TWI774748B - (meth)acrylamide compound containing anionic hydrophilic group, and coating composition comprising the same - Google Patents

Abstract

The present invention provides a novel acrylamide compound containing anionic hydrophilic group, which has an excellent durability under acidic and/or alkaline condition and also has an excellent antifouling property and/or antifogging property, said acrylamide compound being represented by formula (I): ; and a preparation method for the compound; as well as a composition comprising the compound; a coating film comprising the composition; a layered product in which the coating film is formed; and a preparation method for the layered product.

Description

(Meth)acrylamide compound containing anionic hydrophilic group and coating composition containing the same

The present invention relates to a novel (meth)acrylamide compound containing an anionic hydrophilic group and a coating composition containing the compound. Specifically, it relates to an anionic hydrophilic group-containing (meth)acrylamide compound having excellent hydrophilicity, antifouling properties and/or antifogging properties, a method for producing the compound, a composition containing the compound, and a A coating film of a composition, a laminate containing the coating film, and a method for producing the laminate.

To date, several hydrophilic coatings are known. For example, there are reports of hydrophilic paints formed from compounds having (meth)acrylate groups and acrylate resins, and reports of the hydrophilic paints exhibiting antifouling properties, antifogging properties, and the like (Patent Documents 1 and 2) .

However, in general, compounds having a (meth)acrylate group have a problem of poor durability against acidity or alkalinity due to the presence of the ester bond. Therefore, a coating film having durability against acidity or alkalinity may be required.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2007/064003 Pamphlet

[Patent Document 2] Japanese Patent Laid-Open No. 2014-198754

As a result of intensive research by the present inventors, it was found that the (meth)acrylamide compound containing an anionic hydrophilic group has durability against acidity or alkalinity. In addition, the anionic hydrophilic group-containing (meth)acrylamide compound was also found to have hydrophilicity and antifouling properties and/or antifogging properties. Therefore, the present invention provides a novel anionic hydrophilic group-containing (meth)acrylamide compound represented by formula (I) and a method for producing the compound. Furthermore, the present invention also provides a composition containing the compound, a coating film containing the composition, a laminate having the coating film formed thereon, and a method for producing the laminate. In particular, when the (meth)acrylamide compound (meth)acrylamide compound (compound (A)) containing an anionic hydrophilic group represented by the following formula (I) of the present invention and one or more ethylenically unsaturated groups containing at least two or more are combined. When the compound (compound (B)) was polymerized to prepare a composition, it was found that the properties of the composition (such as hydrophilicity, antifouling, antifogging, etc.) ) is more excellent. In addition, it was also found that the composition obtained by mixing the acrylate group-containing fluorine compound with the composition obtained above has good oil repellency.

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

(compound)

[式中，R₁為氫原子或甲基，R₂為陰離子性親水基，X為氫原子、鹼金屬離子、鹼土金屬離子或四級銨型離子，p為1或2，q為0或1，惟，p為1時q為1，p為2時q為0，R為式(II)表示之直鏈或分枝之脂肪族烴基，

[1] A compound represented by formula (I):

[In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is an anionic hydrophilic group, X is a hydrogen atom, an alkali metal ion, an alkaline earth metal ion or a quaternary ammonium ion, p is 1 or 2, and q is 0 or 1. However, when p is 1, q is 1, when p is 2, q is 0, and R is a linear or branched aliphatic hydrocarbon group represented by formula (II),

式中，m為0至12之整數，而且，R₂及X係如上述定義， A存在2個以上時，該A可存在於相同或不同之碳原子上，而且，o為0至6之整數]。 The aliphatic hydrocarbon group may contain at least one group selected from an aliphatic carbocyclic group, an aromatic carbocyclic group, an ether group or an ester group, n is an integer from 1 to 12, and A is each independently represented by formula (III) base,

In the formula, m is an integer from 0 to 12, and R ₂ and X are as defined above, when there are more than 2 A, the A may exist on the same or different carbon atoms, and o is 0 to 6. integer].

[2] The compound according to [1], wherein the anionic hydrophilic group is at least one group selected from CO ₂ ^- , SO ₃ ^- , PO ₄ ^2- or HPO ₄ ^- .

[3] The compound according to [1], wherein the anionic hydrophilic group is SO ₃ ⁻ .

[4] The compound according to any one of [1] to [3], wherein o is 0, and R is a group represented by formula (II-1) or (II-2):

[5] The compound according to any one of [1] to [4], wherein n is an integer of 2 to 8.

[5-1] The compound according to any one of [1] to [4], wherein n is an integer of 2 to 6.

[6] The compound according to any one of [1] to [5], wherein p is 1 and q is 1.

[7] The compound according to [1], wherein the compound is selected from the group consisting of (meth)acrylamide methanesulfonate, (meth)acrylamide ethanesulfonate, and (meth)acrylamide propanesulfonate, (meth)acrylamidobutanesulfonate, (meth)acrylamidopentanesulfonate, (meth)acrylamidohexanesulfonate, (meth)acrylamidoheptsulfonate acid salt, (meth)acrylamidooctanesulfonate, (meth)acrylamidononanesulfonate, (meth)acrylamidodecanesulfonate, (meth)acrylamidododecanesulfonate The group consisting of acid salt, (meth)acrylamido undecanesulfonate and (meth)acrylamidobenzenesulfonate.

(composition)

[8] A composition comprising (A) the compound described in any one of [1] to [7], and B) one or more compounds containing at least two or more ethylenically unsaturated groups.

[9] The composition according to [8], wherein the content of the compound (A) relative to the compound (B) is 0.01 wt % to 30 wt % in weight ratio.

[10] The composition according to [8] or [9], wherein the compound (B) is a urethane (meth)acrylate monomer (oligomer).

[11] The composition according to any one of [8] to [10], further comprising a fluorine-containing (meth)acrylate compound.

[12] The composition according to [11], wherein the fluorine-containing (meth)acrylate compound is selected from the group consisting of (per)fluoroalkyl (meth)acrylate, (per)fluoroether (methyl) ) acrylate or fluorine-containing urethane (meth)acrylate.

[12-1] The composition according to item [11] or [12], wherein the content of the fluorine-containing (meth)acrylate compound is 0.05 wt % relative to the composition. to 5wt%.

(Manufacturing method of composition)

[13] A method for producing the composition according to any one of [8] to [12], comprising (A) the compound according to any one of [1] to [7] and (B) 1 One or more compounds containing at least two or more ethylenically unsaturated groups are reacted in the presence of a cationic polymerization catalyst as a polymerization initiating catalyst.

[13-1] The production method according to [13], wherein the cationic polymerization catalyst is triphenyl perylene tetrafluoroborate.

(coating films, laminates, etc.)

[14] A coating film comprising the composition according to any one of [8] to [12] hardened on a substrate.

[15] A laminate comprising the coating film described in [14] and a base material layer, wherein the coating film is formed on at least one side of the base material layer.

[16] The layered product according to [15], wherein the layered product is a water-touching article.

(use)

[17] An antifouling agent comprising the compound of any one of [1] to [7] or the composition of any one of [8] to [12].

[18] An antifogging agent comprising the compound of any one of [1] to [7] or the composition of any one of [8] to [12].

(Manufacturing method of laminated body)

[19] A method for producing a layered product, comprising (1) applying the composition described in any one of [8] to [12] on a substrate, and (2) subjecting the composition to light step of irradiating, heating, or both.

[19-2] The production method according to [19], wherein in step (2), a coating film is formed by applying light irradiation, heating, or both.

(Production method of compound)

該製造方法包含：將式：

表示之(甲基)丙烯醯基鹵化物化合物或式：

表示之(甲基)丙烯醯酸酐化合物與式：H₂N-R-R₂H [20] A method for producing the compound represented by the formula (I) described in [1],

The manufacturing method comprises: converting the formula:

The (meth)acryloyl halide compound or formula represented by:

The (meth)acrylic anhydride compound represented by the formula: H ₂ NRR ₂ H

表示之胺化合物，和選自氨或有機胺類之X供給源之化合物及選自鹼金屬或鹼土金屬之氫氧化物、碳酸鹽或碳酸氫鹽之X供給源之化合物一起，適當地在聚合抑制劑的存在下進行反應，得到X為四級銨型離子之式(I)表示之化合物；及於期望得到X為鹼金屬或鹼土金屬之離子之式(I)表示之化合物時，將所得到之X為四級銨型離子之式(I)表示 之化合物與選自鹼金屬或鹼土金屬之氫氧化物、碳酸鹽或碳酸氫鹽之X供給源之化合物進行反應，得到X為鹼金屬或鹼土金屬之離子之式(I)表示之化合物。 or

The amine compound represented, together with the compound selected from the X supply source of ammonia or organic amines and the compound selected from the X supply source of alkali metal or alkaline earth metal hydroxide, carbonate or bicarbonate, is suitably polymerized. The reaction is carried out in the presence of an inhibitor to obtain a compound represented by formula (I) where X is a quaternary ammonium ion; and when it is desired to obtain a compound represented by formula (I) where X is an ion of an alkali metal or an alkaline earth metal, the The compound represented by the formula (I) in which the obtained X is a quaternary ammonium ion is reacted with a compound selected from the X supply source of alkali metal or alkaline earth metal hydroxide, carbonate or bicarbonate to obtain X as an alkali metal Or a compound represented by the formula (I) of an ion of an alkaline earth metal.

