a propyl group, two are methyl groups and one is a butyl group, two are methyl groups and one is pentyl Group, hexyl group, octyl group or benzyl group, one allyl group, two methyl groups, one allyl group, two ethyl groups, one allyl group and two propyl groups There can be mentioned one in which one is an allyl group, one is a methyl group and one is an ethyl group, a propyl group, a butyl group, a hexyl group, or an octyl group. Specific examples of the salt of halogen corresponding to the chemical formula (III) include allyltrimethylammonium chloride and diallyldimethylammonium chloride. Commercially available products can be used for these salts.
In addition, R ¹ —O— (AO) _n —SO ₃ H, which is a precursor of an alkali metal salt, is obtained by, for example, converting a compound represented by R ¹ —O— (AO) _n —H to chlorosulfonic acid or sulfuric anhydride. It can be obtained by a method of reacting with (SO ₃ gas) and sulfating. _{^{Incidentally, R 1 -O- (AO) n}} -H in ^R 1, AO, and, n represents, ^R 1, AO in the compound (I), and are the same as n.
^Further, the _{R 1 -O- (AO) n -SO} 3 H , specific examples of _{^{R 1 -O- (AO) n -SO}} 3 H to be used in the neutralization of an amine having a polymerizable unsaturated group Specific examples of the aforementioned salt of R ¹ —O— (AO) _n —SO ₃ ^— and an alkali metal include those in which the alkali metal ion portion is substituted with a hydrogen ion.
In addition, specific examples of amines having a polymerizable unsaturated group include the above-described specific examples of the salt of ammonium and halogen having a polymerizable unsaturated group, one of hydrocarbon groups having no polymerizable property and halogen. Examples include amines removed. Specifically, for example, allyl dimethylamine obtained by removing a methyl group which is a non-polymerizable hydrocarbon group and a halogen chloride from allyltrimethylammonium chloride can be used.

Examples of the compound (I) include those composed of the aforementioned R ¹ —O— (AO) _n —SO ₃ ^— and the aforementioned ammonium having a polymerizable unsaturated group. (Meth) acrylamidopropyltrimethylammonium poly (1-50) oxyethylene methyl ether sulfate, (meth) acrylamidopropyltrimethylammonium poly (1-50) oxyethylene lauryl ether sulfate, (meth) acrylamidopropyltrimethylammonium poly (1-50) Oxyethylene oleyl ether sulfate, diallyldimethylammonium poly (1-50) oxyethylene lauryl ether sulfate, allyldimethylammonium poly (1-50) oxyethylene lauryl ether sulfate, male Midpropylenetrimethylammonium poly (1-50) oxyethylene lauryl ether sulfate, 2-vinylpyridinium poly (1-50) oxyethylene lauryl ether sulfate, 1-vinylimidazolium poly (1-50) oxyethylene lauryl ether sulfate, Examples include styrylmethylenetrimethylammonium poly (1-50) oxyethylene lauryl ether sulfate. In the present invention, poly (1-50) oxyethylene means that n, which is the average added mole number of ethylene oxide groups, is 1-50.

Although it does not specifically limit as said organic solvent used for manufacture of compound (I), From a soluble viewpoint of the compound of the said Chemical formula (I), solubility parameter (POLYMER HANDBOOK THIRD EDITION 1989 by John Wiley & Sons, Inc. An organic solvent having an SP value of 15.0 to 30.0 (MPa) ^1/2 is preferable, and an organic solvent having an SP value of 20.0 to 30.0 (MPa) ^1/2 is more preferable. Figures in parentheses indicate solubility parameters. Aliphatic hydrocarbons such as hexane, alcohols such as methanol, ethanol (26.0), isopropyl alcohol (23.5), methoxyethanol, ethoxyethanol, methoxycarbitol, benzyl alcohol (24.8); acetone ( 20.3), methyl ethyl ketone (19.0), ketones such as methyl isobutyl ketone (17.2); halogen solvents such as methylene chloride and chloroform; ethers such as diethyl ether; toluene (18.3), xylene and the like Aromatic esters such as n-butyl acetate (17.4) and esters such as n-ethyl acetate (18.6); methyl pyrrolidone, dimethyl sulfoxide and the like. Polar solvents such as ketones and esters are preferred. Further, when other components of the coating composition described later, for example, the resin monomer is in a liquid state and is mutually dissolved with the compound of the chemical formula (I), the resin monomer may be used as an organic solvent.

[Coating composition]
The coating composition of the present invention preferably contains a resin modifier and an organic solvent. The resin modifier is preferably used after being dissolved in an organic solvent. As an organic solvent used for a coating composition, the thing similar to the above-mentioned organic solvent used for manufacture of compound (I) is mentioned preferably. The range of suitable solubility parameters (SP values described in POLYMER HANDBOOK THIRD EDITION 1989 by John Wiley & Sons, Inc) is also the same as described above, and the organic is 15.0 to 30.0 (MPa) ^1/2 A solvent is preferable, and an organic solvent that is 20.0 to 30.0 (MPa) ^1/2 is more preferable. From the viewpoint of the solubility of the resin modifier, a polar solvent is preferable, and among these, the alcohols, ketones, and esters described above are preferable. On the other hand, in the case where the resin monomer used in the coating composition is liquid, when the resin monomer dissolves other components including the resin modifier of the present invention, the handling property is improved, and From the viewpoint of process simplification, the resin monomer may be used as an organic solvent.
In the coating composition of the present invention, the content of the resin modifier is preferably 0.5 to 50% by weight, more preferably 0.5 to 30% by weight, further from the viewpoint of antistatic properties, water resistance, and the like. Preferably it is 1-25 weight%, More preferably, it is 2-20 weight%.
The coating composition of the present invention preferably further contains a resin or a resin monomer. The resin or resin monomer to be used is not particularly limited as long as it is a resin or resin monomer suitable for use in coating on a substrate in a solution form with an organic solvent. For example, active energy ray curable Resin or resin monomer may be used, and thermosetting resin or resin monomer may be used. From the viewpoint of the hardness and cost of the coating film, the resin or resin that can react by irradiation with active energy rays It is preferable to use a monomer.
Resin or resin monomer that can react by irradiation of active energy rays is a resin having a functional group that 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 or A resin monomer is shown.

