JP2020070364A - Composition containing acrylamide-based polymer and coating material - Google Patents

Abstract

To provide a composition which is excellent in transparency and water resistance when forming a cured product.SOLUTION: The composition contains a polymer (A) having a structural unit represented by formula (I) and a compound (B) represented by (RR)N-R-Si(RRR). [Ris H or a methyl group; Ris an optionally substituted C1-30 divalent hydrocarbon group; Rand Rare each independently H or an optionally substituted C1-30 monovalent hydrocarbon group; Ris a C1-50 divalent group; Ris an alkoxyl group or a hydroxyl group; and Rand Rare each independently H, a halogen atom, an alkoxyl group, a hydroxyl group, or an optionally substituted C1-30 monovalent hydrocarbon group.]SELECTED DRAWING: None

Description

  Embodiments of the present invention relate to a composition containing an acrylamide polymer, a coating material, a cured product, a substrate with a cured product, and an article.

  In the paint industry, from the viewpoint of environmental compatibility, conversion from organic solvent-based paints to water-based paints is in progress. Emulsion type paints have already been used as building material paints. However, in an emulsion-based paint, since a film is formed by fusion or cross-linking of resin particles, it may be difficult to form a glossy and homogeneous film due to defects in the resin particles. In addition, a film may be formed on the surface of the film due to aggregation of the resin particles, and when bake-curing is performed, water in the film may be difficult to evaporate. As a coating material for solving these problems, a coating composition in which a water-soluble resin is dissolved in water can be mentioned (for example, Patent Documents 1 and 2).

JP, 2017-222818, A JP, 2004-182867, A

  The embodiment of the present invention is made in view of the above, and an object of the present invention is to provide a composition and a paint which are excellent in transparency and water resistance when it is set as a cured product. Moreover, the embodiment of this invention makes it a subject to provide the hardened | cured material excellent in transparency and water resistance, and the base material and article with a hardened material which have the said hardened material.

  The invention includes various embodiments. Examples of the embodiments are listed below. The present invention is not limited to the embodiments below.

〔式（Ｉ）中、Ｒ^１は、水素原子又はメチル基を表し、Ｒ^２は、置換基を有してもよい炭素数１〜３０の２価の炭化水素基を表す。〕

〔式（II）中、Ｒ^３及びＲ^４は、それぞれ独立に、水素原子又は置換基を有してもよい炭素数１〜３０の１価の炭化水素基を表し、Ｒ^５は、炭素数１〜５０の２価の基を表し、Ｒ^６は、アルコキシル基又はヒドロキシル基を表し、Ｒ^７及びＲ^８は、それぞれ独立に、水素原子、ハロゲン原子、アルコキシル基、ヒドロキシル基、又は置換基を有してもよい炭素数１〜３０の１価の炭化水素基を表す。〕 [1] A composition containing a polymer (A) containing a structural unit represented by the following formula (I) and a compound (B) represented by the following formula (II).

[In the formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a divalent hydrocarbon group having 1 to 30 carbon atoms, which may have a substituent. ]

[In the formula (II), R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ⁵ represents the number of carbon atoms. 1 to 50 divalent group, R ⁶ represents an alkoxyl group or a hydroxyl group, R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkoxyl group, a hydroxyl group, or a substituent. It represents a monovalent hydrocarbon group having 1 to 30 carbon atoms which may be possessed. ]

[2] The composition according to the above [1], wherein in the formula (II), R ³ and R ⁴ are both hydrogen atoms.

[3] The composition according to the above [1] or [2], wherein the polymer (A) contains the structural unit represented by the formula (I) in an amount of 30% by mass or more based on the total structural units.

[4] The composition according to any one of [1] to [3] above, wherein the polymer (A) further contains a structural unit having a polar group.

[5] A paint containing the composition according to any one of [1] to [4] above and water.

[6] The composition according to any one of [1] to [4] above, or the cured product of the coating material according to [5] above.

[7] A substrate with a cured product, which comprises the substrate and the cured product according to the above [6].

[8] An article comprising the cured product according to [6] above or the substrate with a cured product according to [7] above.

  According to the embodiments of the present invention, it is possible to provide a composition and a coating which are excellent in transparency and water resistance when they are made into a cured product. Moreover, according to the embodiment of the present invention, it is possible to provide a cured product having excellent transparency and water resistance, and a substrate and an article with a cured product having the cured product.

  Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (components, steps, numerical ranges, etc.) are not essential unless otherwise specified.