The anionic hydrophilic group-containing (meth)acrylamide compound of the present invention is hydrophilic and has excellent durability (stability) under acidic and/or alkaline conditions. In addition, the compound, the composition containing the compound, or the coating film containing the composition can be used for antifouling and/or antifogging. In addition, by mixing the acrylate group-containing fluorine compound in the above-mentioned composition, the effect of easily floating and easy flow of dirt can be exhibited.

Hereinafter, the present invention will be described in more detail.

(definition)

Hereinafter, definitions of terms used in this specification and the scope of the claims are shown. Unless otherwise stated, the original definition indicated by a base or term in this specification applies to the base or term in this specification, either individually or as part of another base.

(Compound of the present invention)

[式中，R₁為氫原子或甲基、R₂為陰離子性親水基、X為氫原子、鹼金屬離子、鹼土金屬離子或四級銨型離子、p為1或2、q為0或1、惟，p為1時q為1,p為2時q為0、R為式(II)表示之直鏈或分枝之脂肪族烴基

As an aspect of the present invention, the present invention provides a compound represented by formula (I)

[In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is an anionic hydrophilic group, X is a hydrogen atom, an alkali metal ion, an alkaline earth metal ion or a quaternary ammonium ion, p is 1 or 2, and q is 0 or 1. However, when p is 1, q is 1, when p is 2, q is 0, and R is a linear or branched aliphatic hydrocarbon group represented by formula (II).

(式中，m為0至12之整數R₂及X係如上述定義) The aliphatic hydrocarbon group contains at least one group selected from aliphatic carbocyclic group, aromatic carbocyclic group, ether group or ester group, n is an integer from 1 to 12, and A is each independently represented by formula (III) base,

(in the formula, m is an integer from 0 to 12 R ₂ and X are as defined above)

When two or more A's are present, the A's may be present on the same or different carbon atoms, and o is an integer of 0 to 6].

In the formula (I), the R ₁ group includes a hydrogen atom and a methyl group. When the R ₁ group is a hydrogen atom, it contains an acryl moiety, and when the R ₁ group is a methyl group, it contains a methacryloyl moiety.

In formula (I), the term "anionic hydrophilic group" as R ₂ group refers to an atomic group which has a negative charge when dissolved in water and forms a weak bond with a water molecule through hydrogen bonding or the like. The presence of this anionic hydrophilic group prevents components that constitute scales such as silicon dioxide, sodium, and potassium in tap water from adhering to the surface of the hydrophilic coating film, and even if it adheres, it can be easily removed because it is not a strong adhesion. , can maintain the hydrophilicity of the coating film for a long time. Specific examples of the anionic hydrophilic group include at least one group selected from CO ₂ ^- , SO ₃ ^- , PO ₄ ^2- , and HPO ₄ ^- , but are not limited to these groups. In one embodiment, the anionic hydrophilic group is preferably SO ₃ ⁻ .

In formula (I), the X group can include hydrogen atom, alkali metal ion, alkaline earth metal ion and quaternary ammonium ion, but it is not limited thereto. From the viewpoint of easily maintaining the hydrophilicity of the anionic hydrophilic group, the above R ₂ group is preferably a counter cation, and examples thereof include alkali metal ions (eg, sodium ion, potassium ion), alkaline earth metal ions (eg, calcium ions) ions) and quaternary ammonium ions (eg ammonium, triethylammonium, tetraethylammonium). Preferred are alkali metal ions or alkaline earth metal ions, and more preferred are alkali metal ions.

The cationic system in the X group can be converted to the desired cation by a generally known cation exchange method (eg, using a cation exchange resin).

In the above formula (I), p is 1 or 2, and q is 0 or 1. However, when p is 1, q is 1 (the following formula I-1), and when p is 2, q is 0 (the following formula I-2).

More preferably, it is a compound represented by (Formula I-1) in which p is 1 and q is 1.

In the formula (I), the R group is a linear or branched aliphatic hydrocarbon group represented by the formula (II).

A straight-chain aliphatic hydrocarbon group is preferred. The term "straight-chain or branched aliphatic hydrocarbon group" may exemplify an alkyl group, an alkenyl group or an alkynyl group, preferably an alkyl group.

The term "alkyl" as used in this specification refers to a straight chain or branched saturated aliphatic hydrocarbon group. Examples include alkyl groups having 1 to 12 carbon atoms (that is, n is an integer of 1 to 12), alkyl groups having 1 to 8 carbon atoms, and alkyl groups having 1 to 6 carbon atoms. , an alkyl group having 2 to 8 carbon atoms or an alkyl group having 2 to 6 carbon atoms, but not limited to these. It is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 2 to 6 carbon atoms (that is, n is an integer of 2 to 6). Specifically, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl base and undecyl, etc.

The term "alkenyl" used in this specification refers to a straight-chain or branched unsaturated aliphatic hydrocarbon group having one or more double bonds. For example, an alkenyl group having 2 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms can be mentioned, but it is not limited thereto. More preferably, it is an alkenyl group having 2 to 6 carbon atoms. Specifically, vinyl, 1-propenyl, 2-butenyl, 2-pentenyl, 2-hexenyl, heptenyl, octenyl, nonenyl, decenyl, and undecenyl can be mentioned. Carbene, etc.

The term "alkynyl" used in this specification refers to a straight-chain or branched unsaturated aliphatic hydrocarbon group having one or more triple bonds. For example, an alkynyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 8 carbon atoms, or an alkynyl group having 2 to 6 carbon atoms can be mentioned, but it is not limited thereto. More preferably, it is an alkynyl group having 2 to 6 carbon atoms. Specifically, ethynyl, 1-propynyl, 2-butynyl, 2-pentynyl, 2-hexynyl, heptynyl, octynyl, nonynyl, decynyl, dodecynyl Carbynyl and undecylynyl, etc.

The aliphatic hydrocarbon group may contain at least one group selected from the group consisting of aliphatic carbocyclic group, aliphatic heterocyclic group, aromatic carbocyclic group, aromatic heterocyclic group, ether group or ester group, but is not limited to the Wait. For example, at least one or more groups selected from aliphatic carbocyclic group, aromatic carbocyclic group, ether group (-O-) or ester group (-CO ₂ -) may be contained, or an aliphatic carbocyclic group may be contained or an aromatic carbocyclic group.

Aliphatic carbocyclyl refers to a saturated or unsaturated non-aromatic carbocyclic ring. Examples include 4- to 9-membered monocyclic or polycyclic (eg, bicyclic) cycloalkyl groups, and specific examples include, but are not limited to, cyclopropyl, cyclohexyl, and the like.

Aliphatic heterocyclyl refers to a saturated or unsaturated aliphatic heterocycle containing 1 to 3 identical or different heteroatoms independently selected from the group consisting of oxygen, sulfur and nitrogen atoms within the ring. Examples include 4- to 9-membered monocyclic or polycyclic (for example, bicyclic) saturated or unsaturated aliphatic heterocycles, and specific examples include azetidinyl, oxetanyl, and pyrrolidine base, tetrahydrothienyl, tetrahydrofuranyl, tetrahydrothiazolyl, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, homomorpholinyl, tetrahydrothiopyranyl, tetrahydropyridine Langji, etc., however, are not limited to these.

Examples of aromatic carbocyclic groups refer to monocyclic, bicyclic or tricyclic aromatic carbocyclic groups of 6 to 14 members. Specific examples include, but are not limited to, phenyl, naphthyl, phenanthryl, anthracenyl, and the like. More preferred is, for example, a phenyl group.

Aromatic heterocyclic group refers to an aromatic heterocyclic ring containing 1 to 3 identical or different heteroatoms independently selected from the group consisting of oxygen atoms, sulfur atoms and nitrogen atoms in the ring. For example, a 5- to 8-membered aromatic heterocyclic ring is exemplified, preferably a 5- or 6-membered ring, and more preferably a 6-membered ring. Specific examples include, but are not limited to, pyrrolyl, furyl, thienyl, pyridyl, pyrimidinyl, and pyridazinyl. More preferred is, for example, pyridyl.

