JP2019023171A - Anionic hydrophilic group-containing (meth) acrylate compound and coating composition containing the compound - Google Patents

Abstract

To provide: a (meth) acrylate compound having two anionic hydrophilic groups in one molecule, and showing excellent antifouling properties and/or anti-fogging properties; and a coating composition.SOLUTION: The present invention provides an anionic hydrophilic group-containing (meth) acrylate compound represented by formula (I), a method for producing the compound, a composition containing the compound, a coating film containing the composition, a laminate having the coating film formed, and a method for producing the laminate.SELECTED DRAWING: None

Description

  The present invention relates to a novel anionic hydrophilic group-containing (meth) acrylate compound and a coating composition containing the compound. More specifically, an anionic hydrophilic group-containing (meth) acrylate compound having two anionic hydrophilic groups in one molecule and having excellent hydrophilicity and antifouling property and / or antifogging property, and production of the compound The present invention relates to a method, a composition containing the compound, a coating film comprising the composition, a laminate comprising the coating film, and a method for producing the laminate.

  To date, several hydrophilic paints are known. For example, a hydrophilic coating formed from a (meth) acrylate compound having at least one anionic hydrophilic group selected from a sulfonic acid group, a carboxyl group, and a phosphoric acid group and an acrylate resin has been reported. It has also been reported that the water-resistant paint exhibits antifouling properties, antifogging properties and the like (Patent Documents 1 and 2).

  However, antifouling properties and antifogging properties are not known for (meth) acrylate compounds having two anionic hydrophilic groups in one molecule.

International Publication No. 2007/064003 JP 2014-198754 A

  As a result of intensive studies by the present inventors, it has been found that a (meth) acrylate compound having two anionic hydrophilic groups in one molecule has hydrophilicity, antifouling property and / or antifogging property. Therefore, the present invention provides a novel anionic hydrophilic group-containing (meth) acrylate compound represented by the formula (I) and a method for producing the compound. Moreover, this invention provides the composition containing this compound, the coating film containing this composition, the laminated body in which this coating film was formed, and the manufacturing method of this laminated body.

  The present invention provides the following aspects, but is not limited thereto.

［式中、Ｒ_１は水素またはメチル基を表し；Ｒ_２はアニオン性親水基を表し；Ｒ_３は直鎖または分岐の脂肪族炭化水素基を表し；Ｘは水素またはアルカリ金属イオンを表し；そして、Ｒは芳香族環状基または脂肪族環状基を表す。］
で示される化合物。
［２］ 該アニオン性親水基が、ＣＯ_２ ⁻、またはＳＯ_３ ⁻から選ばれる基である、項［１］記載の化合物。
［３］ 該アニオン性親水基が、ＣＯ₂ ⁻である、項［１］記載の化合物。
［４］ Ｒ_１が、メチル基である、項［１］から［３］のいずれか１項に記載の化合物。
［５］ Ｒ_３が、エチレン基である、項［１］から［４］のいずれか１項に記載の化合物。
［６］ Ｒが、式（II）：

で示される、項［１］から［５］のいずれか１項に記載の化合物。
［７］ 少なくとも１つのＸがアルカリ金属イオンである、項［１］から［６］のいずれか１項に記載の化合物。
［８］ 式：

［式中、Ｒ_１は水素またはメチル基を表し；そして、Ｘは水素またはアルカリ金属イオンを表し、少なくとも１つはアルカリ金属イオンである］
で示される、項［１］から［７］のいずれか１つに記載の化合物。 (Compound)
[1] Formula (I):

[Wherein R ₁ represents hydrogen or a methyl group; R ₂ represents an anionic hydrophilic group; R ₃ represents a linear or branched aliphatic hydrocarbon group; X represents hydrogen or an alkali metal ion; R represents an aromatic cyclic group or an aliphatic cyclic group. ]
A compound represented by
[2] The compound according to item [1], wherein the anionic hydrophilic group is a group selected from CO ₂ ⁻ or SO ₃ ^— .
[3] The compound according to item [1], wherein the anionic hydrophilic group is CO ₂ ^— .
[4] The compound according to any one of items [1] to [3], wherein R ₁ is a methyl group.
[5] The compound according to any one of items [1] to [4], wherein R ₃ is an ethylene group.
[6] R is the formula (II):

The compound according to any one of Items [1] to [5], which is represented by:
[7] The compound according to any one of items [1] to [6], wherein at least one X is an alkali metal ion.
[8] Formula:

[Wherein R ₁ represents hydrogen or a methyl group; and X represents hydrogen or an alkali metal ion, and at least one is an alkali metal ion]
The compound according to any one of items [1] to [7], which is represented by:

(Composition)
[9] (A) The compound according to any one of items [1] to [8], and (B) one or more compounds containing at least two ethylenically unsaturated groups,
A composition comprising
[10] The composition according to item [9], comprising the compound (A) in a weight ratio of 0.01 wt% to 30 wt% with respect to the compound (B).

(Coating film, laminate, etc.)
[11] A coating film comprising the composition according to any one of items [9] to [10] cured on a substrate.
[12] A laminate comprising the coating film according to item [11] and a base material layer, and the coating film is formed on at least one surface of the base material layer.
[13] The laminate according to item [12], which is a water-borne article.

(Use)
[14] An antifouling agent comprising the compound according to any one of items [1] to [8] or the composition according to any one of items [9] to [10].
[15] An antifogging agent comprising the compound according to any one of items [1] to [8] or the composition according to any one of items [9] to [10].

(Laminate manufacturing method)
[16] (1) A step of applying the composition according to any one of items [9] to [10] to a substrate, and (2) whether the composition is irradiated with light or given heat. Or a process of performing both of the steps.
[17] Item [16], wherein in step (2) of item [16], a coating film is formed by irradiating light, applying heat, or both. Manufacturing method.