In the present disclosure, the numerical range indicated by using "to" indicates the range including the numerical values before and after "to" as the minimum value and the maximum value, respectively.
In the numerical ranges described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value described in another one numerical range. .. Further, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value of each numerical range may be replaced with the numerical values shown in the examples.

  In the present disclosure, each component may include a plurality of types of applicable substances. When there are multiple types of substances corresponding to each component in the composition, the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition unless otherwise specified. Means quantity.

<Composition>
The composition, which is an embodiment of the present invention, contains a polymer (A) containing a structural unit represented by the following formula (I) and a compound (B) represented by the following formula (II). With the composition containing the polymer (A) and the compound (B), a cured product excellent in transparency and water resistance, particularly in water adhesion can be obtained. In the present disclosure, the polymer (A) containing a structural unit represented by the following formula (I) is also referred to as “acrylamide polymer (A)”. In the present disclosure, “adhesion in water” means, for example, adhesion of a cured product to a substrate in water; adhesion of the cured product to a substrate after the cured product and the substrate are immersed in water. Say.

In formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. In the present disclosure, “*” represents a binding site with another structure.

In formula (II), R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ⁵ represents 1 carbon atom. To a divalent group of 50, R ⁶ represents an alkoxyl group or a hydroxyl group, and R ⁷ and R ⁸ each independently have a hydrogen atom, a halogen atom, an alkoxyl group, a hydroxyl group, or a substituent. It represents a monovalent hydrocarbon group having 1 to 30 carbon atoms.

The composition containing the acrylamide polymer (A) can be cured by heat treatment, acid treatment or the like. It is considered that a heat treatment, an acid treatment or the like forms a crosslinked structure due to the “HO—R ² —NH—CO— group” contained in the structural unit represented by the formula (I). In the present disclosure, the composition containing the acrylamide polymer (A) is also referred to as “curable composition”.

Since the curable composition contains the acrylamide polymer (A) and the compound (B), it becomes excellent in transparency and adhesion in water when it is a cured product. The reason is not clear, but it is considered as follows.
The acrylamide polymer (A) is excellent in water solubility and transparency. Further, since the acrylamide polymer (A) can form a crosslinked structure by heat treatment, acid treatment, etc., it exhibits good water resistance upon curing. Further, it is considered that the compound (B) acts between the acrylamide polymer (A) and the base material, the peeling from the base material is suppressed, and the adhesion in water is improved.

Hereinafter, each component contained in the curable composition will be described.
(Acrylamide polymer (A))
The curable composition contains an acrylamide polymer (A). The acrylamide polymer (A) contains a structural unit represented by the following formula (I).

In formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. R ¹ is preferably a hydrogen atom. The number of carbon atoms in the “divalent hydrocarbon group having 1 to 30 carbon atoms” does not include the number of carbon atoms contained in the substituent when the divalent hydrocarbon group has a substituent. .. Hereinafter, the same applies to the “monovalent hydrocarbon group having 1 to 30 carbon atoms”.

  The divalent hydrocarbon group has 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms. As the number of carbon atoms in the hydrocarbon group is smaller, the water solubility of the acrylamide polymer (A) tends to be improved.

  As the hydrocarbon group, methylene group, ethylene group, propylene group, trimethylene group, methylethylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, ethylethylene group, 1,1-dimethylethylene Group, 1,2-dimethylethylene group, pentylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, 1,1-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, propylethylene group, ethylmethylethylene group, hexylene group, 1-methylpentylene group, 2-methylpentylene group, 3-methylpentylene group , 1-ethyltetramethylene group, 2-ethyltetramethylene group, 1-propyltrimethylene group 2-propyltrimethylene group, butylethylene group, 1,1-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 1,4 -Dimethyltetramethylene group, 1,2,3-trimethyltrimethylene group, 1,1,2-trimethyltrimethylene group, 1,1,3-trimethyltrimethylene group, 1,2,2-trimethyltrimethylene group, 1-ethyl-1-methyltrimethylene group, 2-ethyl-2-methyltrimethylene group, 1-ethyl-2-methyltrimethylene group, 2-ethyl-1-methyltrimethylene group, 2,2-ethylmethyl Examples thereof include a trimethylene group, a heptylene group, an octylene group, a nonylene group and a decylene group.

  From the viewpoint of curability, the hydrocarbon group is preferably a methylene group, an ethylene group, a propylene group or a trimethylene group.

  The substituent that the hydrocarbon group may have is not particularly limited, and specific examples thereof include a halogen atom, a hydroxyl group, an alkoxyl group having 1 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms, and the like.