The aliphatic carbocyclic group or the aromatic carbocyclic group may be substituted with one or more (eg, 1 to 3, 1 to 2, or 1) substituents, and the substituents are at least one or more aliphatic groups selected from the above The group of aliphatic carbocyclic group, aliphatic heterocyclic group, aromatic carbocyclic group, aromatic heterocyclic group, ether group, ester group, and anionic hydrophilic group is preferably the above-mentioned anionic hydrophilic group.

，惟，不只限於此。 In the first embodiment, when the aliphatic hydrocarbon group represented by the formula (II) as the R group contains an aromatic carbocyclic group, the R group can be represented by, for example, the formula (II-2), the formula (II-2):

, but not limited to this.

(式中，R₂及X係如上述定義)，包含作為上述R₂X所記載之陰離子性親水基鹽之取代基。 In formula (II), A group is represented by formula (III)

(in the formula, R ₂ and X are as defined above), and include the substituents of the anionic hydrophilic group salts described as the above R ₂ X.

The number of carbon atoms m of the alkylene chain part of the linking group part of the main chain part of the aliphatic hydrocarbon group (-(CH ₂ ) _n -) and the linking group part of the anionic hydrophilic group salt R ₂ X is generally 0 to 10, more than Preferably it has 0 to 6 carbon atoms, more preferably 1 to 6 carbon atoms.

In formula (II), A is substituted on the carbon atom constituting the main chain part of the aliphatic hydrocarbon group, and when two or more A exists, the A may independently exist on the same or different carbon atoms.

In formula (II), o is generally an integer from 0 to 6, for example, an integer from 0 to 3, an integer from 0 to 2, or 0 or 1. Even if the compound of the present invention represented by the formula (I) does not contain an A group (that is, o is 0), the entire compound can ensure hydrophilicity, but by containing one or more A groups, it is possible to impart greater hydrophilicity.

Examples of representative compounds of the compound of the present invention include (meth)acrylamidomethane, (meth)acrylamidoethane, (meth)acrylamidopropane, (meth)acrylamidobutane, (meth)acrylamidobutane, Salts of anionic hydrophilic groups of meth)acrylamidopentane, (meth)acrylamidohexane and (meth)acrylamidobenzene are not limited to these. Specific examples include (meth)acrylamidomethanesulfonate, (meth)acrylamidoethanesulfonate, (meth)acrylamidopropanesulfonate, and (meth)acrylamidobutanesulfonic acid. salts, (meth)acrylamidopentanesulfonate, (meth)acrylamidohexanesulfonate and (meth)acrylamidobenzenesulfonate, but not limited to these.

(The production method of the compound of the present invention)

The (meth)acrylamide compound of the present invention is produced from various raw material compounds by organic synthesis reactions. An example of the manufacturing flow is shown below.

表示之(甲基)丙烯醯基鹵化物化合物(式中，R₁為氫原子時為丙烯醯基化合物，R₁為甲基時為甲基丙烯醯基化合物)(此處，鹵素原子可列舉例如氯原子、溴原子或碘原子)可由商業中購得，亦可藉由將例如(甲基)丙烯酸作為起始原料，與鹵化劑進行反應製造之。該鹵化劑可列舉於有機合成，從羧酸製造羧酸鹵化合物時一般所使用之劑，可列舉例如亞硫醯氯、草醯氯、磷醯氯、磺醯氯、三氯化磷及五氯化磷等，惟，不只限於該等。 First, the formula:

(meth)acryloyl halide compound represented by (in the formula, when R ₁ is a hydrogen atom, it is an acryl compound, and when R ₁ is a methyl group, it is a methacryloyl compound) (here, halogen atoms include For example, a chlorine atom, a bromine atom or an iodine atom) is commercially available, and can also be produced by reacting, for example, (meth)acrylic acid as a starting material with a halogenating agent. Examples of the halogenating agent include those generally used in organic synthesis and production of carboxylic acid halide compounds from carboxylic acids, such as thionyl chloride, oxalyl chloride, phosphonium chloride, sulfonyl chloride, phosphorus trichloride, and pentachloride. Phosphorus chloride, etc., however, are not limited to these.

表示之(甲基)丙烯醯酸酐化合物(式中，R₁為氫原子時為丙烯醯基化合物，R₁為甲基時為甲基丙烯醯基化合物)可由商業購得或根據作為酸酐製造法之一般習知之方法，將例如(甲基)丙烯酸之鹽(例如鈉鹽或鉀鹽等無機鹽)與上述(甲基)丙烯醯基鹵化物化合物進行反應，或是將(甲基)丙烯酸之間進行脫水反應而製造。 or formula:

The (meth)acryloic anhydride compound represented (in the formula, when R ₁ is a hydrogen atom, it is an acryloyl compound, and when R ₁ is a methyl group, it is a methacryloyl compound) can be purchased commercially or according to the production method as an acid anhydride The commonly known method is to react a salt of (meth)acrylic acid (such as an inorganic salt such as a sodium or potassium salt) with the above-mentioned (meth)acryloyl halide compound, or to react a salt of (meth)acrylic acid with the abovementioned (meth)acryloyl halide compound. It is produced by dehydration reaction in between.

Then, in another method, the formula: H ₂ NRR ₂ H

表示之含有陰離子性親水基R₂(例如磺酸基)之胺化合物可由商業購得或使用含有陰離子性親水基R₂之脂肪族烴化合物作為起始原料進行鹵化，得到鹵化脂肪族烴化合物，接著，與氨等進行反應，製造目的之胺化合物。此處，該胺化合物可為經1個HR₂-R基取代之1級胺，亦可為經2個HR₂-R取代之2級胺。 or

The indicated amine compound containing an anionic hydrophilic group R ₂ (such as a sulfonic acid group) can be obtained commercially or halogenated using an aliphatic hydrocarbon compound containing an anionic hydrophilic group R ₂ as a starting material to obtain a halogenated aliphatic hydrocarbon compound, Next, it reacts with ammonia etc., and manufactures the objective amine compound. Here, the amine compound may be a primary amine substituted with one HR ₂ -R group, or may be a secondary amine substituted with two HR ₂ -R groups.

The (meth)acryloyl halide compound prepared above and the amine compound containing an anionic hydrophilic group R ₂ and the X ₁ supply source (ammonia or organic amines) and the X ₂ supply source (alkali metal) are used as the X supply source. or alkaline earth metal hydroxide, etc.), and appropriately react in the presence of a polymerization inhibitor to produce a compound represented by formula (I) when X is a quaternary ammonium ion. Here, p is 1 or 2, and q is 0 or 1, but when p is 1, q is 1, and when p is 2, q is 0.

Next, when the compound of formula (I) in which X is an alkali metal or alkaline earth metal ion is expected, the compound represented by the _formula (I) when X is a quaternary ammonium ion and X as the X supply source can be supplied The source (hydroxide of alkali metal or alkaline earth metal) is reacted, and the compound of formula (I) in which X is an alkali metal or alkaline earth metal ion can be obtained by cation exchange reaction.

The X supply source includes, for example, inorganic bases (such as alkali metals (such as lithium, sodium, potassium), alkaline earth metals (such as magnesium, calcium, barium) hydroxides, carbonates, bicarbonates), ammonia or Organic amines (such as dimethylamine, triethylamine, hexahydropyrazine, pyrrolidine, piperidine, 2-phenylethylamine, benzylamine, ethanolamine, diethanolamine, pyridine, collidine), but, Not limited to such. Typical examples include sodium hydroxide, triethylamine and aqueous solutions of these.

In the above reaction system, a polymerization inhibitor may be appropriately added in order to prevent the polymerization reaction between the (meth)acryloyl halide compounds. Examples of the polymerization inhibitor include compounds generally used for inhibiting the polymerization reaction of polymerizable monomers, and examples thereof include hydrogen roll compounds (for example, hydrogen roll, methyl hydrogen roll, dimethyl hydrogen roll, and 4-methoxyphenol). ), but not limited to such.

In this reaction, the amount ratio of the reaction substrate to the (meth)acryloyl halide compound, the amine compound containing an anionic hydrophilic group to be used is, in molar ratio, for example, about 0.5 to about 2.0 equivalents, preferably is about 1.0 equiv. The amount ratio of the compounds in the X supply source is based on the above-mentioned X ₁ supply source (ammonia or organic amines) and X ₂ supply source (hydroxides of alkali metals or alkaline earth metals, etc.) The number of R ₂ groups contained in the base halide compound is, in molar ratio, for example, about 0.5 to about 2.0 equivalents, preferably about 1.0 equivalents. In addition, the amount ratio of the above-mentioned X ₃ supply source (ammonia or organic amines) is relative to the compound of formula (I) when X obtained above is a quaternary ammonium type ion, and the compound of formula (I) contained in each compound of the formula (I) is used. The number of R ₂ groups in molar ratio is, for example, about 0.5 to about 2.0 equivalents, preferably about 1.0 equivalents.