［式中、Ｒ_１、Ｒ_２、Ｒ_３、ＲおよびＸは、項［１］に定義する通りである］
で示される化合物の製造方法であって、
式（ＩＶ）：

［式中、Ｒは前記の通りであり、そしてＲ_２ ^’はアニオン性親水基の部分を表す］
で示されるハライド化合物を、式（Ｖ）：

［式中、Ｒ_１およびＲ_３は、前記の通りである］
で示される（メタ）アクリレート化合物、および脱酸剤と共に、適宜、重合禁止剤の存在下で反応させる。次いで、Ｘ供給源となるアルカリ金属の水酸化物、炭酸塩または炭酸水素塩から選ばれるＸ供給源の化合物と反応させて、Ｘがアルカリ金属イオンである式（Ｉ）で示される化合物を得ることを含む、該製造方法。 (Method for producing compound)
[18] Formula (I) according to item [1]:

[Wherein R ₁ , R ₂ , R ₃ , R and X are as defined in item [1]]
A process for producing a compound represented by
Formula (IV):

[Wherein R is as defined above, and R ₂ ^′ represents a portion of an anionic hydrophilic group]
A halide compound represented by formula (V):

[Wherein R ₁ and R ₃ are as defined above]
The reaction is carried out in the presence of a polymerization inhibitor, as appropriate, together with the (meth) acrylate compound represented by Next, it is reacted with an X source compound selected from an alkali metal hydroxide, carbonate or bicarbonate serving as an X source to obtain a compound represented by the formula (I) wherein X is an alkali metal ion. The manufacturing method.

  The (meth) acrylate compound having two anionic hydrophilic groups in one molecule of the present invention is hydrophilic, and the composition comprising the compound of the present invention or the coating film comprising the composition is Can be used for antifouling and / or antifogging.

The present invention is described in further detail below.
(Definition)
The definitions of terms used in the present specification and claims are shown below. Unless otherwise indicated, the first definition given for a group or term herein applies to the group or term herein individually or as part of another group.

［式中、Ｒ_１は水素またはメチル基を表し；Ｒ_２はアニオン性親水基を表し；Ｒ_３は直鎖または分岐の脂肪族炭化水素基を表し；Ｘは水素またはアルカリ金属イオンを表し；そして、Ｒは芳香族環状基または脂肪族環状基を表す。］
で示される化合物（以下、「本発明化合物」と呼称する）を提供する。 (Compound of the present invention)
As one aspect of the present invention, the present invention provides:
Formula (I):

[Wherein R ₁ represents hydrogen or a methyl group; R ₂ represents an anionic hydrophilic group; R ₃ represents a linear or branched aliphatic hydrocarbon group; X represents hydrogen or an alkali metal ion; R represents an aromatic cyclic group or an aliphatic cyclic group. ]
(Hereinafter, referred to as “the compound of the present invention”).

Examples of the R ₁ group in the formula (I) include hydrogen and a methyl group. When the R ₁ group is hydrogen, it contains an acryloyl moiety, and when the R ₁ group is a methyl group, it means that it contains a methacryloyl moiety. The R ₁ group is preferably a methyl group.

In the formula (I), the term “anionic hydrophilic group” as the R ₂ group means an atomic group that forms a negative bond with a water molecule, such as a hydrogen bond, which is negatively charged when dissolved in water. Due to the presence of the anionic hydrophilic group, it is possible to prevent components constituting scale such as silica, Na, and K in tap water from adhering to the surface of the hydrophilic coating film, and even when adhering, they do not adhere firmly. Therefore, it can be easily removed and the hydrophilicity of the coating film can be maintained for a long time. Specific examples of the anionic hydrophilic group include, but are not limited to, at least one group selected from CO ₂ ⁻ and SO ₃ ^— . In one embodiment, the anionic hydrophilic group is preferably CO ₂ ^— .

Examples of the X group in the formula (I) include, but are not limited to, hydrogen and alkali metal ions. From the viewpoint of easily maintaining the hydrophilicity of the anionic hydrophilic group as the R ₂ group, a counter cation is preferable, and examples thereof include alkali metal ions (for example, sodium ions and potassium ions).
The cation in the X group can be converted to a desired cation by a generally well-known cation exchange method (for example, use of a cation exchange resin).

In the above formula (I), the R group is an aromatic cyclic group or an aliphatic cyclic group, and is preferably an aromatic carbocyclic group.
As used herein, the term “aromatic cyclic group” includes at least one group selected from an aromatic carbocyclic group or an aromatic heterocyclic group. When the R group is an aromatic cyclic group, the R group is preferably an aromatic carbocyclic group.

  Examples of aromatic carbocyclic groups mean 6 to 14 membered monocyclic, bicyclic or tricyclic aromatic carbocyclic groups. Specific examples include, but are not limited to, phenyl, naphthyl, phenanthryl, anthranyl and the like. For example, phenyl is more preferable.

  The aromatic heterocyclic group means an aromatic heterocyclic group containing the same or different 1 to 3 hetero atoms independently selected from the group consisting of oxygen atom, sulfur atom and nitrogen atom in the ring. To do. For example, a 5-8 membered aromatic heterocyclic group is mentioned, A 5 or 6 membered ring is preferable and a 6 membered ring is more preferable. Specific examples include, but are not limited to, a pyrrolyl group, a furanyl group, a thienyl group, a pyridinyl group, a pyrimidinyl group, and a pyridazinyl group. For example, a pyridinyl group is more preferable.

  As used herein, the term “aliphatic cyclic group” includes at least one group selected from an aliphatic carbocyclic group or an aliphatic heterocyclic group. When the R group is an aliphatic cyclic group, the R group is preferably an aliphatic carbocyclic group.

  An aliphatic carbocyclic group means a saturated or unsaturated non-aromatic carbocyclic group. Examples thereof include 4- to 9-membered monocyclic or polycyclic (for example, bicyclic) cycloalkane groups, and specific examples include, but are not limited to, cyclopropyl, cyclohexyl and the like.

  An aliphatic heterocyclic group is a saturated or unsaturated aliphatic group containing the same or different 1 to 3 hetero atoms independently selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom in the ring. A heterocyclic group is meant. Examples include 4 to 9-membered monocyclic or polycyclic (eg, bicyclic) saturated or unsaturated aliphatic heterocycles, such as azetidinyl, oxetanyl, pyrrolidinyl, tetrahydrothienyl, tetrahydrofuranyl, Examples include, but are not limited to, thiazolidinyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, homomorpholinyl, tetrahydrothiopyranyl, tetrahydropyranyl and the like.

