JP2017043665A - Curable composition and cured article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition having good compatibility and a cured article having high hard coat property and low water swellability.SOLUTION: There are provided a composition containing (A) a metal salt of a polyvalent carboxylic acid compound and (B) a metal salt of a monocarboxylic acid compound, preferably a composition containing further (C) a metal salt of a diene carboxylic acid compound and a cured article obtained from the composition. There is provided a curable composition in which especially preferably the content of the (B) monocarboxylic acid compound and anion thereof is 60 mol% or more based on total 100 mol% of the total carboxylic acid compound and anion thereof.SELECTED DRAWING: None

Description

The present invention relates to a cured product having high hard coat properties, and particularly to a curable composition that can be a cured film formed on a substrate.

  Today, antireflection films with antireflection layers, antiglare films with antiglare layers, optical compensation films with optical compensation layers, transparent conductive films with transparent conductive layers, and antistatic layers are available. Formed antistatic film, metal deposited film with metal or metal oxide layer formed, metal plated film with metal plated layer, gas barrier film with gas barrier layer formed, adhesive tape with adhesive layer formed, Functional films in which various functional layers are formed on a film or sheet-like substrate, such as an optical disk with a hard coat layer, an electromagnetic wave shielding sheet with an electromagnetic wave shielding layer, and plastic glass with a heat ray absorbing layer Or a sheet is used.

  Moreover, in order to express various functions, metal salts of polymerizable unsaturated carboxylic acid compounds have been put to practical use in various applications. The polymerizable unsaturated carboxylic acid metal salt has an unsaturated bond and a metal salt structure, so that it exhibits properties as a reactive compound that can be used for polymerization, curing, etc. It is a compound that can impart an ionic bond between an anion and a metal cation, and properties derived from the metal itself. So far, metal salts of polymerizable unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, and itaconic acid are known. In particular, metal salts of (meth) acrylic acid are industrially important and sodium salts. And potassium salts are widely used as raw materials for aqueous dispersants, detergents and water-absorbing resins, and zinc salts are widely used as rubbers for tires, golf balls and the like, and as crosslinking agents for barrier layers of gas barrier films. In addition, (meth) acrylates such as magnesium, calcium, copper, and aluminum are available as industrial products or reagents. These metal salts of the polymerizable unsaturated carboxylic acid can introduce a metal into a polymerized / cured product through an ionic bond between a carboxylate anion and a metal cation (hereinafter sometimes simply referred to as an ionic bond). Various properties derived from either or both of ionic bonds and metals, such as dispersibility, water absorption, high hardness, high elasticity, and gas barrier properties, can be imparted.

  Furthermore, an ionic composition containing a diene carboxylate anion and a salt thereof (for example, Patent Document 1), a poly (carboxylic acid metal salt) graft rubber having a high modulus property in a cured state (for example, Patent Document) A number of documents are known to improve performance, such as 2).

  However, even in those cases, there is still room for improvement in the performance of the cured product such as the handleability of the composition, the hard coat property, and the water swelling property.

JP 2012-107208 A JP-A-6-206907

  The present invention has been made in view of such circumstances, and an object thereof is to provide a curable composition having good compatibility, and a cured product having high hard coat properties and low water swellability. .

  As a result of intensive studies, the present inventors have found that a specific composition can provide a cured product that has good compatibility and curability, high hard coat properties, and does not exhibit water swellability.

That is, the object of the present invention is achieved by the following (1) to (5).
(1) A composition comprising (A) a metal salt of a polycarboxylic acid compound and (B) a metal salt of a monocarboxylic acid compound. Preferably, the aqueous curable composition containing (A) a polyvalent metal salt of a polyvalent carboxylic acid compound and (B) a polyvalent metal salt of a monocarboxylic acid compound.
(2) The composition according to (1), further comprising (C) a metal salt of a diene carboxylic acid compound.
(3) The content of the (B) monocarboxylic acid compound and anions thereof is 60 mol% or more with respect to 100 mol% in total of all carboxylic acid compounds and anions thereof (1) Or the composition as described in (2).
(4) The composition according to any one of (1) to (3), wherein the (B) monocarboxylic acid compound is a monocarboxylic acid compound having one polymerizable unsaturated group in the molecule. object.
(5) A cured product obtained by curing the composition according to any one of (1) to (4).