  The acrylamide polymer (A) may contain any structural unit in addition to the structural unit represented by the formula (I). The optional structural unit is preferably a structural unit derived from a monomer having an ethylenically unsaturated double bond group. As a monomer having an ethylenically unsaturated double bond group, an acrylamide-based monomer such as (meth) acrylamide, N-methyl (meth) acrylamide: a carboxyl group-containing monomer such as (meth) acrylic acid, fumaric acid, maleic acid, and the like. Salts; (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, and n-butyl (meth) acrylate; vinyl esters such as vinyl acetate; styrene; Examples thereof include styrene-based monomers such as sodium styrenesulfonate; olefins such as butadiene; halogen-containing monomers such as vinyl chloride and tetrafluoroethylene. In the present disclosure, “(meth) acrylic” is used as a generic term for “acrylic” and “methacrylic”.

  From the viewpoint of improving the water solubility of the acrylamide polymer (A), it is preferable that the arbitrary structural unit include a structural unit having a polar group. The polar group is not particularly limited, but a sulfonic acid group, a phosphoric acid group, an anionic substituent such as a carboxyl group and a salt thereof, a group containing ammonium, a substituent containing an onium such as a group containing phosphonium and a salt thereof, Examples include nitrogen atom-containing groups such as carbamoyl groups. The polar group is preferably an anionic substituent or a salt thereof. Examples of the salt include sodium salt, potassium salt, ammonium salt and the like.

  The structural unit having a polar group is preferably a structural unit derived from a monomer having an ethylenically unsaturated double bond group and a polar group. As a monomer having an ethylenically unsaturated double bond group and a polar group, p-styrenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, (meth) acrylic acid, (meth) acrylamidomethylpropanesulfonic acid, salts thereof, etc. Is exemplified. Among them, p-styrene sulfonate is preferable, and sodium p-styrene sulfonate is more preferable.

  Examples of the structural unit having a polar group include structural units represented by the following formula (Ia).

In formula (Ia), R ¹¹ represents a direct bond or a divalent group, and R ¹² represents a group selected from a sulfonic acid group, a phosphoric acid group, a carboxyl group, and salts thereof. The divalent group is not particularly limited, and examples thereof include a divalent group having 1 to 50 carbon atoms. The examples, preferred embodiments and the like of R ⁵ in the formula (II) described later can be applied to R ¹¹ herein.

  In the acrylamide polymer (A), the structural unit represented by the formula (I) may be contained alone or in combination of two or more. The content of the structural unit represented by the formula (I) based on all the structural units contained in the acrylamide polymer (A) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and 60 to 100 mass% is more preferable, and 65 to 100 mass% is especially preferable. When the content of the structural unit represented by the formula (I) is 30% by mass or more, good cured product adhesion in water tends to be easily obtained. On the other hand, considering the content of any structural unit, the content of the structural unit represented by the formula (I) is, for example, preferably 30 to 95% by mass, more preferably 30 to 90% by mass, and 30 to 90% by mass. 85 mass% is more preferable, and 30 to 70 mass% is especially preferable. In the present disclosure, the content of the structural unit can be confirmed by, for example, nuclear magnetic resonance spectroscopy (NMR spectroscopy).

  The acrylamide polymer (A) may contain one type of structural unit having a polar group, or may contain two or more types of structural units. When the acrylamide polymer (A) has a structural unit having a polar group, the content of the structural unit having a polar group based on all the structural units contained in the acrylamide polymer (A) is 5 to 70% by mass. It is preferably 10 to 70% by mass, more preferably 15 to 70% by mass, and particularly preferably 30 to 70% by mass. When the content of the structural unit having a polar group is 5% by mass or more, the acrylamide polymer (A) tends to show better water solubility. On the other hand, considering the water resistance of the acrylamide polymer (A), the content of the structural unit having a polar group is preferably 0 to 70% by mass, more preferably 0 to 50% by mass, and 0 to 40% by mass. More preferably, 0-35 mass% is especially preferable.

  The acrylamide polymer (A) has, for example, a structure represented by the following formula (Ib).

In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. n represents an integer of 1 to 1,500, preferably 2 to 1,000, and more preferably 5 to 500. R ¹ and R ² are as described in formula (I).

  When it contains any structural unit, the acrylamide polymer (A) has, for example, a structure represented by the following formula (Ic).