  The aromatic cyclic group or the aliphatic cyclic group may be substituted with one or more (for example, 1 to 3, 1 to 2, or 1) substituents. The aliphatic carbocyclic group, aliphatic heterocyclic group, aromatic carbocyclic group, aromatic heterocyclic group, ether group, ester group, anionic hydrophilic group and the like are not limited thereto.

で示され得るが、これに限定されない。例えば、１実施態様において、該Ｒ基は、式：

で示され得る。 In one embodiment, when the R group is an aromatic cyclic group, the R group may be, for example, formula (II):

However, the present invention is not limited to this. For example, in one embodiment, the R group has the formula:

Can be shown.

で示され得るが、これに限定されない。例えば、１実施態様において、該Ｒ基は、式：

で示され得る。 In one embodiment, when the R group is an aliphatic cyclic group, the R group may be, for example, formula (III):

However, the present invention is not limited to this. For example, in one embodiment, the R group has the formula:

Can be shown.

The R ₃ group in the formula (I) is a linear or branched aliphatic hydrocarbon group, and examples thereof include, but are not limited to, an alkyl group having 2 to 6 carbon atoms. An alkyl group having 2 to 4 carbon atoms is preferable, and an alkyl group having 2 or 3 carbon atoms is particularly preferable. Specific examples include ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, pentyl and hexyl.

［式中、Ｒ_１は水素またはメチル基を表し；そして、Ｘは水素またはアルカリ金属イオンを表し、少なくとも１つはアルカリ金属イオンである］ In one embodiment, specific examples of compounds of formula (I) include those of the formula:

[Wherein R ₁ represents hydrogen or a methyl group; and X represents hydrogen or an alkali metal ion, and at least one is an alkali metal ion]

まず、式：

で示される、（メタ）アクリレート化合物（式中、Ｒ_１が水素原子である場合はアクリロイル化合物であり、Ｒ_１が水素原子である場合はメタアクリロイル化合物である）（Ｒ_３は直鎖または分岐の脂肪族炭化水素基である）を商業的に入手するか、あるいは例えば（メタ）アクリル酸を出発原料として用いて酸化アルキレン（別名、アルキレンオキシド）と反応させることにより製造することができる。該酸化アルキレンとしては例えば酸化エチレン（別名、エチレンオキシド）、酸化プロピレン（別名、プロピレンオキシド）が挙げられるが、これらに限定されない。 (Method for producing the compound of the present invention)
The (meth) acrylate compound having two anionic hydrophilic groups in one molecule of the present invention is produced according to an organic synthesis reaction, starting from various raw material compounds. An example of the production scheme is shown below.

First, the formula:

(In the formula, when R ₁ is a hydrogen atom, it is an acryloyl compound, and when R ₁ is a hydrogen atom, it is a methacryloyl compound) (R ₃ is linear or branched) For example, (meth) acrylic acid as a starting material, and can be produced by reacting with an alkylene oxide (also called an alkylene oxide). Examples of the alkylene oxide include, but are not limited to, ethylene oxide (also known as ethylene oxide) and propylene oxide (also known as propylene oxide).

で示される、アニオン性親水基Ｒ_２（例えば、カルボン酸基）を含有する芳香族環状カルボン酸ハライドまたは脂肪族環状カルボン酸ハライド（ここで、ハロゲン原子は、例えば塩素原子、臭素原子、またはヨウ素原子が挙げられる）を商業的に入手するか、あるいはアニオン性親水基部分Ｒ_２’含有の芳香族環状カルボン酸、または脂肪族環状カルボン酸を出発原料として用いてハロゲン化剤と反応させることにより製造することができる。該ハロゲン化剤としては有機合成的にカルボン酸からカルボン酸ハロゲン化合物を製造するのに通常使用される剤が挙げられ、例えば塩化チオニル、塩化オキサリル、塩化ホスホリル、塩化スルホリル、三塩化リン、及び五塩化リン等が挙げられるが、これらに限定されない Next, the formula:

An aromatic cyclic carboxylic acid halide or an aliphatic cyclic carboxylic acid halide containing an anionic hydrophilic group R ₂ (for example, a carboxylic acid group), wherein the halogen atom is, for example, a chlorine atom, a bromine atom, or an iodine By atomization) or by reacting with an aromatic cyclic carboxylic acid containing an anionic hydrophilic group moiety R ₂ ′ or an aliphatic cyclic carboxylic acid as a starting material and a halogenating agent. Can be manufactured. Examples of the halogenating agent include agents commonly used for organically producing carboxylic acid halogen compounds from carboxylic acids, such as thionyl chloride, oxalyl chloride, phosphoryl chloride, sulfolyl chloride, phosphorus trichloride, and pentachloride. Examples include, but are not limited to, phosphorus chloride.

A (meth) acrylate anhydride can be produced by reacting the (meth) acrylate compound prepared above with a halide compound containing an anionic hydrophilic group R ₂ . More specifically, first, a solution in which a (meth) acrylate compound and a deoxidizer are dissolved is dropped into a halide compound solution dissolved in a solvent, and stirred for 0.5 to 8 hours. The reaction temperature is −50 to 20 ° C., and more preferably −10 to 10 ° C. from the viewpoint of reaction selectivity. As a reaction ratio between the halide compound and the (meth) acrylate compound, the reaction is performed by using 1 mol or more of the halide compound with respect to 1 mol of the (meth) acrylate compound. The concentration of the solute in the reaction is preferably 1 to 50% by weight, more preferably 20 to 40% by weight. After completion of the reaction, the precipitated hydrochloride is filtered off and washed with a solvent capable of dissolving impurities such as toluene to obtain a (meth) acrylate anhydride. The anhydride may be further dried in vacuum and used for the next alkali metal chloride reaction. In this case, the drying temperature is preferably 30 to 120 ° C., and more preferably 40 to 80 ° C. from the viewpoint of product stability.