The active energy ray-curable resin or resin monomer is preferably an acrylic resin or a monomer thereof from the viewpoint of maintaining transparency. Further, from the viewpoint of improving the hardness of the coating film, the resin or resin 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.
In the coating composition of the present invention, the content of the resin or resin monomer that can react by irradiation with active energy rays is preferably 20 to 80% by weight, more preferably 25%, from the viewpoints of handleability and cost. It is -80 weight%, More preferably, it is 30-75 weight%. In particular, when a resin that can be reacted by irradiation with active energy rays is used for the coating composition and an organic solvent is used (that is, a resin that can react by irradiation with active energy rays is not used as an organic solvent). The above range is preferred.
In the coating composition of the present invention, the amount of the resin modifier is preferably 1 to 50 parts by weight, more preferably 2 parts per 100 parts by weight of the resin or resin monomer that can react by irradiation with active energy rays. -30 parts by weight. In that case, the content of the resin modifier in the coating film to be obtained is preferably 1 to 50 parts by weight, more preferably 100 parts by weight of the resin or resin monomer that can react by irradiation with active energy rays. Is 2 to 30 parts by weight.
In the case where no resin or resin monomer is used in the coating composition of the present invention, the content of the resin modifier in the coating composition is determined from the viewpoint of antistatic properties and wettability. 50% to 100% by weight in the minute is preferred.

  In the coating composition of the present invention, the content of the organic solvent is preferably 10 to 70% by weight, more preferably 20 to 60% by weight, and still more preferably 20 to 55% by weight from the viewpoint of handling properties such as coating. It is. The amount of organic solvent in the coating composition includes the amount of organic solvent brought from the resin modifier solution.

The coating composition of the present invention preferably contains an ionic liquid from the viewpoint of improving antistatic properties under low humidity in addition to water resistance and transparency.
Here, the ionic liquid is preferably a compound represented by the following general formula (VI). X ⁺ and Y ⁻ do not have a polymerizable unsaturated group, that is, a group that is cured by the aforementioned active energy ray.

（但し、式中、Ｘ⁺はカチオン、Ｙ^-はアニオンを示す。）

(In the formula, X ⁺ represents a cation and Y ⁻ represents an anion.)

The molecular weight of the ionic liquid is preferably a molecular weight of 150 to 1,000, more preferably a molecular weight of 180 to 800, from the viewpoint of antistatic properties under low humidity.
Further, from the viewpoint of antistatic properties under low humidity, the melting point is preferably 100 ° C. or lower, more preferably 50 ° C. or lower, and further preferably 30 ° C. or lower. In the present invention, the melting point means a melting point measured by JIS K0064 “Method for measuring melting point and melting range of chemical product” or a freezing point measured by JIS K0065 “Method for measuring freezing point of chemical product”. The melting point of the compound that was solid at room temperature (20 ° C.) was measured, and the freezing point of the compound that was liquid at room temperature (20 ° C.) was measured as the melting point.

The cation represented by X ⁺ is more preferably one or more selected from the group consisting of the following formulas (a) to (d) from the viewpoint of antistatic properties under low humidity.

（式（ａ）中、Ｒ11は、炭素数1〜２０の炭化水素基を表し、Ｒ12は水素原子または炭素数１〜２０の炭化水素基又はヒドロキシル基を表し、Ｒ13は、炭素数1〜２０の炭化水素基または炭化水素基の一つの水素がヒドロシル基に置換した官能基を示す。）
（式（ｂ）中、Ｒ14は水素原子または炭素数１〜２０の炭化水素基又はヒドロキシル基を表し、Ｒ15は、炭素数１〜２０の炭化水素基または炭化水素基の一つの水素がヒドロシル基に置換した官能基を示す。）
（式（ｃ）中、Ｒ16およびＲ17は、それぞれ独立して、炭素数1〜２０の炭化水素基または炭化水素基の一つの水素がヒドロシル基に置換した官能基を示す。）Ｒ11〜17の炭化水素基は、独立して、好ましくは炭素数1〜8、より好ましくは炭素数1〜5、更により好ましくは炭素数1〜3である。
（式（ｄ）中、Xは、窒素原子、硫黄原子、又はリン原子を表し、Ｒ18は水素原子、炭素数１〜２０の炭化水素基、または炭化水素基の一つの水素がヒドロシル基に置換した官能基を示す。Ｒ19、Ｒ20、およびＲ21、はそれぞれ独立して炭素数１〜２０の炭化水素基、または炭化水素基の一つの水素がヒドロシル基に置換した官能基を表す。但しＸが硫黄原子の場合、Ｒ21はない。）Ｒ18の炭化水素基は、好ましくは炭素数6〜18、より好ましくは炭素数8〜18である。Ｒ19〜21の炭化水素基は、独立して、好ましくは炭素数1〜12、より好ましくは炭素数2〜8である。