In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. R ^11's each independently represent a direct bond or a divalent group, and R ^12's each independently represent a group selected from a sulfonic acid group, a phosphoric acid group, a carboxyl group, and salts thereof. n + m represents an integer of 1 to 1,500, preferably 2 to 1,000, and more preferably 5 to 500. R ¹ , R ² , R ¹¹ , and R ¹² are as described in formula (I) and formula (Ia).

  The curable composition may include the acrylamide polymer (A) alone or in combination of two or more. Further, the curable composition may contain an acrylamide polymer other than the acrylamide polymer (A). The other acrylamide polymer is a polymer containing a structural unit derived from an acrylamide monomer such as (meth) acrylamide or N-methyl (meth) acrylamide, and does not contain the structural unit represented by the formula (1). It is a polymer. In the present disclosure, the acrylamide polymer (A) and other acrylamide polymers may be collectively referred to as “acrylamide polymer”. From the viewpoint of transparency and adhesion in water when it is a cured product, the content of the acrylamide polymer (A) is preferably 50% by mass or more and 60% by mass or more based on the total amount of the acrylamide polymer. It is more preferable that the content is 70% by mass or more. The upper limit is 100% by mass.

  The acrylamide polymer (A) can be produced by a known polymerization method. In the polymerization, a chain transfer agent, a reaction initiator, a reaction accelerator and the like can be used as necessary. The terminal structure of the acrylamide polymer (A) is not particularly limited, and usually includes a structure derived from a monomer, a polymerization initiator or the like.

(Compound (B))
The curable composition contains the compound (B). The compound (B) is represented by the following formula (II).

In formula (II), R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 which may have a substituent, and R ⁵ has 1 to 50 carbon atoms. R ⁶ represents an alkoxyl group or a hydroxyl group, and R ⁷ and R ⁸ each independently have a hydrogen atom, a halogen atom, an alkoxyl group, a hydroxyl group, or a substituent. It represents a good monovalent hydrocarbon group of 1 to 30.

R ³ and R ⁴ may be the same or different from each other, and each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms.

  The monovalent hydrocarbon group has 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms. The smaller the number of carbon atoms in the hydrocarbon group, the higher the reactivity with the acrylamide polymer (A) tends to be.

  As the hydrocarbon group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, sec-pentyl group , Neo-pentyl group, t-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-icosanyl group, n-triacontanyl group and the like. Be done.

  The substituent that the hydrocarbon group may have is not particularly limited, and specific examples thereof include a halogen atom, a hydroxyl group, an alkoxyl group having 1 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms, and the like.

From the viewpoint of reactivity with the acrylamide polymer (A), at least one of R ³ and R ⁴ is preferably a hydrogen atom, and more preferably both are hydrogen atoms.

R ⁵ is a divalent group having 1 to 50 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms. The divalent group is a divalent organic group containing at least one carbon atom. As the divalent group, a hydrocarbon group which may have a substituent, an organic group containing an oxy group (-O-), an organic group containing an imino group (-NR- (R is a hydrogen atom, an alkyl group, etc.)) Groups and the like.

  As the hydrocarbon group, methylene group, ethylene group, propylene group, trimethylene group, methylethylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, ethylethylene group, 1,1-dimethylethylene Group, 1,2-dimethylethylene group, pentylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, 1,1-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, propylethylene group, ethylmethylethylene group, hexylene group, 1-methylpentylene group, 2-methylpentylene group, 3-methylpentylene group , 1-ethyltetramethylene group, 2-ethyltetramethylene group, 1-propyltrimethylene group 2-propyltrimethylene group, butylethylene group, 1,1-dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 1,4 -Dimethyltetramethylene group, 1,2,3-trimethyltrimethylene group, 1,1,2-trimethyltrimethylene group, 1,1,3-trimethyltrimethylene group, 1,2,2-trimethyltrimethylene group, 1-ethyl-1-methyltrimethylene group, 2-ethyl-2-methyltrimethylene group, 1-ethyl-2-methyltrimethylene group, 2-ethyl-1-methyltrimethylene group, 2,2-ethylmethyl Alkylene groups such as trimethylene group, heptylene group, octylene group, nonylene group and decylene group; ants such as phenylene group and methylphenylene group Such as Ren group, and the like.

  The substituent that the hydrocarbon group may have is not particularly limited, and specific examples thereof include a halogen atom, an amino group, a hydroxyl group, an alkoxyl group having 1 to 5 carbon atoms, an acyl group having 2 to 5 carbon atoms, and the like. Be done.