  Although it does not specifically limit as a solvent used for manufacture of (meth) acrylate anhydride, Specifically, Aromatic hydrocarbon solvents, such as toluene and xylene, Hydrocarbon solvents, such as hexane and heptane, Tetrahydrofuran, Diethyl ether And ether solvents such as monoethylene glycol dimethyl ether, ketone solvents such as acetone, cyclopentanone and cyclohexanone, and ester solvents such as ethyl acetate and gamma butyrolactone. Of these, toluene and ethyl acetate are preferable from the viewpoint of solubility and stability. These solvents may be used alone or in combination with any of a plurality of solvents.

  Although it does not specifically limit as a deoxidizer used for manufacture of (meth) acrylate anhydride, Specifically, inorganic bases, such as tertiary amines, such as a pyridine and a triethylamine, sodium hydroxide, sodium hydrogencarbonate, are mentioned. It is done. Of these, pyridine is preferred from the viewpoint of reaction selectivity. The amount of these deoxidizers used is 1 molar equivalent or more with respect to the halide compound. Although the upper limit is not particularly limited, an amount of 50 mol equivalent or less, preferably 10 mol equivalent or less is used from an economical viewpoint.

  By reacting the (meth) acrylate anhydride prepared above with water, a ring-opened product in which (meth) acrylate is hydrolyzed (hereinafter referred to as a (meth) acrylate hydrolyzed product) can be produced. Is possible. More specifically, water is added to (meth) acrylate anhydride and stirred for 0.5 to 5 hours. The reaction temperature is 20 ° C. to 60 ° C., more preferably 40 ° C. to 50 ° C. The concentration of the solute in the reaction is 5 to 50% by weight, more preferably 10 to 30% by weight. The (meth) acrylate hydrolyzed ring is further dried and used for the alkali metalation reaction. In this case, the drying temperature is preferably 10 to 100 ° C., and more preferably 30 to 60 ° C. from the viewpoint of product stability.

  Next, when an anionic hydrophilic group-containing (meth) acrylate compound of the formula (I) in which X is an alkali metal or alkaline earth metal ion is desired, an alkali metal or alkaline earth metal water as the X source A compound represented by the formula (I) can be produced by reacting with an oxide or the like in the presence of a polymerization inhibitor as appropriate.

  X sources include, for example, inorganic bases (eg, alkali metals (eg, lithium, sodium, potassium), alkaline earth metals (eg, magnesium, calcium, barium) hydroxides, carbonates, bicarbonates)) However, it is not limited to these. Typical examples include sodium hydroxide, sodium bicarbonate and their aqueous solutions.

  In order to prevent polymerization reaction between anionic hydrophilic group-containing (meth) acrylate compounds in the above reaction, a polymerization inhibitor may be appropriately added. Examples of the polymerization inhibitor include compounds generally used for suppressing the polymerization reaction of polymerizable monomers, such as hydroquinone compounds (for example, hydroquinone, methylhydroquinone, dimethylhydroquinone, 4-methoxyphenol). However, it is not limited to these.

The amount ratio of the compound of the X source is the molar ratio per number of R ₂ groups contained in the anionic hydrophilic group-containing (meth) acrylate compound of the X source (alkali metal or alkaline earth metal hydroxide, etc.) For example, about 0.5 to about 2.0 equivalents, preferably about 1.0 equivalents.
Furthermore, the compound as a polymerization inhibitor is used in a molar ratio with respect to the anionic hydrophilic group-containing (meth) acrylate compound, for example, a catalytic amount to a stoichiometric amount, typically about 0.1 to about 10%. May be.

As a solvent in the reaction of the anionic hydrophilic group-containing (meth) acrylate compound, any solvent that does not affect the reaction may be used. For example, ethers such as THF, halogenated hydrocarbons such as dichloromethane, In water or a mixed solvent thereof, etc.), but more preferably water may be used.
The reaction temperature is not particularly limited as long as the reaction suitably proceeds, and for example, about -25 ° C to about 100 ° C can be mentioned, and typically -10 ° C to 25 ° C can be mentioned. The reaction time can vary depending on other reaction conditions (for example, reaction substrate, reaction solvent, reaction temperature), and examples include several minutes to several days, and typically include several hours to overnight.

(Composition of the present invention)
The composition of the present invention comprises:
(A) a compound represented by the above formula (I) (hereinafter referred to as compound (A) as appropriate), and (B) one or more compounds containing at least two or more ethylenically unsaturated groups (hereinafter referred to as appropriate). (Referred to as compound (B))
including.
In addition, compound (B) is included as a film-forming component for forming a coating film component by polymerization reaction with the acryloyl group or methacryloyl group in compound (A) represented by formula (I).

  In the composition of the present invention, the compound (A) is included as a hydrophilic component, and the compound represented by the formula (I) may be a single compound or a combination of two or more kinds of compounds. May be.

  In the present specification, the compound (B) contains at least two or more ethylenically unsaturated groups in order to form a coating film component by polymerizing with the acryloyl group or methacryloyl group in the compound (A). It is necessary to be a compound of more than species. The ethylenically unsaturated group is a group selected from an acryloyl group, a methacryloyl group, or a vinyl group, preferably an acryloyl group or a methacryloyl group, and more preferably an acryloyl group.

  Examples of the compound (B) include, for example, a (meth) acrylate monomer (oligomer) containing an ethylenically unsaturated group in the molecule, a urethane (meth) acrylate monomer (oligomer) which is a urethane modification product thereof, and an epoxy modification product thereof. Although one or more types of compounds (for example, 2 types, 3 types, 4 types) chosen from the epoxy (meth) acrylate monomer (oligomer) which are these are mentioned, It is not limited to these. Compound (B) can be obtained commercially or can be produced using generally known production methods.