(In the formula (a), R 11 represents a hydrocarbon group having 1 to 20 carbon atoms, R 12 represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a hydroxyl group, and R 13 represents 1 to 20 carbon atoms. Or a hydrocarbon group substituted with a hydrosyl group.)
(In the formula (b), R14 represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydroxyl group, and R15 represents a hydrosyl group in which one hydrogen atom of the hydrocarbon group or hydrocarbon group having 1 to 20 carbon atoms is substituted. Represents a substituted functional group.)
(In the formula (c), R16 and R17 each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a functional group in which one hydrogen of a hydrocarbon group is substituted with a hydrosyl group.) The hydrocarbon group independently preferably has 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms.
(In the formula (d), X represents a nitrogen atom, a sulfur atom, or a phosphorus atom, and R18 represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or one hydrogen of the hydrocarbon group is substituted with a hydrosyl group. R19, R20, and R21 each independently represent a hydrocarbon group having 1 to 20 carbon atoms, or a functional group in which one hydrogen of the hydrocarbon group is substituted with a hydrosyl group, where X is In the case of a sulfur atom, there is no R21.) The hydrocarbon group of R18 preferably has 6 to 18 carbon atoms, more preferably 8 to 18 carbon atoms. The hydrocarbon group of R 19-21 is independently preferably 1 to 12 carbon atoms, more preferably 2 to 8 carbon atoms.

The anion represented by Y ⁻ is aliphatic (carbon number 1 to 20) carboxylic acid, fluoroaliphatic (carbon number 1 to 20) carboxylic acid, poly (average) from the viewpoint of antistatic properties under low humidity. Addition mole number 1-50) oxyalkylene alkyl (carbon number 1-20) ether carboxylic acid, alkyl (carbon number 1-20) sulfate ester, polyoxyalkylene alkyl (carbon number 1-20) sulfate ester, alkane (carbon number) 1-20) sulfonic acid, fluoroalkane (1-20 carbon atoms) sulfonic acid, alkyl (1-20 carbon atoms) benzenesulfonic acid, alkyl (1-20 carbon atoms) phosphate ester, poly (average number of moles added 1) -50) oxyalkylene alkyl (1 to 20 carbon atoms) phosphate ester, bis (perfluoroalkyl (1 to 5 carbon atoms) sulfonyl) imide, tris (perfluoroalkyl (1 to 1 carbon atoms) ) Sulfonyl) methane, ions of organic acids such as tris (perfluoroalkyl (carbon number 1-5)) trifluorophosphate, tetrafluoroboric acid, perchloric acid, hexafluorophosphoric acid, hexafluoroantimonic acid and 6 Examples thereof include ions of inorganic acids such as arsenic fluoric acid, phosphoric acid, sulfuric acid, boric acid, halogen, dicyanoamide, tricyanomethide, tetracyanoborate, thiocyanic acid, and oxalic boric acid.
Specifically, from the viewpoint of antistatic properties under low humidity, [CF ₃ COO ⁻ ], [CH ₃ SO ₄ ⁻ ], [C ₂ H ₅ SO ₄ ⁻ ], [C ₄ H ₉ SO ₄ ⁻ ], [C ₆ H ₁₃ SO ₄ ⁻ ], [C ₈ H ₁₇ SO ₄ ⁻ ], [CH ₃ O (C ₂ H ₄ O) _n SO ₃ ⁻ ] (n represents the average number of added moles, 1 to 5), [CH ₃ SO ₃ ⁻ ], [C ₂ H ₅ SO ₃ ⁻ ], [CF ₃ SO ₃ ⁻ ], [C ₄ F ₉ SO ₃ ⁻ ], [CH ₃ C ₆ H ₄ SO ₃ ⁻ ] , [N (SO ₂ CF ₃ ) ₂ ⁻ ], [(C ₂ F ₅ ) ₃ PF ₃ ⁻ ], [BF ₄ ⁻ ], [PF ₆ ⁻ ], [HSO ₄ ⁻ ], [Cl ⁻ ], [Cl ⁻ ], Br ⁻ ], [I ⁻ ], [N (CN) ₂ ⁻ ], [C (CN) ₃ ⁻ ], [B (CN) ₄ ⁻ ], [SCN ⁻ ], [B (C ₂ O ₄ ) ₂ ^- one or more ionic compound selected from the group consisting of] is preferred.