  Examples of the organic group containing an oxy group include a hydrocarbon group which may have a substituent in which at least one substituted or unsubstituted methylene group is replaced with an oxy group. Examples of the organic group containing an imino group include a hydrocarbon group which may have a substituent in which at least one substituted or unsubstituted methylene group is replaced with an imino group.

R ⁶ represents an alkoxyl group or a hydroxyl group. R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, an alkoxyl group, a hydroxyl group, or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.

  From the viewpoint of hydrolyzability, the alkoxyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and further preferably 1 to 3 carbon atoms.

  Examples of the alkoxyl group include a methyloxy group, an ethyloxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a sec-butyloxy group, a t-butyloxy group, an n-pentyloxy group and an isoalkoxy group. Pentyloxy group, sec-pentyloxy group, neo-pentyloxy group, t-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, Examples thereof include an n-icosyloxy group and an n-triacontyloxy group. Of these, a methyloxy group, an ethyloxy group, an n-propyloxy group, an isopropyloxy group and the like are more preferable from the viewpoint of hydrolysis property and availability.

  Examples of the halogen atom include chlorine atom, bromine atom, iodine atom and the like.

Regarding the monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, “the monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent” in R ³ and R ⁴ ”, Preferred modes, etc. can be applied.

R ⁶ , R ⁷ , and R ⁸ may be the same or different from each other. From the viewpoint of storage stability and hydrolyzability, at least one of R ⁶ , R ⁷ , and R ⁸ is preferably an alkoxyl group, and more preferably all are alkoxyl groups.

  As compound (B), 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, trimethoxy [3- (methylamino) propyl] silane , 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and the like. Among these, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3- (2-aminoethylamino) propyltrimethoxysilane from the viewpoint of the reactivity between the acrylamide polymer (A) and the substrate. , 3-aminopropyldiethoxymethylsilane, and trimethoxy [3- (methylamino) propyl] silane are preferred.

  The curable composition may include the compound (B) alone or in combination of two or more. The content of the compound (B) is preferably 1 to 200 parts by mass, more preferably 5 to 200 parts by mass, and 5 to 160 parts by mass with respect to 100 parts by mass of the acrylamide polymer (A). Is more preferable. In particular, from the viewpoint of obtaining higher transparency of the cured product, it is preferably 10 to 100 parts by mass, more preferably 10 to 50 parts by mass. When the content of the compound (B) is 1 part by mass or more, the effect of improving the adhesion in water tends to be easily obtained. When the content of the compound (B) is 200 parts by mass or less, good transparency of the cured product tends to be easily obtained.

(Arbitrary ingredients)
The curable composition may contain any component in addition to the acrylamide polymer (A) and the compound (B). Examples of optional components include additives and solvents. Examples of additives include pH adjusters, adhesion promoters, surfactants, leveling agents, antioxidants, ultraviolet deterioration inhibitors, sliding agents (polytetrafluoroethylene particles, etc.), light diffusing agents (acrylic crosslinked particles, silicones). Cross-linked particles, ultra-thin glass flakes, calcium carbonate particles, etc.), fluorescent dyes, inorganic phosphors (such as phosphors having aluminate as a mother crystal), antistatic agents, crystal nucleating agents, inorganic antibacterial agents, organic antibacterial agents , Photocatalyst type antifouling agents (titanium oxide particles, zinc oxide particles, etc.), crosslinking agents, curing agents, reaction accelerators, infrared absorbers (heat ray absorbers), photochromic agents and the like. The curable composition preferably contains a pH adjuster.

  Examples of pH adjusters include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid and nitric acid; organic bases such as ammonia, trimethylamine, triethylamine and imidazole; acetic acid and lactic acid. , Organic acids such as citric acid and tosylic acid; salts such as ammonium acetate, ammonium lactate, sodium acetate, sodium citrate, sodium lactate and the like. Among them, it is preferable to use salts such as ammonium acetate, sodium acetate, potassium acetate, etc., which have a buffering ability in the vicinity of neutrality. The pH adjusters may be used alone or in combination of two or more.

  The curable composition preferably has a total light transmittance of 90% or more, more preferably 95% or more, when a cured product having a thickness of 10 μm is formed. From the viewpoint of improving visibility, the composition is more preferably 98% or more. The same applies to the paint described below. As a method for increasing the total light transmittance, the content of the compound (B) is decreased; the structural unit represented by the formula (I) and the structure represented by the formula (Ia) contained in the acrylamide polymer (A). Examples include a method of increasing the content rate of the unit. In the present disclosure, the total light transmittance can be measured according to JIS K7361-1: 1997.