Typical examples of the compound (B) include polyfunctional aromatic urethane acrylates and polyfunctional aliphatic acrylates, where “polyfunctional” means, for example, ethoxylated o-phenylphenol, methoxypolyethylene glycol, Phenoxypolyethylene glycol, isostearyl, fluorene bisphenyl, 2-hydroxy-3-acryloyloxypropyl, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, tricyclodecane dimethanol, 1,6-hexanediol, 1,9- Nonanediol, 1,10-decanediol, dipropylene glycol, tripropylene glycol, pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, ethoxylated group Means serine, propoxylated ethoxylated bisphenol A, ethoxylated bisphenol A, propoxylated bisphenol A, ethoxylated isocyanuric acid, in that it contains one or more functional groups selected from ε- caprolactone-modified isocyanurate. Specific examples of the compound (B) include propoxylated ethoxylated bisphenol A diacrylate, 1,6-hexanediol diacrylate, ethoxylated isocyanuric acid triacrylate, ethoxylated glycerin triacrylate, ε-caprolactone modified tris- (2- Examples include, but are not limited to, (acryloxyethyl) isocyanurate, oligourethane acrylate, phenyl glycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer, epoxidized glycerin triacrylate, cresol novolac type epoxy acrylate, and the like. You may use these compounds in combination of 2 or more types (for example, 2 types, 3 types, 4 types).
These are NSC-7350 (manufactured by Nippon Seika Co., Ltd.), NSC-7355 (manufactured by Nippon Seika Co., Ltd.), EBECRYL220 (manufactured by Daicel Ornex), GX-8801A (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), A-GLY- It can be obtained and used as 9E (manufactured by Shin-Nakamura Chemical Co., Ltd.), A9300-1CL (manufactured by Shin-Nakamura Industrial Co., Ltd.) or the like.

  The composition of the present invention contains the compound (A) in a weight ratio with respect to the compound (B), usually within a range of 0.01 wt% to 30 wt%, preferably within a range of 0.05 wt% to 10 wt%. More preferably, it is contained within the range of 0.5 wt% to 5 wt%.

The composition of the present invention further includes a compound (C) as a polymerizable compound containing one ethylenically unsaturated group in the molecule other than the compound (B) in addition to the compound (A) and the compound (B). You may go out. The selection and addition amount of the compound (C) can be appropriately determined according to the properties required for the obtained polymer. Examples of the compound (C) include compounds having volatility. The volatile compound refers to a compound having a boiling point range of 260 ° C. or lower or a saturated vapor pressure of 10 ⁻² kPa or higher at 25 ° C. in the classification of volatile organic compounds by WHO.

  If necessary, the composition of the present invention may optionally contain an antioxidant, a leveling agent, a dye, and a bond as long as the hydrophilicity, antifouling property, or antifogging property of the composition of the present invention is not impaired. It may contain generally well-known additives for resin compositions, such as an agent.

(Coating film and laminate)
The composition of the present invention comprises a compound (A) component and a compound (compounds) contained in the composition by irradiating light, applying heat (for example, hot air), or by performing both. By subjecting the component B) to a polymerization reaction, a coating film component can be formed on the surface of the substrate.

  In order to polymerize the composition of the present invention, the composition of the present invention is optionally a polymerization initiator and radical generator as long as the hydrophilicity, antifouling property, or antifogging property of the composition of the present invention is not impaired. , Catalysts, polymerization accelerators, ultraviolet absorbers, infrared absorbers, radical scavengers, polymerization inhibitors, light stabilizers (for example, hindered amine light stabilizers (HALS)) and the like for generally well-known polymerization reactions An additive may be included.

  When the composition of the present invention is copolymerized with radiation, for example, ultraviolet rays, a known photopolymerization initiator such as a photo radical polymerization initiator, a photo cationic polymerization initiator, or a photo anion polymerization initiator can be used. A radical polymerization agent is preferred.

  Specific examples of the photo radical polymerization agent include Irgacure 651 (manufactured by BASF), Irgacure 184 (manufactured by the company), Irgacure 500 (manufactured by the company), Irgacure 2959 (manufactured by the company), and Irgacure 127 (manufactured by the company). IRGACURE 907 (manufactured by the company), IRGACURE 369 (manufactured by the company), IRGACURE 1300 (manufactured by the company), IRGACURE 819 (manufactured by the company), IRGACURE 1800 (manufactured by the company), IRGACURE OXE01 (manufactured by the company), Irga Examples include, but are not limited to, Cure OXE02 (manufactured by the company), Darocur 1173 (manufactured by the company), Darocur TPO (manufactured by the company), Darocur 4265 (manufactured by the company), and the like.

  The amount of the radical photopolymerization agent used is usually in the range of 0.1 to 20 parts by weight, preferably 100 parts by weight in total with the compound (A), the compound (B) and the compound (C), preferably It is in the range of 0.5 to 10 parts by weight, more preferably in the range of 1 to 5 parts by weight.

  In the composition of the present invention, a solvent may be added as necessary in order to improve the wettability to the substrate and adjust the viscosity of the paint. Specifically, alcohol (for example, methanol, ethanol, isopropanol, n-butanol, methoxyethanol, 1-methoxy-2-propanol, glycerin), ketone (for example, acetone), polar aprotic solvent (for example, dimethylformamide) (DMF)), water and the like, and a mixed solvent of two or more of these solvents may be used.

  The polymerization reaction of the present invention may be performed in an air atmosphere, but may be performed in an inert gas (for example, nitrogen, argon) atmosphere from the viewpoint of reaction time and reaction efficiency.

  When the polymerization reaction is performed by light irradiation, the reaction temperature is usually 10 to 150 ° C., preferably 30 to 80 ° C., depending on the reaction conditions such as the reaction substrate and the polymerization means. The reaction time is usually 1 second to 30 minutes (minutes or hours), preferably 1 second to 5 minutes (minutes or hours).

  When the polymerization reaction is carried out by heat, the reaction temperature is usually from room temperature to 300 ° C., preferably from 30 to 80 ° C., depending on the reaction conditions such as reaction substrate and polymerization means. The reaction time is usually 1 to 180 minutes (minutes or hours), preferably 2 to 120 (minutes or hours). Further, a radical generator (for example, organic peroxide) may be added to the reaction system.

  When performing both operations of light irradiation and heating for the polymerization reaction, after performing one operation, the other operation can be performed, and either operation may be performed first.

Examples of the radiation include visible light of 400 to 800 nm, ultraviolet light of 400 nm or less, and an electron beam, and ultraviolet light that can be easily and quickly performed is preferable. Examples of the ultraviolet light source include, but are not limited to, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a gallium lamp, an ultraviolet laser, and sunlight. Irradiation may be performed in an air atmosphere or an inert gas atmosphere such as nitrogen or argon.
The irradiation integrated light quantity is usually 100 to 5000 mJ, for example, 100 mJ, and may be further irradiated with 500 mJ.