Preferred examples of the ionic liquid represented by the formula (VI) include the following.
As the imidazolium compound (the compound in which the cation represented by X ⁺ is represented by the formula (a)), 1-ethyl-3-methylimidazolium tri (pentafluoroethyl) trifluorophosphate (melting point (hereinafter referred to as “melting point”) (Also referred to as “mp”): −1 ° C.), 1-butyl-3-methylimidazolium dicyanoamide (mp: <−20 ° C.), 1-butyl-2,3-dimethylimidazolium tetrafluoroborate (mp: 40 ° C), 1-butyl-2,3-dimethylimidazolium chloride (mp: 99 ° C), 1-butyl-3-methylimidazolium trifluoromethanesulfonate (mp: 17 ° C), 1-hexyl-3-methyl Imidazolium bis (trifluoromethylsulfonyl) imide (mp: -9 ° C.), 1-butyl-2,3-dimethylimidazolium hexafluorophor Fate (mp: 42 ° C.), 1-ethyl-3methylimidazolium tetrafluoroborate (mp: 14 ° C.), 1-ethyl-3 methyl imidazolium bromide (mp: 65 ° C.), 1-hexyl-3 methyl imidazolium Chloride (mp: <-20 ° C), 1-butyl-3methylimidazolium tetrafluoroborate (mp: <-20 ° C), 1-butyl-3methylimidazolium hexafluorophosphate (mp: 12 ° C), 1 -Ethyl-3-methylimidazolium chloride (mp: 88 ° C), 1-methyl-3-octylimidazolium chloride (mp: <-20 ° C), 1,3-dimethylimidazolium methyl sulfate (mp: 45 ° C) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (mp: -12 ° C.), 1-butyl-3-methylimidazolium methylsulfur (Mp: 13 ° C), 1-hexyl-3-methylimidazolium tetrafluoroborate (mp: <-20 ° C), 1-hexyl-3-methylimidazolium hexafluorophosphate (mp: <-20 ° C) ), 1-hexyl-3-methylimidazolium tri (pentafluoroethyl) trifluorophosphate (mp: -14 ° C), 1-butyl-3-methylimidazolium chloride (mp: 73 ° C), 1-butyl-3 -Methylimidazolium bromide (mp: 76 ° C), 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (mp: 2 ° C), 1-butyl-2,3-dimethylimidazolium trifluoromethanesulfur Phonate (mp: 41 ° C.), 1-ethyl-3-methylimidazolium trifluoroacetate (mp: <−20 ° C.), 1-butyl-3-methyl Louis imidazolium trifluoroacetate (mp: <-20 ° C), 1-ethyl-3-methylimidazolium dicyanamide (mp: <-20 ° C), 1-ethyl-3-methylimidazolium methyl sulfate (mp: <- 20 ° C), 1-ethyl-3-methylimidazolium p-toluenesulfonate (mp: 56 ° C), 1-butyl-3-methylimidazolium octyl sulfate (mp: 32 ° C), 1-butyl-3-methylimidazolium Iodide (mp: <-20 ° C), 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (mp: -15 ° C), 1-butyl-2,3-dimethylimidazolium iodide (mp: 97 ° C), 1-ethyl-3-methylimidazolium thiocyanate (mp: -20 ° C), 1-methyl-3-propylimidazolium (Mp: <-20 ° C), 1-ethyl-3-methylimidazolium octyl sulfate (mp: 11 ° C), 1-butyl-3-methylimidazolium hydrogen sulfate (mp: 38 ° C), 1-ethyl- 3-methylimidazolium tetracyanoborate (mp: 13 ° C), 1-butyl-3-methylimidazolium tri (pentafluoroethyl) trifluorophosphate (mp: 3 ° C), 1-decyl-3-methylimidazolium tetra Cyanoborate (mp: 18 ° C), 1-cyanomethyl-3-methyl-imidazolium bis (trifluoromethylsulfonyl) imide (mp: <-20 ° C), 1- (2-hydroxyethyl) -3-methylimidazolium Bis (trifluoromethylsulfonyl) imide (mp: <-20 ° C.), 1-ethyl-3-methylimidazolium methanesulfonate (Mp: 35 ° C.), 1-butyl-3-methylimidazolium methanesulfonate (mp: 75 ° C.), 1-ethyl-3-methylimidazolium 2 (2-methoxyethoxy) ethyl sulfate (mp: 15 ° C.) 1-ethyl-3-methylimidazolium normal butyl sulfate (mp: 24 ° C), 1-ethyl-3-methylimidazolium normal hexyl sulfate (mp: 7 ° C), 1-butyl-3-methylimidazolium tricyanomethide ( mp: <-20 ° C), 1- (2-hydroxyethyl) -3-methylimidazolium tri (pentafluoroethyl) trifluorophosphate (mp: <-20 ° C), 1-ethyl-3-methylimidazolium iodide (Mp: 69 ° C.), 1-ethyl-3-hydroxyethylimidazolium bromide (mp: <−20 ° C.), 1-ethyl-3-hy B propyl imidazolium bromide (mp: <- 20 ℃), and the like.

Examples of the pyridium compound (the compound in which the cation represented by X ⁺ is represented by the formula (b)) include N-butyl-3-methylpyridinium tetrafluoroborate (mp: <−20 ° C.), N-butyl. -3-methylpyridinium hexafluorophosphate (mp: 46 ° C), N-hexyl-4-dimethylamino-pyridium bis (trimethylsulfonyl) imide (mp: <-20 ° C), N- (3-hydroxypropyl) Pyridinium bis (trimethylsulfonyl) imide (mp: <-20 ° C), N-ethyl-3-hydroxymethylpyridium ethyl sulfate (mp: <-20 ° C), N-ethyl-3-methylpyridium ethyl sulfate (mp : <-20 ° C.), N-butyl-3-methylpyridinum dicyanamide (mp: 16 ° C.), N- (3-hydroxypropyl) pyridium tri (pentafur) Roechiru) trifluoro phosphate (mp: <- 20 ℃), and the like.

Examples of the pyrrolidinium compound (the compound in which the cation represented by X ⁺ is represented by the formula (c)) include N-butyl-1-methylpyrrolidinium dicyanoamide (mp: <−20 ° C.), N-butyl. -1-methylpyrrolidinium bis (trifluoromethylsulfonyl) imide (mp: -6 ° C), N-butyl-1-methylpyrrolidinium tri (pentafluoroethyl) trifluorophosphate (mp: 4 ° C), N -Butyl-1-methylpyrrolidinium tetracyanoborate (mp: 22 ° C), N- (methoxyethyl) -1-methylpyrrolidinium bis (trimethylsulfonyl) imide (mp: <-20 ° C), N-butyl -1-methylpyrrolidinium bis (oxalate (2-)-0,0 ′) borate (mp: 55 ° C.), N- (2-methoxyethyl) -1-methylpyrrolidinium Li (pentafluoroethyl) trifluorophosphate (mp: <-20 ° C) and the like.

Examples of ammonium compounds and phosphonium compounds (compounds in which the cation represented by X ⁺ is represented by the formula (d)) include trihexyl (tetradecyl) phosphonium tri (pentafluoroethyl) trifluorolophosphate (mp: <-20 ° C), trihexyl (tetradecyl) phosphonium bis (trifluoromethylsulfonyl) imide (mp: <20 ° C), tetrabutylammonium bis (trifluoromethylsulfonyl) imide (mp: 92 ° C), ethyl-dimethyl-propylammonium bis ( Trifluoromethylsulfonyl) imide (mp: −11 ° C.), N-ethyl-N, N-dimethyl-2-methoxyethylammonium tri (pentafluoroethyl) trifluorophosphate (mp: <− 20 ° C.), triethylamine nitrate ( mp: 12 ° C.).