In addition, the compound as a polymerization inhibitor can be used in a molar ratio, for example, from a catalyst amount to a stoichiometric amount relative to the (meth)acryloyl halide compound, and generally, about 0.1 to about 10% can be used.

The solvent used in the above reaction may be any suitable solvent (such as ethers such as THF, halogenated hydrocarbons such as dichloromethane, water or a mixed solvent thereof, etc.) as long as it does not affect the reaction.

The reaction temperature is not particularly limited as long as it is suitable for the temperature at which the reaction proceeds, and examples thereof include about -25°C to about 100°C, and generally -10°C to room temperature. In order to avoid the polymerization reaction between the (meth)acryloyl halide compounds, it is preferable to add the (meth)acryloyl halide compound dropwise, for example, under ice-cooling. The reaction time can be changed according to other reaction conditions (eg, reaction substrate, reaction solvent, and reaction temperature), for example, several minutes to several days, and generally several hours to overnight.

(The composition of the present invention)

The composition of the present invention includes (A) a compound represented by the above formula (I) (hereinafter referred to as a suitable compound (A)) and (B) one or more compounds containing at least two or more ethylenically unsaturated groups (hereinafter referred to as a compound) , referred to as the appropriate compound (B)).

Furthermore, the compound (B) is contained as a film-forming component for polymerizing the acryl group or the methacryloyl group in the compound (A) represented by the above formula (I) to form a coating film component.

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

In the specification of this patent application, in order to form a coating film component by polymerizing the compound (B) with the acryl group or the methacryloyl group in the compound (A), as long as it is necessary to contain at least two or more vinylic What is necessary is just a compound of an unsaturated group, and although specific examples are described below, it is not limited to these examples. The ethylenically unsaturated group is a group selected from acryl group, methacryl group or vinyl group, preferably acryl group or methacryl group, more preferably acryl group.

Examples of the compound (B) include, for example, one or more types (for example, two types, three types, four types) selected from (meth)acrylate monomers (or oligomers thereof) containing an ethylenically unsaturated group in the molecule. , urethane (meth)acrylate monomer (oligomer) of its urethane modification and epoxy (meth)acrylate monomer (oligomer) of its epoxy modification compounds), but not limited to these. Preferred are urethane (meth)acrylate monomers (oligomers). Compound (B) can be obtained commercially, or can be produced by a generally known production method.

Typical examples of the compound (B) include polyfunctional aliphatic urethane (meth)acrylates, polyfunctional aromatic urethane (meth)acrylates, and polyfunctional aliphatic acrylates, preferably It is a polyfunctional aliphatic urethane (meth)acrylate.

Here, "multifunctional" means containing one or more kinds selected from, for example, ethoxylated o-phenylphenol, methoxypolyethylene glycol, phenoxypolyethylene glycol, isostearyl, and perylene glycol. base, 2-hydroxy-3-propenyloxypropyl, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, tricyclodecane dimethanol, 1,6-hexanediol, 1,9-nonane Diol, 1,10-Decanediol, Dipropylene Glycol, Tripropylene Glycol, Neopentaerythritol, Dinepentaerythritol, Trimethylolpropane, Di-trimethylolpropane, Ethoxylated Glycerin, Propoxylated Functional groups of ethoxylated ethoxylated bisphenol A, ethoxylated bisphenol A, propoxylated bisphenol A, ethoxylated trimeric isocyanate, ε-caprolactone modified trimeric isocyanate.

The compound (B) can be produced by using a commercially available product or by a generally known organic chemical synthesis method. For example, the above-mentioned urethane acrylates can be produced by addition-reacting dipivoerythritol pentaacrylate or neotaerythritol triacrylate to isocyanate. Specifically, the addition reaction of dipivalerythritol acrylate to the cyanate body of hexamethylene diisocyanate (HDI) (that is, the trimeric isocyanate body) can be used to obtain the number of acryl functional groups. Urethane acrylate of 15 (CAS number: 167972-43-2). In addition, the urethane acrylate having 9 acryl functional groups can be obtained by adding neotaerythritol triacrylate to the cyanate ester of the same HDI.

Specific examples of the compound (B) include propoxylated ethoxylated bisphenol A diacrylate, 1,6-hexanediol diacrylate, ethoxylated isocyanuric acid triacrylate, ethoxylated Alkylated glycerol triacrylate, ε-caprolactone modified tris-(2-propenyloxyethyl) isocyanate, oligomeric urethane acrylate, phenyl glycidyl ether acrylate hexamethylene Diisocyanate urethane prepolymer, epoxidized glycerol triacrylate, cresol novolac epoxy acrylate, etc., but not limited to these. Two or more types (for example, two types, three types, four types) of these compounds may be used in combination.

Such systems can be, for example, NSC-7350 (manufactured by Nippon Seika Co., Ltd.), NSC-7355 (manufactured by Nippon Seika Co., Ltd.), EBECRYL220 (manufactured by Daikyo-Orix Co., Ltd.), GX-8801A (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) , A-GLY-9E (manufactured by Shin-Nakamura Chemical Industries, Ltd.), A9300-1CL (manufactured by Shin-Nakamura Chemical Industries, Ltd.), U-15HA, U-9HA and U-6HA (manufactured by Shin-Nakamura Chemical Industries, Ltd.), Beamset575 and Beamset577 ( Arakawa Chemical Industry Co., Ltd.), UV-1700B (Nippon Synthetic Chemical Industry Co., Ltd.), etc. were purchased and used.

Relative to compound (B), the composition of the present invention generally contains compound (A) in the range of 0.01wt% to 30wt%, preferably in the range of 0.05wt% to 10wt%, more preferably in the range of 0.01wt% to 30wt%. In the range of 0.5wt% to 5wt%.

In addition to the above-mentioned compound (A) and compound (B), the composition of the present invention may further contain a polymerizable compound having one ethylenically unsaturated group in the molecule other than the compound (B) (hereinafter, referred to as an appropriate compound ( C)). The selection of the compound (C) and the addition amount thereof can be appropriately determined depending on the properties required for the polymer to be obtained. Examples of the compound (C) include volatile compounds. The volatile compounds refer to compounds with a boiling point range below 260°C or a saturated vapor pressure at 25°C above 10 ^-2 kPa according to the WHO classification of volatile organic compounds.

The composition of the present invention may further contain a fluorine-containing (meth)acrylate compound (hereinafter, referred to as a suitable compound (D)). By adding the fluorine-containing (meth)acrylate compound, the oil contact angle can be increased, and the effect of easy floating of dirt and easy flow of dirt can be obtained.

Examples of the fluorine-containing (meth)acrylate compound include (per)fluoroalkyl (meth)acrylate, (per)fluoroether (meth)acrylate, or fluorine-containing urethane (meth)acrylate. )Acrylate.

Specific examples of the fluorine-containing (meth)acrylate compound include trifluoroethyl (meth)acrylate, pentafluoropropyl (meth)acrylate, hexafluoroisopropylacrylate, and tetrafluoropropyl acrylate. Methacrylate, Octafluoropentyl (meth)acrylate, Pentafluorooctyl (meth)acrylate, Tridecafluorooctyl (meth)acrylate, Heptafluorodecyl (meth)acrylate Esters, 2,2,3,3-tetrafluoropropylacrylate, 1H,1H,5H-octafluoropentylacrylate, 1,6-bis(acryloyloxy)-2,2,3,3 ,4,4,5,5-octafluorohexane; 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl acrylate, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl methacrylate, 2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl, 1H,1H,2H,2H-heptadecafluorodecyl acrylate, 1,1,1, acrylate 3,3,3-hexafluoroisopropyl, 1H,1H,2H,2H-nonafluorohexyl acrylate, 1H,1H,5H-octafluoropentyl acrylate, 1H,1H-pentadecafluoron-octyl acrylate, 2,2,3,3,3-Pentafluoropropyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1H acrylate ,1H,2H,2H-tridecafluoro-n-octyl ester, 1H,1H,2H,2H-tridecafluoro-n-octyl methacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate , 2,2-trifluoroethyl ester, etc. Preferable examples include 2,2,3,3-tetrafluoropropyl acrylate, 1H,1H,5H-octafluoropentyl acrylate, pentafluorooctyl acrylate, and tridecafluorooctyl acrylate.