  Examples of the method for applying the composition of the present invention to a substrate include generally known application methods, specifically brush coating, various coating methods (for example, spray coating, dip coating, spin coating) and the like. There are known methods.

  The thickness of the coating is usually applied to the surface of the base so that it is in the range of 0.1 to 300 μm, preferably in the range of 1 to 100 μm.

  In this specification, the term “base” means, for example, an inorganic material (eg, glass, silica, metal, metal oxide, etc.), an organic material (eg, polymethyl methacrylate, polyethylene terephthalate, polycarbonate, polyurethane, polyethylene, polypropylene). , Polystyrene, epoxy resins, or films thereof, or paper, pulp), and combinations of these inorganic and organic materials.

The laminate of the present invention is
(1) The process of apply | coating the composition of this invention to a base material,
(2) A step of forming a coating film by irradiating the composition with light or applying heat or both.
By the method including the above, it is possible to produce a laminate comprising a coating film and a base material layer, and the coating film is formed on at least one surface of the base material layer.

  As used herein, the term “laminate” refers to glass, display material surfaces (eg, displays, television films), or water-related articles (eg, bathroom wall materials, bathroom floor materials, wash mirrors, washstands, kitchen counters) , Toilet bowl, toilet seat) and the like.

(Use)
The compound of the present invention or a composition containing the compound can be used as an antifouling agent. Moreover, the compound of this invention or the composition containing this compound can be used as an antifogging agent.

  In addition, since the coating film comprising the composition of the present invention exhibits antifouling properties and / or antifogging properties, the laminated film on which the coating film is formed is variously laminated as an antifouling film, an antifogging film or the like. It can be applied to articles such as the body.

  The coating film comprising the composition of the present invention has a water contact angle of 70 ° or less, preferably 40 ° or less. Therefore, the coating film exhibits good hydrophilicity.

Hereinafter, the present invention will be described more specifically with reference to production examples and test examples of compounds, compositions and the like, but the present invention is not limited to these examples. The compound was identified by analysis of various spectroscopic analyses. Specifically, in NMR, a nuclear magnetic resonance ( ¹ H-NMR) having a resonance frequency of 300 MHz was used. The symbols used in NMR are as follows: s is a single line, d is a double line, dd is a double double line, t is a triple line, td is a triple double line, q is a quadruple line, quin is a five line A double line, sept is a seven-fold line, m is a multiple line, br is wide, brs is a wide single line, brd is a wide double line, brt is a wide triple line, and J is a coupling constant.

Production examples of the compound of the present invention will be shown.
Example 1
Synthesis of 4-methacryloxyethyl trimellitic anhydride (4-META) 42.0 g (199.5 mmol) of trimellitic anhydride chloride, 170.0 g of toluene, and 15.8 g of pyridine were added to a nitrogen-substituted 300 mL four-necked flask. (199.7 mmol) was added and dissolved, and then cooled to 5 to 15 ° C. Next, 26.0 g (199.8 mmol) of 2-hydroxyethyl methacrylate was slowly added dropwise so as not to exceed 15 ° C. After stirring for 4 hours, the produced pyridine hydrochloride was filtered off, and 60 g of heptane was added to the filtrate. The solution was heated to 75 ° C. and dissolved, then cooled to 5 ° C., and the precipitated crystals were separated by filtration. The obtained crystals were recrystallized from 78.0 g of ethyl acetate and dried in vacuo at 50 ° C. for 12 hours to obtain a white powder (yield 71%).
¹ H NMR (300 MHz, CDCl 3) 8.65-8.69 (ds, 1H), 8.51-8.62 (dd, 1H), 8.09-8.22 (d, 1H), 6.09 -6.15 (s, 1H), 5.57-5.64 (s, 1H), 4.43-4.70 (td, 4H), 1.89-2.01 (s, 3H)

(Example 2)
Preparation of 4-methacryloxyethyl trimellitic acid monosodium salt (4-MET 1Na salt) (present compound 1) 4-Methacryloxyethyl trimellitic anhydride (4-META) to 5.1 g (16.4 mmol) 39.8 g of water was added, and the mixture was stirred at 50 ° C. for 1 hour. After the completion of the reaction, 4.52 g of the lower layer which had been separated was taken out and dried by blowing at 40 ° C. for 12 hours to obtain 3.91 g of 4-methacryloxyethyl trimellitic acid (4-MET). Next, 5.04 g of water was added to and suspended in 0.5 g (1.55 mmol) of 4-MET obtained, and 62.0 mg (1.55 mmol) of sodium hydroxide was further added and dissolved, followed by stirring. Then, it filtered with the syringe filter and obtained 4.08 g of 4-MET 1Na salt 9.1% aqueous solution which is a hydrophilic material.
¹ H NMR (300 MHz, D ₂ O) 8.07-8.20 (ds, 1H), 7.86-7.98 (dd, 1H), 7.48-7.53 (d, 1H), 5 .92 (s, 1H), 5.50 (s, 1H), 4.36-4.50 (td, 4H), 1.56-1.74 (s, 3H)

(Example 3)
Preparation of 4-methacryloxyethyl trimellitic acid disodium salt (4-MET 2Na salt) (Compound 2 of the present invention) 4-methacryloxyethyl trimellitic acid (4-MET) 0.092 g (0.29 mmol) in water 0 .92 g was added and suspended, and further 23.2 mg (0.58 mmol) of sodium hydroxide was added and dissolved, followed by stirring. Then, it filtered with the syringe filter and obtained 0.85 g of 4-MET 2Na salt 9.1% aqueous solution which is a hydrophilic material.
¹ H NMR (300 MHz, D ₂ O) 7.9-8.00 (ds, 1H), 7.85-7.93 (dd, 1H), 7.36-7.40 (d, 1H), 5 .96-6.00 (s, 1H), 5.53-5.54 (s, 1H), 4.39-4.51 (td, 4H), 1.72-1.77 (s, 3H)