In the coating composition of the present invention, the content of the ionic liquid is preferably 0.3 to 20% by weight, more preferably 0.5 to 15% by weight, and still more preferably, from the viewpoint of antistatic properties under low humidity. Is 1 to 10% by weight.
The weight ratio of the resin modifier to the ionic liquid (resin modifier / ionic liquid) in the coating composition of the present invention is 50/50 to 99/1 from the viewpoint of antistatic properties under low humidity. Is preferable, 55/45 to 95/5 is more preferable, and 60/40 to 90/10 is still more preferable. In addition, when the ionic liquid used in the coating composition of the present invention dissolves other components including the resin modifier of the present invention, from the viewpoint of improving handleability and simplifying the process, It can also be used as an organic solvent.

In addition to water resistance and transparency, the coating composition of the present invention preferably contains a conductive polymer from the viewpoint of improving antistatic properties under low humidity.
The conductive polymer in the present invention refers to a π-conjugated conductive polymer and a σ-conjugated conductive polymer, and is preferably a π-conjugated conductive polymer from the viewpoint of industrial availability. Examples of the π-conjugated conductive polymer include polythiophene, polypyrrole, polyisothianaphthene, polyaniline, polyacetylene, polyparaphenylene, polyphenylene vinylene, polychenylene vinylene, and derivatives thereof. These conductive polymers can be used alone or in admixture of two or more.
Among the conductive polymers, from the viewpoint of industrial availability, polythiophene, polypyrrole, polyaniline, polyisothianaphthene and derivatives thereof are preferable, and polythiophene, polypyrrole, polyaniline and derivatives thereof are more preferable.
Specific examples of the polythiophene derivative include alkyl group-containing polythiophenes such as poly (3-methylthiophene), poly (3-hexylthiophene), poly (3-octylthiophene), poly (3-dodecylthiophene), poly (3- Sulfone such as ether group-containing polythiophene such as methoxythiophene), poly (3-ethoxythiophene), poly (3,4-ethylenedioxythiophene), poly (3-sulfoethylthiophene), poly (3-sulfobutylthiophene) Examples thereof include carboxylic acid-containing polythiophenes such as acid group-containing polythiophene and poly (3-carboxythiophene).
Specific examples of the polypyrrole derivatives include alkyl group-containing polypyrrole such as poly (3-methylpyrrole), poly (3-butylpyrrole), poly (3-decylpyrrole), poly (3,4-dimethylpyrrole), poly ( 3-methoxypyrrole), ether group-containing polypyrrole such as poly (3-octoxypyrrole), hydroxy group-containing polypyrrole such as poly (3-hydroxypyrrole), poly (3-carboxylpyrrole), poly (3-methyl-4) -Carboethoxypyrrole), poly (3-methyl-4-carbobutoxypyrrole) and other carboxylic acid or carboxylic acid ester group-containing polypyrrole content.
Specific examples of the polyisothianaphthene derivative include sulfonic acid group-containing polyisothianaphthene such as poly (4-sulfoisothianaphthene).
Specific examples of the polyaniline derivatives include alkyl group-containing polyanilines such as poly (2-methylaniline) and poly (2-octylaniline), poly (2-sulfoaniline), poly (2-sulfo-5-methoxyaniline) and the like. And sulfonic acid group-containing polyaniline.
The weight average molecular weight of the conductive polymer is preferably 200 to 1000000, more preferably 300 to 500000, and more preferably 500 to 300000 from the viewpoint of antistatic properties under low humidity.
In the coating composition of the present invention, the content of the conductive polymer is preferably 0.1 to 20% by weight, and preferably 0.5 to 10% by weight from the viewpoint of antistatic property and transparency under low humidity. More preferably, it is 1 to 5% by weight.
The weight ratio of the resin modifier to the conductive polymer (resin modifier / conductive polymer) in the coating composition of the present invention is 30/70 from the viewpoint of antistatic properties under low humidity. -99/1 are preferable, 50 / 50-99 / 1 are more preferable, and 60 / 40-98 / 2 are still more preferable.
The conductive polymer may be used together with the ionic liquid, or a conductive polymer may be used instead of the ionic liquid.

  Although the coating composition of the present invention can contain water, the content of water in the coating composition is 5% from the viewpoint of suppressing deterioration of the coating film properties such as strength and transparency of the resulting coating film. %, More preferably less than 1% by weight, and still more preferably substantially free of water.

In addition to the above components, the coating composition of the present invention includes commonly used initiators, curing agents such as diisocyanate compounds, pigments / dyes, 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 coating composition of the present invention preferably contains an initiator such as a UV initiator or a photocationic initiator from the viewpoint of curing acceleration. For example, acetophenones, benzophenones, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkylcion compounds, disulfide compounds, thiuram compounds, fluoroamine compounds and the like are used. More specifically, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzyldimethylketone, 1- (4-dodecylphenyl) Examples include 2-hydroxy-2-methylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, and benzophenone.

  The coating composition of the present invention comprises the resin modifier of the present invention, if necessary, a resin or resin monomer that can react with the coating composition by irradiation with active energy rays, an organic solvent, an ionic liquid, a conductive polymer, and It can be produced by mixing with other components such as an initiator and stirring. The mixing order of each component is not particularly limited, but from the viewpoint of the solubility of the resin modifier of the present invention, the resin modifier of the present invention and the organic solvent are first mixed and the other components are mixed. Is preferred. 0-50 degreeC is preferable and the temperature at the time of mixing has more preferable 5-40 degreeC.