  The composition of the present invention has good compatibility and curability, and the resulting cured product has high hard coat properties, does not exhibit water swellability, and is excellent in adhesion to a substrate when used as a cured film. It was a thing.

  The composition of the present invention contains (A) a metal salt of a polyvalent carboxylic acid compound and (B) a metal salt of a monocarboxylic acid compound. The (A) polyvalent carboxylic acid compound and the (B) monocarboxylic acid compound are each a compound that has no polymerizable unsaturated group in the molecule or one polymerizable unsaturated group in the molecule. . The metal salt is preferably a polyvalent metal salt.

  The (A) polycarboxylic acid compound will be described. The polyvalent carboxylic acid compound is a compound having at least two carboxylic acid groups (carboxyl groups) in one molecule, and preferably has no polymerizable unsaturated group (polymerizable unsaturated bond) in the molecule. . Examples of the polyvalent carboxylic acid compound include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, malic acid, maleic acid, fumaric acid, maleic acid, fumaric acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, Hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenone dicarboxylic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl ether tetracarboxylic An acid etc. are mentioned, Preferably a succinic acid and fumaric acid are mentioned. These may be used alone or in combination of two or more.

  Next, (B) the monocarboxylic acid compound will be described. The monocarboxylic acid compound in the present invention is a compound having one carboxylic acid group in the molecule. Further, it preferably has one polymerizable unsaturated group in the molecule. For example, acrylic acid, dimer of acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, crotonic acid, α-cyanocinnamic acid, cinnamic acid, and saturated or unsaturated dibasic acid anhydrides And a half ester which is a reaction product of a (meth) acrylate derivative having one hydroxyl group per molecule; or a half reaction product of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound. Examples include esters, preferably acrylic acid and methacrylic acid. These may be used alone or in combination of two or more.

  The metal constituting the metal salt of the carboxylic acid compound of (A) and (B) is preferably a polyvalent metal, and examples thereof include zinc, aluminum, magnesium, calcium, barium, tin, nickel, cobalt, and strontium. Of these, zinc, nickel and aluminum are preferred, with zinc being particularly preferred.

  The method for synthesizing the metal salt of the carboxylic acid compound (A) or (B) is not particularly limited, but after the carboxylic acid compound is dissolved in an aqueous caustic soda solution or ammonia water, In a method obtained by metathesis with an aqueous solution of a water-soluble salt, or in an organic solvent such as methyl isobutyl ketone, toluene, xylene, chlorobenzene, a carboxylic acid compound is ammonium bicarbonate and an oxide of a polyvalent metal, hydroxide or There is a method of heating to carbonate to form a polyvalent metal salt.

  Furthermore, the metal salt of the (C) diene-type carboxylic acid compound used suitably as an arbitrary component is demonstrated. The (C) diene carboxylic acid compound used in the present invention may be a monocarboxylic acid compound or a polyvalent carboxylic acid compound, but is preferably a monocarboxylic acid compound. 1,6-diene-2-carboxylate anion represented by the following general formula (1) described in JP-A-2012-107208 or 1,5-diene-2 represented by the following general formula (2) A metal salt of a diene carboxylic acid compound containing a carboxylate anion and a metal ion as a counter cation is preferable.

式中、Ｒは水素原子、またはメチル基を表す。Ｘ^１、Ｙ^１、Ｚ^１、Ｘ^２およびＹ^２は、同一若しくは異なって、メチレン基、水素原子がメチル基で置換されたメチレン基、酸素原子、硫黄原子、または、イミノ基を表す。ただし、Ｘ^１、Ｙ^１およびＺ^１のうち、少なくとも１つは、酸素原子、硫黄原子、または、イミノ基であり、Ｘ^２およびＹ^２のうち、少なくとも１つは、酸素原子、硫黄原子、または、イミノ基である。点線および実線で表される酸素原子−炭素原子−酸素原子の結合は、この結合中に含まれる２つの炭素原子−酸素原子結合が等価であり、酸素原子−炭素原子−酸素原子の結合全体で１価の陰イオンとなっていることを表す。