Example 4
Synthesis of 4-methacryloyloxyethyl-1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride (4-MECHA) 1,2,4-cyclohexanetricarboxylic acid-1, 2-Anhydride-4-chloride (18.3 g, 84.5 mmol) and toluene (35.8 g) were added and dissolved to obtain solution A. Next, in another container, 1.0 g (84.5 mmol) of 2-hydroxyethyl methacrylate 1, 36.6 g of toluene, and 6.7 g (84.7 mmol) of pyridine were added and dissolved to obtain a solution B. Next, A liquid was cooled to 0-5 degreeC, and B liquid was dripped slowly into A liquid so that 10 degreeC might not be exceeded. After stirring for 4 hours, the produced pyridine hydrochloride was filtered off, and 3.9 mg of methoquinone was added to the filtrate. Concentration was carried out at 45 ° C. under reduced pressure, followed by vacuum drying at 45 ° C. for 12 hours to obtain a slightly yellow liquid (yield 87%).
¹ H NMR (300 MHz, CDCl 3) 6.11-6.12 (s, 1H), 5.59-5.62 (s, 1H), 4.32-4.37 (s, 4H), 3.11 -3.40 (m, 2H), 2.01-2.52 (m, 5H) 1.89-1.94 (s, 3H), 1.58-1.68 (m, 2H)

(Example 5)
4-Methacryloyloxyethyl-1,2,4-cyclohexanetricarboxylic acid monosodium salt (4-MECH 1Na salt) (present compound 3) 4-Methacryloyloxyethyl-1,2,4-cyclohexanetricarboxylic acid 30.9 g of water was added to 10.6 g (34.2 mmol) of -1,2-anhydride (4-MECHA), and the mixture was stirred at 50 ° C. for 1 hour. 8.52 g of the lower layer separated after completion of the reaction was extracted, and blown and dried at 40 ° C. for 12 hours to obtain 8.29 g of 4-methacryloyloxyethyl-1,2,4-cyclohexanetricarboxylic acid (4-MECH). . Next, 4.66 g of water was added to and suspended in 0.47 g (1.42 mmol) of 4-MECH obtained, and 56.8 mg (1.42 mmol) of sodium hydroxide was further added and dissolved, followed by stirring. Then, it filtered with the syringe filter and obtained 4.25 g of 4-MECH 1Na salt 9.1% aqueous solution which is a hydrophilic material.
¹ H NMR (300 MHz, D ₂ O) 5.96 (s, 1H), 5.57 (s, 1H), 4.27 (s, 4H), 2.90-2.95 (m, 1H), 2.29-2.42 (m, 2H), 1.96-2.16 (m, 1H), 1.70-1.80 (s, 3H), 1.17-1.81 (m, 5H) )

(Example 6)
Preparation of 4-methacryloyloxyethyl-1,2,4-cyclohexanetricarboxylic acid disodium salt (4-MECH 2Na salt) (present compound 4) 0.92 g of water was added to 0.092 g (0.28 mmol) of 4-MECH. The suspension was added, and 22.4 mg (0.56 mmol) of sodium hydroxide was further added and dissolved, followed by stirring. Then, it filtered with the syringe filter and obtained 0.70 g of 4-MECH2Na salt 9.1% aqueous solution which is a hydrophilic material.
¹ H NMR (300 MHz, D ₂ O) 5.96 (s, 1H), 5.57 (s, 1H), 4.21-4.30 (s, 4H), 2.79-2.85 (m , 1H), 2.22-2.31 (m, 2H), 1.93-2.14 (m, 1H), 1.68-1.81 (s, 3H), 1.13-1.99. (M, 5H)

Next, production examples of the composition of the present invention are shown.
(Example 7)
Production of Composition Containing 4-MET 1Na Salt (Composition 1 of the Present Invention) 2.1 g of Compound NSC-7350 (manufactured by Nippon Seika Co., Ltd.) having an acryloyl group as a hydrophilic component (A) 4-MET 1Na salt (present) Invention compound 1) Add 0.55 g of 9.1% aqueous solution, add 2.80 g of 1-methoxy-2-propanol as a solvent, 0.064 g of DAROCURE1173 (manufactured by BASF) as a photopolymerization initiator, mix and dissolve, A composition of the invention was prepared.

(Example 8)
Preparation of Composition Containing 4-MET 2Na Salt (Invention Composition 2) According to the method described in Example 7, 4-MET 1Na salt was replaced with 4-MET 2Na salt to prepare the composition of the present invention. .

Example 9
Preparation of Composition Containing 4-MECH 1Na Salt (Invention Composition 3) According to the method described in Example 7, 4-MET 1Na salt was replaced with 4-MECH 1Na salt to prepare the composition of the present invention. .

(Example 10)
Preparation of Composition Containing 4-MECH 2Na Salt (Invention Composition 4) According to the method described in Example 7, 4-MET 1Na salt was replaced with 4-MECH 2Na salt to prepare the composition of the present invention. .

(Comparative Example 1)
Production of Composition Containing 4-META (Comparative Composition 1) According to the method described in Example 7, a 9.1% aqueous solution of 4-MET 1Na salt 0.55 g was replaced with 0.05 g of 4-META. One composition was prepared.

(Comparative Example 2)
Preparation of Composition Containing 4-MET (Comparative Composition 2) According to the method described in Example 7, a 9.1% aqueous solution of 4-MET 1Na salt, 0.55 g was replaced with 0.05 g of 4-MET, and Comparative Example Two compositions were prepared.

(Comparative Example 3)
Preparation of Composition Containing 4-MECHA (Comparative Composition 3) According to the method described in Example 7, the composition of Comparative Example 3 was replaced with 4-METCHA 9.1% aqueous solution 9.1% aqueous solution 0.55 g. A product was prepared.

(Comparative Example 4)
Preparation of Composition Containing 4-MECH (Comparative Composition 4) According to the method described in Example 7, the composition of Comparative Example 4 was changed by replacing 4-METH with 0.55 g of 4-MET 1Na salt 9.1% aqueous solution. A product was prepared.