For example, commercially available Viscoat 4F (manufactured by Osaka Organic Chemical Industries, Ltd.), Viscoat 8F (manufactured by Osaka Organic Chemical Industries, Ltd.), EBECRYL 8110 (manufactured by Daikyo-Orix Co., Ltd.), and Fluorolink AD 1700 (manufactured by Solvay Corporation) , Fluorolink MD 700 (manufactured by SOLVAY) and the like.

These fluorine-containing (meth)acrylate compounds can be added to the extent that the hydrophilicity and antifouling properties of the composition are not impaired. Preferably, it contains 0.1 wt % to 2 wt %.

When necessary, the composition of the present invention may contain any commonly known resins such as antioxidants, leveling agents, pigments, binders, etc., within the scope of not impairing the hydrophilicity, antifouling properties or antifogging properties of the composition of the present invention. Additives for composition.

(Coating film and laminate)

The composition of the present invention is irradiated with light or heated (for example, hot air) or both, and the compound (A) and the compound (B) contained in the composition undergo a polymerization reaction to form a coating film on the surface of the substrate Element.

In order to polymerize the composition of the present invention, the composition of the present invention may optionally contain a polymerization initiator, a free radical generator, a catalyst, a polymerization accelerator, and a Additives commonly known as additives for polymerization, such as UV absorbers, infrared absorbers, radical scavengers, polymerization inhibitors, light stabilizers (such as hindered amine light stabilizers (HALS)).

As the polymerization initiator, for example, at least one kind selected from the group consisting of ionic polymerization initiators (eg, cationic polymerization initiators, anionic polymerization initiators), radical polymerization agents, and the like can be mentioned, and two or more kinds thereof may be used in combination. From the viewpoint of the properties of the obtained composition (for example, hydrophilicity, antifouling property, and antifogging property), an ionic polymerization initiator is preferable, and a cationic polymerization initiator is more preferable.

Examples of the cationic polymerization initiator include electrophiles (for example, protonic acids, Lewis acids, halogen molecules, carbocations, etc.), and specific examples include triphenyl perylene tetrafluoroborate, bis(4-tert-butylphenyl) Idium hexafluorophosphate, bis(4-fluorophenyl) iodonium trifluoromethanesulfonate, cyclopropyldiphenyl perylene tetrafluoroborate, dimethylbenzyl methyl perylene tetrafluoroborate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroarsenate, diphenyl iodonium trifluoromethanesulfonate, 2-(3,4-dimethoxystyryl)-4,6-bis( Trichloromethyl)-1,3,5-triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine oxazine, 4-isopropyl-4'-methyldiphenyl iodonium tetrakis(pentafluorophenyl)borate, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6 -Bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine , 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, (2-methylphenyl)(2,4,6- Trimethylphenyl) iodonium trifluoromethanesulfonate, (3-methylphenyl)(2,4,6-trimethylphenyl) iodonium trifluoromethanesulfonate, (4-methylphenyl) ) (2,4,6-trimethylphenyl) iodo trifluoromethanesulfonate, 4-nitrobenzene tetrafluoroborate diazonium salt, (4-nitrophenyl) (phenyl) iodo trifluoromethane Sulfonate, Phenyl[4-(trimethylsilyl)thiophen-3-yl] iodotrifluoromethanesulfonate, Phenyl[4-(trimethylsilyl)thiophen-3-yl] iodotri Fluoromethanesulfonate, Triphenylperylium Bromide, Tris-p-Tolylperium Hexafluorophosphate, Tris-p-Tolylperyltrifluoromethanesulfonate, [3-(trifluoromethyl)phenyl ](2,4,6-trimethylphenyl) iodotrifluoromethanesulfonate, [4-(trifluoromethyl)phenyl](2,4,6-trimethylphenyl) iodotrifluoro Mesylate, etc., however, are not limited to these. This cationic polymerization initiator may be a commercial item, and may be manufactured by a conventional manufacturing method.

Nucleophilic agents (for example, n-butyllithium) are mentioned as an anionic polymerization initiator, however, it is not limited to these. This anionic polymerization initiator may be a commercial item, and may be manufactured by a conventional manufacturing method.

Examples of the radical polymerization initiator include azo compounds and peroxides, but are not limited to these. This radical polymerization initiator may be a commercial item, and may be manufactured by a conventional manufacturing method.

Conventional photopolymerization initiators such as photoradical polymerization initiators, photocationic polymerization initiators or photoanionic polymerization initiators can be used when the composition of the present invention is copolymerized with radiation such as ultraviolet rays. A photopolymerization initiator may be a commercial item, and may be manufactured by a conventional manufacturing method.

Specific examples of the photo-radical polymerization agent include Irgacure-651 (manufactured by BASF), Irgacure-184 (manufactured by the same company), Irgacure-500 (manufactured by the same company), Irgacure-2959 (manufactured by the same company), Irgacure-127 ( same company), Irgacure-907 (same company), Irgacure-369 (same company), Irgacure-1300 (same company), Irgacure-819 (same company), Irgacure-1800 (same company), Irgacure-OXE01 (manufactured by the same company), Irgacure-OXE02 (manufactured by the same company), Darocur 1173 (manufactured by the same company), Darocur TPO (manufactured by the same company), Darocur 4265 (manufactured by the same company), etc., but not limited to these.

The usage amount of the polymerization initiator used in the manufacture of the composition, relative to the total amount of compound (A), compound (B), and compound (C), can be used in an amount of catalyst (for example, about 10 ^-3 to about 10 of the reaction matrix). ^-1 mol%) to several molar equivalent %, but, preferably, the amount of catalyst. For example, relative to 100 parts by weight of compound (A), compound (B) and compound (C) in total, the amount of the cationic polymerizer used is generally in the range of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight range, more preferably in the range of 0.1 to 5 parts by weight.

With respect to the total of 100 parts by weight of compound (A), compound (B) and compound (C), the amount of the photo-radical polymerization agent used is generally in the range of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight , more preferably in the range of 1 to 5 parts by weight.

For the composition of the present invention, in order to improve the coating properties on the substrate and adjust the viscosity of the coating, a solvent may be added if necessary. Specifically, alcohol (for example, methanol, ethanol, isopropanol, n-butanol, methoxyethanol, 1-methoxy-2-propanol, glycerol), ketone (for example, acetone), polar aprotic As a solvent (for example, dimethylformamide (DMF)), water, etc., the mixed solvent of 2 or more types of these solvents can also be used.

The polymerization reaction of the present invention can be carried out in an atmospheric environment, and can be carried out in an inert gas (eg nitrogen, argon) environment from the viewpoints of reaction time and reaction efficiency.

When the polymerization is carried out by heat, the reaction temperature is generally from room temperature to a temperature below 300°C, preferably from 30 to 80°C, corresponding to the reaction conditions such as the reaction substrate and the polymerization method. Also, the reaction time is generally 1 to 180 minutes (minutes or hours), preferably 2 to 120 minutes (minutes or hours).

Moreover, when using a radical polymerization initiator, a radical generator (for example, an organic peroxide) can be added to a reaction system.

When the polymerization is carried out by light irradiation, the reaction temperature is generally 10 to 150°C, preferably 30 to 80°C, corresponding to the reaction conditions such as the reaction substrate and the polymerization method. In addition, the reaction time is generally 1 second to 30 minutes (minutes or hours), preferably 1 second to 5 minutes (minutes or hours).

For the polymerization reaction, when both the light irradiation and the heating are performed, one operation may be performed first and then the other operation may be performed, and either operation may be performed first.

Examples of the radiation include visible light of 400 to 800 nm, ultraviolet rays of 400 nm or less, and electron beams, and ultraviolet rays that can be easily carried out in a short period of time are preferable. The ultraviolet generating source includes, but is not limited to, ultraviolet rays such as low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, potassium lamps, ultraviolet lasers, and sunlight. Irradiation can be carried out in an atmospheric environment or in an inert gas environment such as nitrogen and argon.

The cumulative light amount of irradiation is generally, for example, 100 to 5000 mJ, for example, 100 mJ, and 500 mJ can be irradiated.

As a method for applying the composition of the present invention to a substrate, generally known coating methods can be used, and specifically, brush coating, various coating methods (eg, spray coating, dip coating, spin coating, etc.) can be exemplified. method) and other conventional methods.

The thickness of the coating film is generally in the range of 0.1 to 300 μm, preferably in the range of 1 to 100 μm, by coating the surface of the base.

The term "base agent" in this specification can include, for example, inorganic materials (such as glass, silica, metals, metal oxides, etc.), organic materials (such as polymethyl methacrylate, polyethylene terephthalate, polycarbonate, polyurethane, polyethylene, polypropylene, polystyrene, epoxy resin or films of these or paper, wood pulp) and combinations of these inorganic and organic materials.