The curable composition was formed by forming a cured product having a thickness of 10 μm on a glass substrate and immersing the glass substrate with the cured product in water and performing an adhesion (cross-cut method) test. Is preferably 70 or more, more preferably 80 or more, and more than 90, based on 100 cross-cut portions before immersion. Is more preferable. The same applies to the paint described below. As a method for increasing the number of remaining crosscut portions, the content of the compound (B) is increased; in the formula (II), a compound in which at least one of R ³ and R ⁴ is a hydrogen atom, and preferably both are hydrogen atoms. The method of increasing the content of the structural unit represented by the formula (I) contained in the acrylamide polymer (A) can be used. In the present disclosure, the adhesion (cross-cut method) test can be performed according to JIS K 5600-5-6: 1999.

<Paint>
A coating material, which is an embodiment of the present invention, contains the curable composition and a solvent. The solvent preferably contains water. The larger the content of water contained in the solvent, the more preferable it can be used as an aqueous paint having excellent environmental compatibility.

  The content of the solvent is preferably 100 to 9,500 parts by mass, and preferably 300 to 9,000 parts by mass, based on 100 parts by mass of the total amount of the acrylamide polymer (A) and the compound (B). More preferably, it is more preferably 500 to 8,500 parts by mass. When the content of the solvent is 100 parts by mass or more, the acrylamide polymer (A) tends to be well dissolved. When the content of the solvent is 9,500 parts by mass or less, as a cured product, for example, a thick film can be obtained with a small number of times of coating, and the time required for drying can be suppressed, resulting in excellent workability. Tends to be obtained.

  The solvent may contain an organic solvent as a solvent other than water. As the organic solvent, a solvent that can dissolve the components contained in the paint is preferably used. As the organic solvent, methanol, ethanol, n-propanol, isopropanol, dioxane, diethyl ether, acetone, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, Propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dimethyl sulfoxide, ethylene glycol and the like can be mentioned. These organic solvents may be used alone or in combination of two or more. From the viewpoint of reducing the amount of the volatile organic compound used, the content of the organic solvent is preferably 0 to 30 parts by mass with respect to 100 parts by mass of the total amount of the solvent (total amount of water and the organic solvent). It is more preferably 0 to 15 parts by mass, further preferably 0 to 5 parts by mass, and particularly preferably 0 parts by mass.

  When the coating material contains an additive, the content of the additive is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on the mass of the coating material. More preferably, it is 0.3 to 1% by mass.

<Cured product, substrate with cured product, article>
A cured product that is an embodiment of the present invention is a cured product of the curable composition or the paint. The shape of the cured product is not particularly limited, and examples thereof include a film shape. The cured product in the form of a film can be produced, for example, by the following method.
The curable composition or paint is applied to at least a part of the surface of the substrate to form the curable composition layer. The curable composition layer thus formed is dried to remove the solvent from the curable composition layer, or after the solvent is removed, the curable composition layer is cured.

  The method for applying the curable composition or the coating material to the substrate is not particularly limited as long as it is a method capable of forming the curable composition layer in an arbitrary shape on an arbitrary place on the substrate. Examples include dipping, spraying, screen printing, spin coating, spin coating, and bar coating.

  The base material is not particularly limited, and inorganic materials such as glass, semiconductors, metal oxide insulators (titanium oxide, silicon oxide, etc.) and silicon nitride; triacetyl cellulose, polyimide, polycarbonate, acrylic polymer, cycloolefin resin. Examples of the resin include a base material formed using a metal such as aluminum, an aluminum alloy, copper, and stainless steel. The substrate may be transparent or opaque. The shape of the base material is not particularly limited, and may be, for example, a plate shape or a film shape. The curable composition or the coating composition can be suitably used for a substrate that is easily attacked by an organic solvent by suppressing the content of the organic solvent.

  The method for curing the curable composition layer is not particularly limited, and it can be cured by heat treatment, acid treatment or the like. Curing by heat treatment is preferable because it is simple. Curing should be performed using a box dryer, hot air conveyor dryer, quartz tube furnace, hot plate, rapid thermal annealing, vertical diffusion furnace, infrared curing furnace, electron beam curing furnace, microwave curing furnace, etc. You can

  The atmosphere for curing may be selected from the atmosphere, an inert atmosphere such as nitrogen, or the like. The temperature and time of the heat treatment for curing can be arbitrarily set in view of the composition conditions, work efficiency, etc., and can be set at 60 to 200 ° C. for about 10 minutes to 24 hours.