Next, a film forming method will be described.
(Example 11)
The coating compositions obtained in Examples 7 to 10 and Comparative Examples 1 to 4 were applied to the surface of a polyethylene terephthalate (PET) film having a thickness of 188 μm and subjected to an easy adhesion treatment with a bar coater # 8. The coated PET film was allowed to stand in a warm air oven at a temperature of 80 ° C. for a drying time of 2 minutes, and then irradiated with ultraviolet rays having an integrated light amount of 500 mJ to form a hydrophilic coating film.

表１（続き）

本発明組成物１〜２の塗膜は、本発明組成物３〜４及び比較組成物１〜４の塗膜と比較して優れた防汚性を示した。 Furthermore, a test example is shown.
(Test Example 1)
Antifouling test First, the results of the antifouling test are shown.
The antifouling property test of the coating film manufactured in Examples 7-10 and Comparative Examples 1-4 was done. Specifically, after marking using an oil-based marker “Mackey Extra Fine” (manufactured by ZEBRA), a mark that can be wiped off by dropping distilled water on the surface was marked with ◯, and a mark that could not be wiped was marked with x.
The measurement results comparing the coating film of the present invention and the coating film of the comparative example are shown in Table 1 below.
Table 1. Antifouling test results

Table 1 (continued)

The coating film of this invention composition 1-2 showed the antifouling property outstanding compared with the coating film of this invention composition 3-4 and comparative composition 1-4.

Next, the results of a hydrophilicity test and an antifogging property test are shown.
(Test Example 2)
Hydrophilic test As a hydrophilic test, the water contact angle was measured.
Specifically, a water contact angle device DMs-401 manufactured by Kyowa Interface Science Co., Ltd. was used, and a static contact angle 20 seconds after dropping a water droplet of 1 μL at room temperature was measured by the θ / 2 method. The measurement was performed at three locations after forming the hydrophilic coating film, and the average was taken as the value of the contact angle.

表２（続き）

本発明組成物１〜２の塗膜は、いずれの場合でも２０°以下の水接触角を示した。
本発明組成物１〜２由来の塗膜は、本発明組成物３〜４及び比較組成物１〜４由来の塗膜と比較して優れた親水性および防曇性を示した。 (Test Example 3)
Anti-fogging test In the anti-fogging test, the surface on which the hydrophilic coating film was formed was vertically applied to steam at 50 ° C, and it was visually observed whether it was cloudy or not cloudy. The case where it did not become cloudy for 5 seconds or more was marked with ◯, and the case where cloudy occurred was marked with ×.
The measurement results comparing the coating film of the present invention and the coating film of the comparative example are shown in Table 2 below.
Table 2. Results of hydrophilicity test and antifogging test

Table 2 (continued)

The coating films of the present compositions 1-2 showed a water contact angle of 20 ° or less in any case.
The coating films derived from the compositions 1 to 2 of the present invention exhibited excellent hydrophilicity and antifogging properties as compared with the coating compositions derived from the compositions 3 to 4 of the present invention and the comparative compositions 1 to 4.

  According to the present invention, a (meth) acrylate compound having two anionic hydrophilic groups in one molecule, which is excellent in hydrophilicity, antifouling property, or antifogging property, can be obtained. In addition, a coating film produced from the (meth) acrylate compound having these functions is useful as a surface of a display material such as glass or a display, or as a laminated film for water-related articles, and has high industrial utility value. .

Claims (18)

Formula (I):

[Wherein R ₁ represents hydrogen or a methyl group; R ₂ represents an anionic hydrophilic group; R ₃ represents a linear or branched aliphatic hydrocarbon group; X represents hydrogen or an alkali metal ion; R represents an aromatic cyclic group or an aliphatic cyclic group. ]
A compound represented by The compound according to claim 1, wherein the anionic hydrophilic group is at least one group selected from CO ₂ ⁻ and SO ₃ ^— . The compound according to claim 1, wherein the anionic hydrophilic group is CO ₂ ^— . The compound according to any one of claims 1 to 3, wherein R ₁ is a methyl group. The compound according to any one of claims 1 to 4, wherein R ₃ is an ethylene group. R is the formula (II):

The compound of any one of Claims 1-5 shown by these.   7. A compound according to any one of claims 1 to 6, wherein at least one X is an alkali metal ion. formula:

[Wherein R ₁ represents hydrogen or a methyl group; and X represents hydrogen or an alkali metal ion, and at least one is an alkali metal ion]
The compound of any one of Claims 1-7 shown by these. (A) the compound according to any one of claims 1 to 8, and (B) one or more compounds containing at least two or more ethylenically unsaturated groups,
A composition comprising   The composition of Claim 9 which contains this compound (A) by 0.01 wt%-30 wt% by weight ratio with respect to this compound (B).   A coating film comprising the composition according to any one of claims 9 to 10 cured on a substrate.   A laminate comprising the coating film according to claim 11 and a base material layer, wherein the coating film is formed on at least one surface of the base material layer.   The laminate according to claim 12, which is a water-borne article.   An antifouling agent comprising the compound according to any one of claims 1 to 8 or the composition according to any one of claims 9 to 10.   An antifogging agent comprising the compound according to any one of claims 1 to 8 or the composition according to any one of claims 9 to 10. (1) Applying the composition of any one of claims 9 to 10 to a substrate, and (2) irradiating the composition with light or applying heat, or both The manufacturing method of the laminated body characterized by including the process to perform.   The process according to claim 16, wherein in step (2) of claim 16, a coating film is formed by irradiating light, applying heat, or both. Formula (I) according to claim 1:

[Wherein R ₁ , R ₂ , R ₃ , R and X are as defined in claim 1]
A process for producing a compound represented by
Formula (IV):

[Wherein R is as defined above, and R ₂ ^′ represents a portion of an anionic hydrophilic group]
A halide compound represented by formula (V):

[Wherein R ₁ and R ₃ are as defined above]
In the presence of a polymerization inhibitor, the reaction is carried out together with the (meth) acrylate compound represented by the formula (II) and a deoxidizer, and then selected from alkali metal hydroxides, carbonates or bicarbonates to be the X source. Reacting with a compound from an X source to obtain a compound of formula (I) wherein X is an alkali metal ion.