The lamination system of the present invention can be formed by comprising the following steps: (1) a step of coating the composition of the present invention on a substrate, (2) a step of irradiating the composition with light, heating, or both to form a coating film In the method, a coating film and a base material layer are formed, and the coating film is formed on at least one side of the base material layer to manufacture a laminate.

The term "laminated body" in this specification may enumerate glass, display material surfaces (such as monitors, TV films) or water-touching items (such as bathroom wall materials, bathroom floor materials, wash mirrors, washstands, kitchen countertops, bedpans, toilet seats) ), etc., but not limited to such.

(use)

The compound of the present invention or a composition containing the compound can be used as an antifouling agent. In addition, the compound of the present invention or a composition containing the compound can be used as an antifogging agent.

Since the compound of the present invention has a (meth)acrylamide skeleton, compared with the conventional compounds having a (meth)acrylamide skeleton, even under acidic and/or basic conditions, it is less susceptible to hydrolysis reaction, thereby improving stability. Excellent. Therefore, it can be used in combination with alkaline chemicals, such as a mold remover (for example, a mold remover) used for cleaning a bathroom, etc., for example.

Furthermore, since the coating film containing the composition of the present invention exhibits antifouling properties and/or antifogging properties, the laminated film formed by the coating film can be applied to various articles such as laminates as antifouling films, antifogging films, etc. .

Properties of Products (eg, Compositions) of the Invention

(hydrophilic)

The coating film containing the composition of the present invention has a water contact angle of 70° or less, preferably 40° or less, and more preferably 10° or less. Therefore, the coating film exhibits good hydrophilicity.

(oil repellency)

The coating film comprising the composition of the present invention has an oil contact angle of 15° to 40°, preferably 20° to 35°, more preferably 20° to 30°. Therefore, the coating film has good hydrophilicity and exhibits oil repellency.

(Anti-fouling and anti-fogging)

The coating film comprising the composition of the present invention exhibits good antifouling properties and good antifogging properties.

(durability)

The coating film containing the composition of the present invention is excellent in durability under acidic and/or alkaline conditions.

[Example]

Hereinafter, production examples and test examples of compounds, compositions, etc. are given to illustrate the present invention in more detail, but the present invention is not limited to these examples. Identification of compounds was carried out by analysis of various spectroscopic analyses. Specifically, in NMR, a resonance frequency of 300 MHz was used for hydrogen nuclear magnetic resonance ( ¹ H-NMR). Symbols used in NMR, s is a singlet, d is a doublet, dd is a doublet doublet, t is a triplet, td is a triplet doublet, q is a quartet, quin is a quintet, sept is septet, m is multiplet, br is broad, brs is broad singlet, brd is broad doublet, brt is broad triplet and J is coupling constant.

A production example of the compound of the present invention is shown.

(Example 1)

Production of acrylamide methanesulfonic acid sodium salt (compound 1 of the present invention)

To 10.0 g (90 mmol) of aminomethanesulfonic acid, 25 g of water was added, and 9.11 g (90 mmol) of triethylamine and 36.0 g (90 mmol) of a 10% aqueous sodium hydroxide solution were added and dissolved. 0.0181 g (90 mmol) of 4-methoxyphenol as a polymerization inhibitor was added, and the mixture was stirred under ice-cooling. Then, 8.15 g (90 mmol) of acryl chloride was gradually added dropwise, and after stirring for 1 hour, the reaction was performed at room temperature for 4 hours.

After completion of the reaction, water was removed under reduced pressure, 50 g of methanol was added, the mixture was stirred for 1 hour, and filtered. The filtrate was dried in an evaporator, added with 50 g of water and 36.0 g of a 10% aqueous sodium hydroxide solution, stirred for 0.5 hours, and then removed the solvent under reduced pressure, and then dried with a vacuum pump to obtain a hydrophilic material, acrylamide methanesulfonic acid sodium salt 16.9 g.

(Example 2)

Production of acrylamide ethanesulfonic acid sodium salt (compound 2 of the present invention)

According to the method described in Example 1, 10 g of 2-aminoethanesulfonic acid was used instead of aminomethanesulfonic acid to obtain 16.1 g of acrylamideethanesulfonic acid sodium salt.

(Example 3)

Production of acrylamide propanesulfonic acid sodium salt (compound 3 of the present invention)

According to the method described in Example 1, 10 g of 3-amino-1-propanesulfonic acid was used instead of aminomethanesulfonic acid to obtain 15.5 g of acrylamide propanesulfonic acid sodium salt.

¹ H NMR (300MHz, D ₂ O) 6.16-5.82 (m, 2H), 5.48-5.62 (dd, 1H), 3.26-3.21 (t, 2H), 2.81-2.75 (t, 2H), 1.87-1.76 ( m, 2H)

(Example 4)

Production of Acrylamidobutanesulfonic Acid Sodium Salt (Compound 4 of the Invention)

According to the method described in Example 1, 3 g of 4-amino-1-butanesulfonic acid was used instead of aminomethanesulfonic acid to obtain 4.5 g of acrylamidebutanesulfonic acid sodium salt.

¹ H NMR (300MHz, D ₂ O) 6.05-5.89 (m, 2H), 5.53-5.49 (dd, 1H), 3.17-3.13 (t, 2H), 2.81-2.76 (t, 2H), 1.62-1.53 ( m,4H)

(Example 5)

Production of Acrylamidopentanesulfonic Acid Sodium Salt (Compound 5 of the Invention)

According to the method described in Example 1, 4-amino-1-pentanesulfonic acid was used instead of aminomethanesulfonic acid to obtain acrylamidepentanesulfonic acid sodium salt. The structure was identified by ¹ H NMR.

(Example 6)

Production of acrylamide hexanesulfonic acid sodium salt (compound 6 of the present invention)

According to the method described in Example 1, 4-amino-1-hexanesulfonic acid was used instead of aminomethanesulfonic acid to obtain acrylamide hexanesulfonic acid sodium salt. The structure was identified by ¹ H NMR.

(Example 7)

Production of acrylamide heptanesulfonic acid sodium salt (compound 7 of the present invention)

According to the method described in Example 1, 4-amino-1-heptanesulfonic acid was used instead of aminomethanesulfonic acid to obtain acrylamide heptanesulfonic acid sodium salt. The structure was identified by ¹ H NMR.

(Example 8)

Production of acrylamide octanesulfonic acid sodium salt (compound 8 of the present invention)

According to the method described in Example 1, 4-amino-1-octanesulfonic acid was used instead of aminomethanesulfonic acid to obtain acrylamide octanesulfonic acid sodium salt. The structure was identified by ¹ H NMR.

(Example 9)

Production of acrylamide nonanesulfonic acid sodium salt (compound 9 of the present invention)

According to the method described in Example 1, 4-amino-1-nonanesulfonic acid was used instead of aminomethanesulfonic acid to obtain acrylamide nonanesulfonic acid sodium salt. The structure was identified by ¹ H NMR.

(Example 10)

Production of acrylamide decanesulfonic acid sodium salt (compound 10 of the present invention)

According to the method described in Example 1, 4-amino-1-decanesulfonic acid was used instead of aminomethanesulfonic acid to obtain acrylamide decanesulfonic acid sodium salt. The structure was identified by ¹ H NMR.

(Example 11)

Production of acrylamide dodecanesulfonic acid sodium salt (compound 11 of the present invention)

According to the method described in Example 1, 4-amino-1-dodecanesulfonic acid was used instead of aminomethanesulfonic acid to obtain acrylamidedodecanesulfonic acid sodium salt. The structure was identified by ¹ H NMR.

(Example 12)

Production of acrylamide undecanesulfonic acid sodium salt (compound 12 of the present invention)

According to the method described in Example 1, 4-amino-1-undecanesulfonic acid was used instead of aminomethanesulfonic acid to obtain acrylamide undecanesulfonic acid sodium salt. The structure was identified by ¹ H NMR.

(Example 13)

Production of acrylamide propanesulfonic acid triethylamine salt (compound 13 of the present invention)

12.5 g of water was added to 5 g (36 mmol) of 3-amino-1-propanesulfonic acid, and 3.64 g (36 mmol) of triethylamine and 13.05 g (36 mmol) of a 10% aqueous sodium hydroxide solution were added and dissolved. 0.008 g of 4-methoxyphenol as a polymerization inhibitor was added, and the mixture was stirred under ice-cooling. Then, 2.95 g (36 mmol) of acryl chloride was gradually added dropwise, and the mixture was stirred for 1 hour. Then the reaction was carried out at room temperature for 4 hours.

After completion of the reaction, water was removed under reduced pressure, methanol was added, and the mixture was stirred for 1 hour and then filtered. The filtrate was dried to obtain 10.6 g of acrylamide propanesulfonic acid triethylamine salt.