In the formula, R represents a hydrogen atom or a methyl group. X ¹ , Y ¹ , Z ¹ , X ² and Y ² are the same or different and each represents a methylene group, a methylene group in which a hydrogen atom is substituted with a methyl group, an oxygen atom, a sulfur atom or an imino group. However, at least one of X ¹ , Y ¹ and Z ¹ is an oxygen atom, a sulfur atom or an imino group, and at least one of X ² and Y ² is an oxygen atom, a sulfur atom, Or it is an imino group. The bond of oxygen atom-carbon atom-oxygen atom represented by a dotted line and a solid line is equivalent to the two carbon atom-oxygen atom bond contained in the bond, and the entire bond of oxygen atom-carbon atom-oxygen atom It represents a monovalent anion.

  Particularly preferred is a metal salt of a diene carboxylic acid compound containing an α- (meth) allyloxymethyl acrylate anion represented by the following general formula (3) and a metal ion as a counter cation.

式中、Ｒは、水素原子、またはメチル基を表す。点線および実線で表される酸素原子−炭素原子−酸素原子の結合は、この結合中に含まれる２つの炭素原子−酸素原子結合が等価であり、酸素原子−炭素原子−酸素原子の結合全体で１価の陰イオンとなっていることを表す。
対カチオンとして金属イオンを含むジエン系カルボン酸金属塩をさらに含有する組成物を重合・硬化させ、重合・硬化物中に金属を導入すると、さらに表面硬度や耐擦傷性などの、いわゆるハードコート性が向上する。また、同時にパッシブ型のバリア性（酸素バリア性・水蒸気バリア性等）も向上する場合もある。さらに、ジエン系カルボン酸陰イオンの一般式（１）におけるＺ^１あるいは一般式（２）におけるＹ^２がメチレン基であるような場合、即ちジエン系カルボン酸陰イオンが（メタ）アリル基を構造中に含む場合は、酸素に対して、アクティブ機構（化学的に酸素を吸収する機構）によりバリア性を発揮することも可能である。そのため、ハードコート材料、封止剤、保護膜、成形材料、ガスバリア材料、水蒸気バリア材料等に好適に用いることができる。このような効果は、金属イオンの価数が高く、金属が媒介するイオン結合により高密度な架橋体構造を形成する場合に、発現することが多い。したがって、対カチオンに含まれる金属としては、アルカリ土類金属、周期表１２〜１６族の典型金属、周期表３〜１１族の遷移金属のような、２価以上の価数を取れる多価金属が好ましい。金属の入手性や、合成の容易さを考慮すれば、さらに好ましくは、マグネシウム、カルシウム、ストロンチウム、バリウム、スカンジウム、イットリウム、ランタノイド、チタン、ジルコニウム、バナジウム、ニオブ、タンタル、クロム、モリブデン、タングステン、マンガン、鉄、ルテニウム、コバルト、ロジウム、イリジウム、ニッケル、パラジウム、白金、銅、銀、金、亜鉛、アルミニウム、ガリウム、インジウム、ケイ素、ゲルマニウム、スズ、鉛、アンチモン、ビスマスが挙げられる。クロム、マンガン、鉄、コバルト等、遷移金属元素は着色する場合が多いため、できるだけ着色させたくない場合は、マグネシウム、カルシウム、ストロンチウム、バリウム、亜鉛、アルミニウム、ガリウム、インジウム、ゲルマニウム、スズ、鉛、アンチモン、ビスマス等の典型金属、イットリウム、ランタンなどの３族、チタン、ジルコニウム等の４族の遷移金属が、特に好ましく使用できる。
上記（Ａ）〜（Ｃ）のカルボン酸化合物の多価金属塩を形成する多価金属イオンは、カルボン酸化合物に対して、そのカルボキシル基の９０モル％〜１００モル％、好ましくは９５〜１００モル％、より好ましくは９８〜１００モル％を中和する量で用いられる。この百分率を中和度と呼ぶ。