  The thickness of the cured product may be appropriately set according to the application. For example, it is 0.1 to 500 μm, preferably 1 to 100 μm, and more preferably 2 to 80 μm.

  The cured product may be provided on at least a part of the surface of the base material, and may be provided on only one surface of the base material or on both surfaces. The cured product may have a structure including only one layer or a structure including a plurality of layers in which two or more layers are laminated.

  The substrate on which the cured product is formed can be used as it is as a substrate with a cured product. Alternatively, the cured product may be used after being peeled from the substrate.

  The cured product has a total light transmittance of 90% or more, more preferably 95% or more, and 98% or more from the viewpoint of visibility when converted into a value for a thickness of 10 μm. Is more preferable. Further, the cured product preferably has a total light transmittance within the above range regardless of the thickness.

  When an adhesiveness (cross-cut method) test is performed after immersion in water, the number of remaining cross-cut portions is 70 or more, based on 100 cross-cut portions before dipping. The number is preferably 80, more preferably 80 or more, still more preferably 90 or more.

  Since the cured product has good transparency and excellent adhesion in water, an article containing a cured product or a substrate with a cured product is preferably used for applications where transparency and water resistance of the cured product are required. be able to. Examples of the article include vehicles such as automobiles, railway vehicles, aircraft, and ships; buildings having roofs, outer walls, windows, and the like; home appliances, electronic devices, packaging containers, civil engineering members, building materials, and the like.

  Hereinafter, the present invention will be described more specifically based on Examples and Comparative Examples. However, the present invention is not limited to the following examples.

<(A) component (acrylamide polymer (A))>
According to the following synthesis examples 1 to 5, solutions (A1) to (A5) of the component (A) (acrylamide polymer (A)) were prepared.

(Synthesis example 1)
In a reaction vessel of 500 mL equipped with a stirrer, a thermometer, and a cooler, N-methylol acrylamide (NMA, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and water in the compounding amounts (unit: parts by mass) shown in Table 1 were used. The mixture was added, mixed, and bubbled with nitrogen at room temperature for 1 hour. 2-Propanol (IPA, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as a chain transfer agent, ammonium persulfate (APS, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as a reaction initiator, and N, N, N ′ as a reaction accelerator. N'-Tetramethylethylenediamine (TMEDA, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at room temperature for 3 hours. After 3 hours, triethylamine was added to the reaction solution to adjust the pH to 7 to 8 to obtain a solution (A1) of the component (A). The concentration of the component (A) based on the mass of the solution (A1) was 10% by mass.

(Synthesis examples 2-5)
A solution of an acrylamide polymer in the same manner as in Synthesis Example 1 except that NMA and sodium p-styrenesulfonate (StSNa, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were used as monomers at the compounding ratios shown in Table 1. (A2) to (A5) were obtained. The concentration of the component (A) based on the mass of the solution was 10 mass%.

(viscosity)
The viscosity of the solution of the component (A) was measured according to JIS Z 8803-10: 2011 using a viscometer "TVE-22L" manufactured by Toki Sangyo Co., Ltd. As a measurement sample, 0.8 g of the solution of the component (A) was weighed and measured at 25 ° C., and a stable value after 1 to 2 minutes from the start of measurement was adopted as the measured value. The results are shown in Table 1.

  When the acrylamide polymer (A) contains the structural unit represented by the formula (I) and the structural unit having a polar group, the viscosity of the solution containing the acrylamide polymer (A) could be lowered.

<Component (B) (Compound (B))>
The following compounds were used as the component (B).
3-aminopropyltriethoxysilane (B1), 3-aminopropyltrimethoxysilane (B2), 3- (2-aminoethylamino) propyltrimethoxysilane (B3), 3-aminopropyldiethoxymethylsilane (B4) , And trimethoxy [3- (methylamino) propyl] silane (B5) (both manufactured by Tokyo Chemical Industry Co., Ltd.) were used.

<(C) component (additive)>
Water and potassium acetate were mixed (mass ratio water: potassium acetate = 100: 2.5) to prepare a solution (C1) of the component (C) (additive).