[Method for producing coating film]
In the coating film of the present invention, the coating composition containing the above-described resin modifier of the present invention is coated on a substrate, dried as necessary, and then irradiated with active energy rays. Can be obtained. The coating composition preferably further contains a resin or a resin monomer from the viewpoint of the hardness of the coating film.
The substrate on which the coating composition of the present invention 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 resin , Nitrile resin, polyether ketone resin, polyamide resin and the like.
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 preferably 10 to 500 mJ when ultraviolet rays are used as the active energy ray from the viewpoint of suppressing damage to the resin base material to which the coating composition is applied.

[Coating film]
The coating film of the present invention is preferably a coating film obtained by the production method described above.

The coating film of the present invention is also a coating film having a structure represented by the above formula (IV) at least partially. In the formula (IV), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , n, and AO are the same as in the case of the compounds (I) and (II).

  Whether the structure represented by the formula (IV) exists in the coating film is extracted with an organic solvent, and the extract is analyzed by NMR, IR, or the surface of the coating film is directly TOF. -It can confirm by performing a mass spectrometry by SIMS.

The coating film of the present invention is also a coating film having a structure represented by the above formula (V) at least partially. In the formula (V), R ¹ , R ⁸ , R ⁹ , n, and AO are the same as those in the compounds (I) and (III).

  Whether the structure represented by the formula (V) is present in the coating film can be determined by the same method as described above.

The surface resistivity 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 antistatic properties. 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 1 × 10 ¹³ Ω or less, more preferably 5 × 10 ¹² Ω or less, and more preferably from the viewpoint of maintaining water resistance. Preferably it is 1 × 10 ¹² Ω or less.

  Further, 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.

  Moreover, the contact angle with respect to the water of the coating film of this invention is 30 degrees or less from a viewpoint of maintaining anti-fogging property. The contact angle can be measured according to the method described in the examples.

  The coating film of the present invention can be used for various image devices such as LCD (liquid crystal display), touch panel, PDP (plasma display panel), EL (electroluminescence), optical disk surface protection, and various lens coatings.

  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.