(Example 14)

Production of acrylamide benzenesulfonic acid sodium salt (compound 14 of the present invention)

According to the method described in Example 1, 10 g of 4-aminobenzenesulfonic acid was used instead of aminomethanesulfonic acid to obtain 13.2 g of acrylaminobenzenesulfonic acid sodium salt.

(Example 15)

Production of methacrylamidoethanesulfonic acid sodium salt (Compound 15 of the present invention)

70 g of water was added to 15.0 g (120 mmol) of aminoethanesulfonic acid, and 4.8 g (120 mmol) of sodium hydroxide and 21.9 g (216 mmol) of triethylamine were added and dissolved. 0.056 g of 4-methoxyphenol as a polymerization inhibitor was added, and the mixture was stirred under ice-cooling. Then, 27.8 g (180 mmol) of methacrylic anhydride was gradually added dropwise, and the mixture was stirred for 1 hour. The reaction was then carried out at room temperature for 16 hours.

After the completion of the reaction, the solvent was removed under reduced pressure, 150 g of acetone was added, and the mixture was stirred for 1 hour and then filtered. It was dried with a vacuum pump to obtain 25.8 g of methacrylamidoethanesulfonic acid sodium salt as a hydrophilic material.

Next, the production example of the composition of this invention is shown.

(Production of composition by cationic polymerization)

(Example 16)

Production of a composition containing (meth)acrylamidoethanesulfonic acid sodium salt (the present composition 1)

0.4 g of acrylamide ethanesulfonic acid sodium salt (compound 2 of the present invention) as a hydrophilic component (A), 33.0 g of NSC-7350 (manufactured by Nippon Seika Co., Ltd.) as a compound having an acryl group, and tridecafluorooctane 0.35 g of acrylic acid ester and 0.01 g of triphenyl perylene tetrafluoroborate were mixed and dissolved in 62.7 g of 1-methoxy-2-propanol as a solvent to prepare Composition 1 of the present invention. In the same manner, the composition 1' of the present invention was produced by using methacrylamidoethanesulfonic acid sodium salt (present compound 15) instead of acrylamideethanesulfonic acid sodium salt.

(Example 17)

According to the method described in Example 16, any one of the compounds (A) produced in Example 1 and Examples 3 to 12 was used instead of acrylamide ethanesulfonic acid sodium salt, respectively. Each of the compositions 2 to 12 of the present invention was prepared by cationic polymerization. In the same operation, the corresponding methacrylamidosulfonic acid sodium salts were used to replace the various acrylimidosulfonic acid sodium salts produced in Example 1 and Examples 3 to 12 to prepare the compositions 2' to 12 of the present invention. '.

(Production of composition by radical polymerization)

(Example 18)

Production of a composition containing (meth)acrylamidobutanesulfonic acid sodium salt (the composition 13 of the present invention)

0.038 g of acrylamide butanesulfonic acid sodium salt (compound 4 of the present invention) as the hydrophilic component (A) was dissolved in 0.342 g of water, and NSC-7350 (Nihon Seika Co., Ltd.) was added as a compound having an acryl group. Production) 1.5 g, 1.95 g of 1-methoxy-2-propanol as a solvent, and 0.045 g of Irgacure-2959 (manufactured by BASF) as a photopolymerization initiator were mixed and dissolved to prepare Composition 13 of the present invention. In the same operation, the composition 13' of the present invention was produced by using methacrylamidobutanesulfonic acid sodium salt instead of acrylamidebutanesulfonic acid sodium salt.

(Example 19)

According to the method described in Example 18, any one of the compounds (A) produced in Examples 1 to 3 and Examples 5 to 12 was used in place of the sodium salt of acrylamide butanesulfonate, and each of the present invention was prepared by radical polymerization reaction. Compositions 14 to 24. In the same operation, the corresponding methacrylamidoalkanesulfonic acid sodium salt was used to replace the various acrylamide alkylsulfonic acid sodium salts produced in Examples 1 to 3 and 5 to 12 to prepare the composition of the present invention. 14' to 24'.

(Comparative Example 1)

Manufacture of a composition (comparative composition 1) containing 2-propenamide-2-methylpropanesulfonic acid sodium salt

According to the method described in Example 19, the composition of Comparative Example 1 was prepared by using 2-acrylamido-2-methylpropanesulfonic acid sodium salt instead of acrylamide butanesulfonic acid sodium salt.

Next, the method of film formation is shown.

(Example 20)

The coating compositions obtained in the above Examples 16 to 17, Examples 18 to 19 and Comparative Example 1 were coated on an easily adhesive polyethylene terephthalate (PET) film with a thickness of 188 μm using a coating bar #8 surface. The coated PET film was placed in a warm air oven at a temperature of 60°C for 2 minutes and then irradiated with ultraviolet rays with an accumulated light amount of 100 mJ. In addition, in order to promote hardening, an additional accumulated light amount of 500 mJ was irradiated to form a hydrophilic coating film.

(Example 21)

An example of producing the coating film of the present invention is shown.

0.3 g of sodium methacrylamidoethanesulfonate, 10 g of Beamset 577 (manufactured by Arakawa Chemical Co., Ltd.), 0.86 g of pentafluorooctyl acrylate, 0.1 g of triphenyl tetrafluoroborate, 1-methyl methacrylate 11.2 g of oxy-2-propanol were mixed to obtain composition 25' of the present invention as a coating agent. In the same operation, acrylamide ethanesulfonic acid sodium salt was used in place of methacrylamidoethanesulfonic acid sodium salt to produce Composition 25 of the present invention.

The obtained composition of the present invention was coated on a PET film A4300 manufactured by Toyobo Co., Ltd. using a coating bar to obtain a coating film. The properties of the resulting coating films were measured.

(Example 22)

According to the method described in Example 21, methacrylamidoethanesulfonic acid sodium salt was used instead of acrylamide ethanesulfonic acid sodium salt to obtain the coating film of the present invention.

In addition, test examples are shown.

(Test Example 1)

Antifouling test

First, the results of the antifouling test are presented.

The antifouling test of the coating films produced in Examples 20 and 21 was carried out. Specifically, after marking with an oil-based strange pen "McKee Extreme" (manufactured by ZEBRA), distilled water was run down on the surface, and those that could be wiped off were indicated by ○, and those that could not be wiped off by ×.

In the case of the coating film of the present invention, the results of observing any of the compositions 1 to 25 and 1' to 25' were ○. On the other hand, in the case of the comparative composition 1, the result of x was shown. Therefore, any of the coating films derived from the compositions 1 to 25 and 1' to 25' of the present invention exhibited superior antifouling properties as compared with the coating films of the comparative composition 1.

Next, the results of the hydrophilicity test and the durability test are presented.

First, the following composition 26 of the present invention was prepared as the composition of the present invention.

(Composition 26 of the present invention)

0.01 g of acrylamide propanesulfonic acid sodium salt (compound 3 of the present invention), which is a hydrophilic component, was dissolved in 0.19 g of water, and 1.5 g of NSC-7355 (manufactured by Nippon Seika Co., Ltd.) as an acryl group compound was added thereto. , 0.82 g of 1-methoxy-2-propanol as a solvent, 1.13 g of 95% ethanol, and 0.045 g of Irgacure-2959 (manufactured by BASF) as a photopolymerization initiator, mixed and dissolved to prepare the composition of the present invention 26.

Next, compositions of comparative examples described below were produced.

(Comparative Composition 2)

0.35 g of sulfopropyl acrylate potassium salt as a hydrophilic component, 0.09 g of hydroxyester P-2M (manufactured by Kyoeisha Chemical Co., Ltd.), and A-GLY-9E (Shin Nakamura Chemical Industry Co., Ltd.) as a compound having an acryl group Manufacturing) 5.86 g, A9300-1C1 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 0.98 g, U-15HA (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 12.7 g, 12.03 g of 1-methoxy-2-propanol as a solvent, and water 3.01 g and 0.6 g of Darocur 1173 (manufactured by BASF Corporation) as a photopolymerization initiator were mixed and dissolved to prepare Comparative Composition 2.

Contact angle measurement test

The coated PET film was attached to a glass plate, and the contact angle was measured using a contact angle meter DMs-401 manufactured by Kyowa Interface Science Co., Ltd. The measurement system used water and oleic acid.

(Test Example 2)

Hydrophilic test

The water contact angle was measured as a hydrophilicity test.