In the formula, R represents a hydrogen atom or a methyl group. The bond of oxygen atom-carbon atom-oxygen atom represented by a dotted line and a solid line is equivalent to the two carbon atom-oxygen atom bond contained in the bond, and the entire bond of oxygen atom-carbon atom-oxygen atom It represents a monovalent anion.
When a composition further containing a diene carboxylic acid metal salt containing a metal ion as a counter cation is polymerized / cured, and a metal is introduced into the polymerized / cured product, the surface hardness, scratch resistance, and other so-called hard coat properties Will improve. At the same time, passive barrier properties (oxygen barrier properties, water vapor barrier properties, etc.) may be improved. Further, when Z ¹ in the general formula (1) of the diene carboxylate anion or Y ² in the general formula (2) is a methylene group, that is, the diene carboxylate anion has a (meth) allyl group. When it is contained, it is possible to exert barrier properties against oxygen by an active mechanism (a mechanism that chemically absorbs oxygen). Therefore, it can be suitably used for hard coat materials, sealants, protective films, molding materials, gas barrier materials, water vapor barrier materials, and the like. Such an effect is often manifested when a metal ion has a high valence and a high-density crosslinked structure is formed by metal-mediated ionic bonds. Therefore, as a metal contained in the counter cation, a polyvalent metal capable of taking a valence of 2 or more, such as an alkaline earth metal, a typical metal of Groups 12 to 16 of the periodic table, and a transition metal of Groups 3 to 11 of the periodic table Is preferred. In view of the availability of metals and the ease of synthesis, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanoids, titanium, zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese are more preferable. , Iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, aluminum, gallium, indium, silicon, germanium, tin, lead, antimony, bismuth. Since transition metal elements such as chromium, manganese, iron, and cobalt are often colored, if you do not want to color as much as possible, magnesium, calcium, strontium, barium, zinc, aluminum, gallium, indium, germanium, tin, lead, Typical metals such as antimony and bismuth, group 3 metals such as yttrium and lanthanum, and group 4 transition metals such as titanium and zirconium can be particularly preferably used.
The polyvalent metal ion forming the polyvalent metal salt of the carboxylic acid compound of (A) to (C) is 90 to 100 mol%, preferably 95 to 100 mol% of the carboxyl group with respect to the carboxylic acid compound. It is used in an amount that neutralizes mol%, more preferably 98 to 100 mol%. This percentage is called the degree of neutralization.

  If the chemical equivalent of the polyvalent metal ion with respect to the carboxyl group is too small and the degree of neutralization is too low, the hard coat properties of the resulting cured product under high humidity conditions are reduced. If the chemical equivalent of the polyvalent metal ion with respect to the carboxyl group becomes too large and the neutralization degree becomes excessive, the solubility of the metal ion is lowered, and a uniform aqueous composition cannot be obtained, or a cured product produced Becomes cloudy. The amount of polyvalent metal ions and the degree of neutralization are preferably adjusted in consideration of the type of carboxylic acid compound to be used, the type and valence of the polyvalent metal compound, and the like.

  The composition used in the present invention is a water-based curable composition containing 20 to 85% by mass of water based on the total amount of the composition. If the water content is too small, it becomes difficult to uniformly dissolve or disperse the carboxylic acid compound and the polyvalent metal compound. In the composition, it is preferable that the carboxylic acid compound and the polyvalent metal compound are uniformly dissolved. If the water content is too high, gel is deposited in the process of polymerizing the wet coating film, and the appearance of the cured product is lowered, or it is difficult to remove water after polymerization.

  Although content of water is based also on the solubility with respect to the water of the polyvalent metal compound to be used, it is preferably 25 to 85% by mass, more preferably 30 to 80% by mass based on the total amount of the composition. In order to balance the polymerization reactivity in the wet coating film with the water removal efficiency after polymerization, the water content is more preferably 40 to 75% by mass.

  In this invention, solid content concentration of this composition is 15-80 mass%, Preferably it is 15-75 mass%, More preferably, it is 20-70 mass%. In the present invention, “solid content concentration” means mass% of components (total amount) other than water and other volatile solvents.

  In the present invention, the composition uses water as a solvent, but does not inhibit the uniform dissolution or dispersion of each component and does not inhibit the polymerization reaction. ) May be added.