[Preparation of resin modifier solution]
In this example, first, a resin modifier solution is prepared, and the prepared resin modifier solution, a resin monomer, a curing agent (UV initiator), and an organic solvent are mixed, and the process is performed. The coating compositions of Examples 1-30 and Comparative Examples 1-20 were prepared. However, in Examples 15 to 25 and Comparative Examples 12 to 18, an ionic liquid was further mixed. Moreover, about Examples 26-30 and Comparative Examples 19-20, the conductive polymer was further mixed. At this time, the resin modifier solution according to this example was obtained by salt exchange or neutralization using a specific sulfate salt aqueous solution or sulfate composition and a specific ammonium salt or amine. Below, the manufacturing method of sulfate salt aqueous solution is demonstrated first, and the method of preparing resin modifier solution by salt exchange using manufactured sulfate salt aqueous solution and ammonium salt first is demonstrated. Thereafter, a method for preparing a sulfate composition as a production intermediate of an aqueous sulfate salt solution and a resin modifier solution by neutralization of amine will be described. Table 1 shows combinations of the raw material for the anion part and the raw material for the cation part of the resin modifiers a to j, m, n, and o to be produced.
<1. Production of sulfate salt aqueous solution>
(Production Example 1)
500 g of aliphatic alcohol having 12 carbon atoms (product name: Calcoal 2098) and 0.75 g of KOH were charged into an autoclave equipped with a stirrer, temperature controller, and automatic introduction device, and dehydrated at 110 ° C. and 13 hPa for 30 minutes. Went. After dehydration, nitrogen substitution was performed, the temperature was raised to 120 ° C., and 355 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, 0.8 g of acetic acid was added to the autoclave, and the mixture was stirred at 80 ° C. for 30 minutes, and then extracted to obtain an alkoxylate having an average EO addition mole number of 3 mol.
The resulting alkoxylate was sulfated in a falling film reactor using SO ₃ gas to obtain a poly (3) oxyethylene lauryl ether sulfate composition. 100 g (A) of the composition was neutralized dropwise to 322 g of a 3.1 wt% NaOH aqueous solution to obtain a poly (3) sodium oxyethylene lauryl ether sulfate aqueous solution. The effective component concentration (% by weight) was 25% by weight as measured by the Epton method (JIS K3306). In the present invention, poly (3) oxyethylene means that n, which is the average number of added moles of ethylene oxide groups, is 3. The same applies hereinafter.
(Production Example 2)
The same operation as in Production Example 1 was performed using 500 g of aliphatic alcohol having 12 carbon atoms (product name: Calcoal 2098), 0.75 g of KOH, 2011 g of EO, and 0.8 g of acetic acid. 17) A sodium oxyethylene lauryl ether sulfate aqueous solution (effective content 25% by weight) was obtained.
(Production Example 3)
The same operation as in Production Example 1 was carried out using 300 g of aliphatic alcohol having 12 carbon atoms (product name: Calcoal 2098), 0.45 g of KOH, 3550 g of EO, and 0.48 g of acetic acid. 50) An aqueous sodium oxyethylene lauryl ether sulfate solution (effective content: 25% by weight) was obtained.
(Production Example 4)
The same operation as in Production Example 1 was carried out using 300 g of oleyl alcohol having 18 carbon atoms (reagent) manufactured by Wako Pure Chemical Industries, Ltd., 0.31 g of KOH, 1133 g of EO, and 0.33 g of acetic acid. A sodium oxyethylene oleyl ether sulfate aqueous solution (effective weight 25% by weight) was obtained.
(Production Example 5)
Using 500 g of poly (3) oxyethylene methyl ether (manufactured by Nippon Emulsifier Co., Ltd., product name methyl triglycol) as the alkoxylate, the same sulfation and neutralization operations as in Production Example 1 were performed, and poly (3) oxyethylene methyl was obtained. A sodium ether sulfate aqueous solution was obtained. However, the effective content of the compound was the residual content (solid content) 52% by weight after drying under reduced pressure at 70 ° C., 200 hPa for 5 hours.
(Production Example 6)
The same procedure as in Production Example 1 was performed using 300 g of palmityl alcohol having 16 carbon atoms (product name: Calcoal 6098), 0.35 g of KOH, 55 g of EO, and 0.38 g of acetic acid. 1) An aqueous sodium oxyethylene palmityl ether sulfate solution (effective content: 10% by weight) was obtained.
(Production Example 7)
Using 300 g of decyl alcohol having 10 carbon atoms (product name: Calcoal 1098), 0.53 g of KOH, 167 g of EO, and 0.57 g of acetic acid, the same operation as in Production Example 1 was performed, and poly (2 ) An aqueous sodium oxyethylene decyl ether sulfate solution (effective content 25% by weight) was obtained.
<2. Preparation of resin modifier solution>
Resin modifier solutions aj, m, n, and o were obtained according to the following method. Each compounding amount is as shown in Table 1.
[Production Method 1]
(Resin modifier solution a)
100 g of the poly (3) oxyethylene lauryl ether sulfate aqueous solution obtained in Production Example 1 and 16.4 g of 1- (acrylamidopropyl) trimethylammonium chloride were placed in an eggplant flask, and a rotary evaporator (ROTARY EBAPORATOR manufactured by TOKYO RIKAKIKAI CO., LTD. N-1000), and rotating and stirring (rotation speed: SPEED 4) at room temperature (25 ° C.) and normal pressure (1013 hPa) for 5 minutes. Thereafter, moisture was removed while applying air leaked at 40 ° C. and 300 hPa to the sample, and then moisture was removed at 40 ° C. and 1 hPa for 2 hours. Thereafter, 45 g of isopropyl alcohol was added to the eggplant flask, and then the mixture was rotationally stirred with a rotary evaporator at room temperature for 30 minutes. The obtained suspension was subjected to 0.2 μm membrane filtration to obtain a resin modifier solution a (solid content: 43% by weight).
(Resin modifier solutions b to d, f to i, m, n, o)
Resin modifier except that 100 g of poly (3) oxyethylene lauryl ether sulfate aqueous solution and 16.4 g of 1- (acrylamidopropyl) trimethylammonium chloride were changed to the materials in Table 1 and the amounts used in Table 1 were used. Resin modifier solutions b to d, f to i, m, n, and o were obtained by the same preparation method as that for solution a.
[Production Method 2]
(Resin modifier solution e)
The poly (3) oxyethylene lauryl ether sulfate composition obtained as an intermediate of Production Example 1 was used as an effective content of 100% by weight. 41.2 g of poly (3) oxyethylene lauryl ether sulfate composition was dropped into a 4-neck flask equipped with a stirrer charged with 50 g of isopropyl alcohol and 8.8 g of allyldimethylamine over 20 minutes while cooling with ice in a nitrogen stream. did. Further, aging was performed for 10 minutes to obtain a resin modifier solution e. The residue (solid content) after drying under reduced pressure at 120 ° C. and 200 hPa for 5 hours was 50% by weight.
(Resin modifier solution j)
A resin modifier solution j was obtained by the same preparation method as the resin modifier solution e except that 8.8 g of allyldimethylamine was changed to 15.4 g of triethanolamine.
<3. Production of ionic liquid>
In this example, commercially available reagents were used except for 1-ethyl-3-hydroxyethylimidazolium bromide.
(Production Example 8) Production of 1-ethyl-3-hydroxyethylimidazolium bromide A 4-necked flask equipped with a stirrer and charged with 150 g of 2-bromoethanol (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) under a nitrogen stream, While cooling with ice, 173 g of 1-ethylimidazole (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 2 hours. Next, ice cooling was removed, and the temperature inside the reaction system was brought to room temperature (25 ° C.). 10 minutes after returning to room temperature, it heated in the 60 degreeC water bath. After heating for 15 hours, the water bath was removed and the temperature was returned to room temperature. The reaction product was transferred to a separatory funnel and washed 5 times with 500 ml of diethyl ether and further 5 times with 500 ml of ethyl acetate. The solvent which melt | dissolved the obtained washing | cleaning material at 70 degreeC and 10 hPa was removed, and 238g of the target 1-ethyl-3-hydroxyethyl imidazolium bromide was obtained.

Next, preparation of the coating composition will be described. Tables 2 to 6 and Table 9 are tables showing the compositions of the coating compositions (Examples 1 to 30 and Comparative Examples 1 to 20) and their physical properties. In Tables 2 to 6 and Table 9, resin modifiers a to j, m, n, and o represent resin modifiers produced by the combinations shown in Table 1.
[Preparation of coating composition]
Acrylic resin (DPHA [dipentaerythritol hexaacrylate] manufactured by Daicel-Cytec Corp.) as a resin that can react upon irradiation with active energy rays, Irgacure 184 (Ciba Specialty Chemicals Corp.) as a curing agent, and organic Examples 1 to 14 and comparison of coating compositions containing the resin modifiers having the compositions shown in Tables 2 to 4 by mixing the solvent and the aforementioned resin modifier solution as a resin modifier Prepared as Examples 1-10. For Examples 15 to 25 and Comparative Examples 11 to 18, in addition to the above, an ionic liquid was further mixed to prepare a coating composition containing a resin modifier having the composition shown in Tables 5 and 6. Moreover, about Examples 26-30 and Comparative Examples 19-20, the conductive polymer was further mixed and the coating composition containing the resin modifier of the composition shown in Table 9 was prepared.
In Examples 1 to 30 and Comparative Examples 1 to 4, 7, 8, 10 to 14, and 17 to 20, isopropyl alcohol is used as the organic solvent, and in Comparative Examples 5, 6, 9, 15, and 16, , Methanol was used. Each blending amount was as shown in Tables 2 to 6 and Table 9. In addition, each compounding amount shown in Tables 2 to 4 is when the total weight (solid content) of the resin, the curing agent, and the effective component of the resin modifier that can react by irradiation with active energy rays is 100 parts by weight. Each part by weight is shown. Each compounding amount shown in Tables 5 and 6 is 100 parts by weight of the total weight (solid content) of the resin, the curing agent, the effective part of the resin modifier, and the ionic liquid that can be reacted by irradiation with active energy rays. The parts by weight are shown. Moreover, each compounding amount shown in Table 9 is 100 parts by weight of the total weight (solid content) of the resin, the curing agent, the effective component of the resin modifier, and the conductive polymer that can react by irradiation with active energy rays. The parts by weight are shown.