<Curable composition>
Solutions of the component (B) and the component (C) were mixed in the proportions shown in Table 2. The obtained solution was added to the solution of the component (A) and mixed to obtain curable compositions of Examples 1-15 and Comparative Examples 1-4. In addition, the numerical value in the parenthesis in a table | surface represents the compounding quantity (unit: mass part). "-" Represents that the component is not contained. In Comparative Example 3, a 10 mass% aqueous solution of polyacrylamide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used in place of the solution of the component (A), and in Comparative Example 4, triethoxy (propyl) was used in place of the component (B). ) Silane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

<Base material with cured product and evaluation>
Using the curable composition as a paint, a substrate with a cured product was prepared by the following method, and the cured product was evaluated.
The curable composition was applied onto a glass substrate having a thickness of 1.3 mm (large slide glass "S9213" manufactured by Matsunami Glass Industry Co., Ltd.) by a bar coating method to form a curable composition layer. Then, by drying and curing for 1 hour on a hot plate heated to 120 ° C., a substrate with a cured product (cured film) having a thickness of 10 μm was obtained.
The cured product was evaluated for adhesion, adhesion in water, and total light transmittance. The evaluation method is as follows. The evaluation results are shown in Table 3. "-" Indicates that the item has not been evaluated.

(Adhesion)
The adhesion of the cured product to the glass substrate was evaluated by the cross-cut method according to JIS K 5600-5-6: 1999. Using a cutter knife, 22 cuts (11 cuts × 2 directions) were made perpendicularly at 1 mm intervals to form 100 cross-cut portions (1 mm × 1 mm). A tape (Cellotape (R) "CT-18" manufactured by Nichiban Co., Ltd.) was attached to 100 cross-cut portions, and the number of cross-cut portions remaining after peeling off the tape was counted.

(Adhesion in water)
The adhesion of the cured product to the glass substrate in water was evaluated according to the following method.
A cut was made in the cured product in the same manner as in the evaluation of the adhesiveness. Then, the glass substrate was immersed in pure water at room temperature (25 ° C.), taken out after 24 hours, and extra pure water attached to the glass substrate was wiped off with a Kim towel (Nippon Paper Crecia Co., Ltd.). Immediately thereafter, a tape (Cellotape (R) "CT-18" manufactured by Nichiban Co., Ltd.) was attached to 100 cross-cut portions, and the number of cross-cut portions remaining after peeling off the tape was counted.

(Total light transmittance)
The total light transmittance (Tt) of the cured product (thickness 10 μm) was measured using a haze meter “NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K 7361-1: 1997. The total light transmittance of the cured product was determined using a glass substrate on which the cured product was not formed for reference measurement.

  As shown in Comparative Example 1, when the curable composition did not contain the compound (B), the cured product was completely peeled off after immersion in water.

  As shown in Comparative Example 2, when the curable composition did not contain the acrylamide polymer (A), even if only the compound (B) was cured, a cured product having excellent adhesion in water could not be obtained.

  As shown in Comparative Example 3, when the curable composition contains polyacrylamide having no hydroxyl group in place of the acrylamide polymer (A), the adhesion in water is improved even if the compound (B) is used. I didn't.

  As shown in Comparative Example 4, the adhesion in water was not improved even when the curable composition contained triethoxy (propyl) silane having no amino group in place of the compound (B).

  On the other hand, as shown in Examples 1 to 15, when the curable composition contained the acrylamide polymer (A) and the compound (B), the adhesion in water was improved.

  As shown in Examples 12 to 15, the adhesion in water was good even when the acrylamide polymer (A) contained a structural unit having a polar group. Moreover, the curable compositions of Examples 12 to 15 had low viscosities according to the viscosities of the solutions (A2) to (A5) of the acrylamide polymer (A).

Claims (8)

A composition comprising a polymer (A) containing a structural unit represented by the following formula (I) and a compound (B) represented by the following formula (II).

[In the formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a divalent hydrocarbon group having 1 to 30 carbon atoms, which may have a substituent. ]

[In the formula (II), R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and R ⁵ represents the number of carbon atoms. 1 to 50 divalent group, R ⁶ represents an alkoxyl group or a hydroxyl group, R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkoxyl group, a hydroxyl group, or a substituent. It represents a monovalent hydrocarbon group having 1 to 30 carbon atoms which may be possessed. ] The composition according to claim 1, wherein in the formula (II), R ³ and R ⁴ are both hydrogen atoms.   The composition according to claim 1, wherein the polymer (A) contains the structural unit represented by the formula (I) in an amount of 30% by mass or more based on the total structural units.   The composition according to claim 1, wherein the polymer (A) further contains a structural unit having a polar group.   A paint containing the composition according to any one of claims 1 to 4 and water.   The composition according to any one of claims 1 to 4, or the cured product of the coating material according to claim 5.   A substrate with a cured product, comprising the substrate and the cured product according to claim 6. An article comprising the cured product according to claim 6 or the substrate with the cured product according to claim 7.