  In the composition comprising a salt of a carboxylic acid compound and a polyvalent metal ion of the present invention, by containing both a monovalent carboxylic acid compound (monocarboxylic acid compound) and a polyvalent carboxylic acid compound as the carboxylic acid compound, It can be used as a coating agent that imparts high hard coat properties. The (B) monocarboxylic acid compound and its anion content are 60 mol% or more with respect to the total of 100 mol% of the total carboxylic acid compound and its anion, so that the composition is highly compatible and uniform. It becomes a thing. Preferably they are 65 mol% or more and 95 mol% or less, Most preferably, they are 70 mol% or more and 90 mol% or less.

  In the composition of the present invention, when the metal salts of the carboxylic acid compounds of (A) and (B) or (A) to (C) are contained, they are synthesized separately, It is preferable to mix. Each carboxylic acid compound can be identified by single crystal X-ray structure analysis, Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, gas chromatography, or the like.

  The composition thus obtained is usually further blended with other components to form a coating liquid. This will be described in detail below.

The curable composition of the present invention may contain a polymerization initiator as necessary. As the polymerization initiator, a photopolymerization initiator and a thermal polymerization initiator are representative. A photopolymerization initiator and a thermal polymerization initiator may be used in combination. Thermal polymerization initiators also include azo compounds and peroxides that are activated by irradiation with ionizing radiation.
When irradiating the wet coating film with ultraviolet rays, it is preferable to include a photopolymerization initiator in the curable composition of the present invention. Photoinitiators are sometimes simply referred to as photoinitiators or sensitizers. Examples of the photopolymerization initiator include acetophenones, benzophenones, Michler ketones, benzyls, benzoins, benzoin ethers, benzyl dimethyl ketals, thioxanthones, and mixtures of two or more thereof.
Preferred specific examples of the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, m-chloroacetophenone, p-tert-butyltrichloroacetophenone, acetophenones such as 4-dialkylacetophenone, benzophenones such as benzophenone, Michler's ketone Michler's ketones such as benzyl; benzyls such as benzyl methyl ether; benzoins such as benzoin and 2-methylbenzoin; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin butyl ether; Benzyl dimethyl ketals; thioxanthones such as thioxanthone; propiophenone, anthraquinone, acetoin Butyroin, Toruoin, benzoyl benzoate, alpha-acyloxime esters may be mentioned carbonyl compounds such as.
Examples of the photopolymerization initiator include sulfur compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide, thioxanthone, 2-chlorothioxanthone; azobisisobutyronitrile, azobis- Azo compounds such as 2,4-dimethylvaleronitrile; peroxides such as benzoyl peroxide and di-tert-butyl peroxide;
When these photopolymerization initiators are added to the curable composition, they are usually added to the curable composition in a proportion of 0.001 to 10% by mass, preferably 0.01 to 5% by mass. The photopolymerization initiator is not necessarily added, but when polymerization is performed by irradiation with ultraviolet rays, it is preferable to add a photopolymerization initiator in order to increase the polymerization efficiency. When a hydrogen abstraction type photopolymerization initiator such as benzophenone is used, a part of the carboxylic acid compound (metal salt) having a polymerizable unsaturated group is grafted to a plastic film used as a substrate, Interlayer adhesion between the ion-crosslinked polycarboxylic acid polymer film layer can be enhanced. General-purpose additives such as other sensitizers and light stabilizers may be added together with the photopolymerization initiator.
When performing thermal polymerization by heating a wet coating film, it is preferable to use a thermal polymerization initiator that is thermally dissociated to exhibit a function as an initiator. Examples of the thermal polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate; 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis. [2-Methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide], 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 4,4′-azobis ( 4-cyanovaleric acid), 2,2′-azobis (methylisobutyrate), 1,2′-azobis (N, N′-dimethyleneisobutylamidine) dihydrochloride, 2,2′-azobis [2-methyl Azo-based polymerization initiators such as —N- (2-hydroxyethyl) -propionamide and 1,1′-azobis (cyclohexane-1-carbonitrile; Hydroperoxides such as loperoxide; di-tert-butyl peroxide, dicumyl peroxide, lauroyl peroxide, benzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, tert-hexylperoxy-2 -Ethylhexanoate, tert-butyl peroxypivalate, di-isopropyl peroxydicarbonate, di-tert-butyl peroxyisophthalate, 1,1 ', 3,3'-tetramethylbutylperoxy-2- Peroxides such as ethyl hexanoate and tert-butyl peroxybutyrate, etc. When a thermal polymerization initiator is used, it is usually 0.001 to 10% by mass in the curable composition, preferably Is added at a ratio of 0.01 to 5% by mass.
The curable composition to be used in the present invention includes other carboxylic acid compounds having a polymerizable unsaturated group (metal salt) and other ionic cross-linking reactions with polyvalent metal ions, as necessary, within a range not inhibiting the polymerization. Polymers (eg, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, chitosan, etc.), glycerin, thickeners, inorganic layered compounds, dispersants, surfactants, softeners, thermal stabilizers, antioxidants, oxygen absorbers , Coloring agents, antiblocking agents, polyfunctional monomers and the like can be contained.
Examples of the polyfunctional monomer include diethylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol 400 diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, and 1,6-hexanediol diacrylate. , Diethylene glycol diacrylate, neopentyl glycol diacrylate, hydroxypivalate ester neopentyl diacrylate, tripropylene glycol diacrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, 1,4-butanediol diglycidyl ether diacrylate, Diethylene glycol diglycidyl ether diacrylate, dipropylene glycol diglycidyl ether Diacrylates such as diacrylate; Dimethacrylates such as ethylene glycol dimethacrylate and dipropylene glycol dimethacrylate; Triacrylates such as trimethylolpropane triacrylate and pentaerythritol triacrylate; Trimethylolethane trimethacrylate and trimethylolpropanetri And polyfunctional (meth) acrylates such as trimethacrylates such as methacrylate; tetrafunctional or higher acrylates such as dipentaerythritol hexaacrylate and polymethylolpropane polyacrylate;