[Production of coating film]
Each coating composition obtained was coated on 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 (bar coater (gap: 9-13 μm)) Was applied to almost one surface and dried under the drying conditions shown in Tables 2 to 4, Table 7, Table 8, and Table 10. The dried film was subjected to UV irradiation (200 mJ) under a nitrogen stream with a UV irradiation apparatus (HTE-505HA, manufactured by Hitec Co., Ltd., UV lamp is USH-500 MB) to obtain a coating film (thickness 4 μm). In addition, the coating thickness measured three points, the upper part, the center, and the lower part on the center line of the width | variety of a coating surface, and used the average value.

[Surface specific resistance value of coating film (antistatic property)]
The coating films (Examples 1 to 11, Examples 15 to 30, Comparative Examples 1 to 7 and Comparative Examples 11 to 20) were adjusted to a temperature of 25 ° C. and a relative humidity of 45%, and the A-4329 type high Using a resistance meter (manufactured by Yokogawa YHP), the surface specific resistance value at the center of the membrane was measured. The surface specific resistance value indicates that the smaller the value, the better the antistatic property.
The results are shown in Table 2, Table 3, Table 7, Table 8, and Table 10.

[Surface specific resistance value of coating film (low-humidity antistatic property)]
About coating films (Examples 15 to 30 and Comparative Examples 11 to 20), in a dry room (manufactured by Gowa Industry Co., Ltd.) having a temperature of 25 ° C. and a dew point temperature adjusted to −60 ° C. to −70 ° C., 72 hours After storage, the measurement was performed in the dry room by the method described above.
The results are shown in Table 7, Table 8, and Table 10.

[Surface specific resistance value after washing of coating film (water resistance)]
The coating films (Examples 1 to 11, Examples 15 to 30, Comparative Examples 1 to 7, and Comparative Examples 11 to 20) were washed with water, and then the surface resistivity was measured. The water washing conditions were as follows: tap water was passed from a tap with an inner diameter of 14 mm at a flow rate of 10 L / min, and a test film was placed 10 cm directly below the tap so that the tap water hits vertically, and the coating surface was uniform for 30 seconds. It went while moving as if taking. Thereafter, the moisture on the coating surface was removed with a hyper dry paper towel manufactured by Nippon Paper Crecia Co., Ltd., and air was blown at a temperature of 25 ° C. and a humidity of 45% until the water droplets disappeared. 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 2, Table 3, Table 7, Table 8, and Table 10.

[Haze value of coating film (transparency)]
For coating films (Examples 1 to 11, Examples 15 to 30, Comparative Examples 1 to 7, and Comparative Examples 11 to 20), JIS K 7105 Plastic Optical Properties Test Method (5.5 and 6.4) The haze value was determined with a haze meter HM-150 manufactured by Murakami Color Research Laboratory. Specifically, the diffuse transmittance and the total light transmittance were measured 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 2, Table 3, Table 7, Table 8, and Table 10.

[Contact angle of coating film]
For the coating films (Examples 12 to 14 and Comparative Examples 8 to 10), the contact angle with water was measured using a contact angle meter CA-A manufactured by Kyowa Interface Chemical Co., Ltd. Note that the smaller the value of the contact angle with respect to water, the more wet and spreads when water coagulates, so that irregular reflection does not occur, and as a result, an antifogging effect is obtained.
The results are shown in Table 4.

Claims (10)

A resin modifier which is an antistatic agent represented by the following formula (I).

(In the formula, R ¹ is a hydrocarbon group having 1 to 22 carbon atoms, AO is an alkylene oxide group having 2 to 3 carbon atoms, n is an average added mole number of AO, a positive number of 100 or less, B ⁺ Represents an ammonium ion (C) having a polymerizable unsaturated group.)   The resin modifier according to claim 1, which has active energy ray curability. The resin modifier according to claim 1 or 2, wherein the ammonium ion (C) is represented by the following formula (II) or the following formula (III).

(In the formula, R ² , R ³ and R ⁴ are each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ⁵ is an alkylene group having 2 to ⁵ carbon atoms, and R ⁶ is a hydrogen atom or (Methyl group, X represents O or NH)

(In the formula, R ⁷ and R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ⁹ represents a hydrocarbon group having 1 to 8 carbon atoms.)   The coating composition containing the resin modifier and organic solvent in any one of Claims 1-3.   Furthermore, the coating composition of Claim 4 containing the resin or resin monomer which can react by irradiation of an active energy ray.   Furthermore, the coating composition of Claim 4 or 5 containing an ionic liquid.   Furthermore, the coating composition in any one of Claims 4-6 containing a conductive polymer. The conductivity of the conductive polymer is 3 × 10 ³ The coating composition according to claim 7, which is S / cm or more. After coating the coating composition according to the substrate in any one of claims 4-8, by irradiation with active energy rays, the production method of the coating film to form a coating film on the substrate. A coating film obtained by the production method according to claim 9 .