Specifically, based on the general measurement method, using the water contact angle device DMs-401 manufactured by Kyowa Interface Science Co., Ltd., the static contact after dropping 1 μL of water droplets at room temperature for 1 second was measured by the θ/2 method. horn. The measurement is that after the hydrophilic coating film is formed, the hydrophilic coating film is washed with distilled water and then dried. After each drying and after the acid-resistance and alkali-resistance chemical tests described later, three measurements were performed, and the average was taken as the value of the contact angle.

The coating films of the present invention prepared using the compositions 1 to 12 and 1' to 12' of the present invention produced in Examples 16 to 17 and the compositions 25 and 25' of the present invention produced in Example 21 are shown in any case. Water contact angle below 10°. In addition, the coating films of the present invention prepared using the compositions 13 to 24 and 13' to 24' of the present invention produced in Examples 18 to 19 also exhibited a water contact angle of 40° or less in any case.

(Test Example 3)

Oil repellency test

As the oil repellency test, the oil contact angle was measured by an oil contact angle device DMs-401 manufactured by Kyowa Interface Science Co., Ltd. based on a general measurement method, using oleic acid as the oil. When the oil contact angle is an appropriate size, the dirt written with the oil-based pen will float up quickly in the antifouling test, and when water is poured, the dirt will float up and be easy to clean.

Measurement of the water contact angle and oleic acid contact angle of the coating films of the present invention prepared using the compositions of the present invention produced in Examples 16 to 17 using the compounds (A) shown in Table 1 below The results are shown in Table 1 below. In addition, the measurement results of the water contact angle and the oleic acid contact angle of the coating film of the present invention prepared by using the composition 25 of the present invention are shown in Table 2 below.

In any case, the coating film of the present invention exhibits an oil contact angle of 20° to 28° or less.

(Test Example 4)

Drug Durability Test

For the coating film forming the hydrophilic coating film, the durability test of the medicine was carried out under each condition of acidity and alkalinity.

Specifically, it was immersed for 24 hours, immersed in 5% hydrochloric acid water for 24 hours, thoroughly washed with running water, and then dried. After drying, water contact angle and antifouling tests were performed to evaluate acid resistance.

Moreover, similarly, it was immersed in a mildew remover for 24 hours, rinsed well with running water, and then dried. After drying, perform water contact angle and antifouling tests to evaluate the alkali resistance.

The measurement results of comparing the coating film of the present invention obtained by using the composition 26 of the present invention and the coating film of the comparative example are shown in Table 3 below.

Compared with the coating film of the comparative composition 2, the coating film of the composition 26 of the present invention exhibits excellent hydrophilicity and antifouling properties under acidic and alkaline conditions.

(Test Example 5)

Anti-fog test

The anti-fogging test is to place the surface on which the hydrophilic coating film is formed perpendicular to the vapor at 50°C to visually observe whether there is fog. The case where there is no fog for more than 5 seconds is ○, and the case where fog is generated is ×. The coating film of the present invention obtained by using the composition of the present invention exhibits antifogging properties.

[Industrial Availability]

According to the present invention, a (meth)acrylamide compound excellent in durability under acidic and/or alkaline conditions and excellent in antifouling properties and/or antifogging properties can be obtained. In addition, the coating film produced from the (meth)acrylamide compound having these functions can be used as a laminated film on the surface of display materials such as glass and displays, or on articles that touch water, and has high industrial utility value.

Claims (18)

A composition comprising (A) a compound represented by formula (I), and (B) one or more compounds containing at least two or more ethylenically unsaturated groups, wherein the compound is more The content of (A) is 0.01wt% to 30wt% in terms of weight ratio,

In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is an anionic hydrophilic group, X is a hydrogen atom, an alkali metal ion, an alkaline earth metal ion or a quaternary ammonium ion, p is 1 or 2, and q is 0 or 1 , but, when p is 1, q is 1, when p is 2, q is 0, and R is a linear or branched aliphatic hydrocarbon group represented by formula (II),

The aliphatic hydrocarbon group may contain at least one group selected from an aliphatic carbocyclic group, an aromatic carbocyclic group, an ether group or an ester group, n is an integer from 1 to 12, and A is each independently represented by formula (III) base,

In the formula, m is an integer from 0 to 12, and R ₂ and X are as defined above, when there are more than 2 A, the A may exist on the same or different carbon atoms, and o is 0 to 6. Integer. The composition according to claim 1, wherein the anionic hydrophilic group is at least one group selected from CO ₂ ^- , SO ₃ ^- , PO ₄ ^2- or HPO ₄ ^- . The composition according to claim 1, wherein the anionic hydrophilic group is SO ₃ ⁻ . The composition according to any one of items 1 to 3 of the claimed scope, wherein, o is 0, and the R is a group represented by formula (II-1) or (II-2):

In the formula, n is an integer from 1 to 12. The composition according to any one of items 1 to 3 of the claimed scope, wherein, n is an integer of 2 to 8. The composition according to any one of Claims 1 to 3, wherein p is 1 and q is 1. The composition as described in item 1 of the claimed scope, wherein the compound (A) is selected from (meth)acrylamidomethanesulfonate, (meth)acrylamidoethanesulfonate, (meth)acrylamidopropanesulfonate, (meth)acrylamidobutane Sulfonate, (meth)acrylamidopentanesulfonate, (meth)acrylamidohexanesulfonate, (meth)acrylamidoheptanesulfonate, (meth)acrylamidooctanesulfonic acid salt, (meth)acrylamidononanesulfonate, (meth)acrylamidodecanesulfonate, (meth)acrylamidododecanesulfonate, (meth)acrylamidoundecane The group consisting of sulfonate and (meth)acrylamide benzene sulfonate. The composition according to any one of claims 1 to 3 of the claimed scope, wherein the compound (B) is a urethane (meth)acrylate monomer (oligomer). The composition according to any one of items 1 to 3 of the claimed scope, further comprising a fluorine-containing (meth)acrylate compound. The composition of claim 9, wherein the fluorine-containing (meth)acrylate compound is selected from the group consisting of (per)fluoroalkyl (meth)acrylate, (per)fluoroether (methyl) ) acrylate or fluorine-containing urethane (meth)acrylate. A method for producing the composition described in any one of the claims 1 to 10 of the scope of the application, which is to combine (A) the formula (I) described in any one of the claims 1 to 10 of the scope of the application The represented compound and (B) one or more compounds containing at least two or more ethylenically unsaturated groups are reacted in the presence of a cationic polymerization catalyst as a polymerization initiating catalyst. A coating film, which is composed of hardening on a substrate as claimed in the first patent scope To the composition described in any one of 10 items. A laminated body is composed of the coating film as described in claim 12 and a base material layer, wherein the coating film is formed on at least one side of the base material layer. The laminated body according to claim 13, wherein the laminated body is a water-touching article. An antifouling agent, comprising the composition described in any one of items 1 to 10 of the patent application scope. An anti-fogging agent comprising the composition described in any one of items 1 to 10 of the patent application scope. A method for manufacturing a laminate, comprising the steps of coating a substrate with the composition described in any one of claims 1 to 10 of the scope of the application, and subjecting the composition to light irradiation, heating, or a combination of both. step. A manufacturing method, which is a manufacturing method of a compound represented by formula (I),

In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is an anionic hydrophilic group, X is a hydrogen atom, an alkali metal ion, an alkaline earth metal ion or a quaternary ammonium ion, p is 1 or 2, and q is 0 or 1 , but, when p is 1, q is 1, when p is 2, q is 0, and R is a linear or branched aliphatic hydrocarbon group represented by formula (II),

The aliphatic hydrocarbon group may contain at least one group selected from an aliphatic carbocyclic group, an aromatic carbocyclic group, an ether group or an ester group, n is an integer from 1 to 12, and A is each independently represented by formula (III) base,

In the formula, m is an integer from 0 to 12, and R ₂ and X are as defined above, when there are more than 2 A, the A may exist on the same or different carbon atoms, and o is 0 to 6. Integer; the manufacturing method comprises: converting the formula:

The (meth)acryloyl halide compound or formula represented by:

(meth)acrylic anhydride compound represented by the formula: H ₂ NRR ₂ H or

The amine compound represented, together with the compound selected from the X supply source of ammonia or organic amines and the compound selected from the X supply source of alkali metal or alkaline earth metal hydroxide, carbonate or bicarbonate, suitably in Carry out the reaction in the presence of a polymerization inhibitor to obtain the compound represented by the formula (I) in which X is a quaternary ammonium ion; and when it is desired to obtain the compound represented by the formula (I) in which X is an ion of an alkali metal or an alkaline earth metal, the The compound represented by the formula (I) in which the obtained X is a quaternary ammonium ion is reacted with a compound selected from the X supply source of alkali metal or alkaline earth metal hydroxide, carbonate or bicarbonate to obtain X as an alkali metal Or a compound represented by the formula (I) of an ion of an alkaline earth metal.