The curable composition used in the present invention can obtain a cured film (cured product) having a high hard coat property without adding a polyfunctional monomer, but it is necessary to increase the degree of crosslinking. The polyfunctional monomer can be added in a small amount. The polyfunctional monomer is used in a proportion of preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and particularly preferably 10 parts by mass or less with respect to 100 parts by mass of all carboxylic acid compounds (metal salts). When using a polyfunctional monomer, the lower limit of the amount used is preferably 0.001 part by mass with respect to 100 parts by mass of all carboxylic acid compounds (metal salts).
The cured film (cured product) of the present invention is obtained by applying the coating liquid on a sheet-like substrate, drying and curing.

Although it does not specifically limit as a base material, Paper and a plastic film (a sheet | seat is included) are used preferably. The substrate is generally used in the form of a film or a sheet, but may be a molded body having a three-dimensional shape such as a plastic container if desired. Examples of the other substrate include a glass plate, a metal plate, and an aluminum foil. The substrate used to apply the curable composition of the present invention functions as a support for the coating film.
The type of plastic constituting the plastic film of the base material is not particularly limited. For example, high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, polypropylene, poly-4-methylpentene, and cyclic polyolefin Olefin polymers such as, and acid-modified products thereof; vinyl acetate polymers such as polyvinyl acetate, ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, polyvinyl alcohol, and modified products thereof; polyethylene terephthalate Polyesters such as polybutylene terephthalate and polyethylene naphthalate; aliphatic polyesters such as poly ε-caprolactone, polyhydroxybutyrate and polyhydroxyvalerate; nylon 6, nylon 66, nylon 12, Polyamides such as Iron 6/66 copolymer, nylon 6/12 copolymer, metaxylene adipamide / nylon 6 copolymer; polyethers such as polyethylene glycol, polyethersulfone, polyphenylene sulfide, polyphenylene oxide; Halogenated polymers such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, and polyvinylidene fluoride; acrylic polymers such as polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, and polyacrylonitrile; polyimide resin Other alkyd resin, melamine resin, acrylic resin, nitrified cotton, urethane resin, unsaturated polyester resin, phenol resin, amino resin, fluorine resin, epoxy resin, etc. used for coatings; cell Natural polymer compounds such as loin, starch, pullulan, chitin, chitosan, glucomannan, agarose and gelatin;
As a base material, the unstretched film or stretched film which consists of these plastics is preferable. If necessary, the plastic film can be subjected to pretreatment such as etching, corona discharge, plasma treatment, electron beam irradiation, or an adhesive can be applied in advance. It is possible to use, as a base material, an inorganic material such as silicon oxide, aluminum oxide, aluminum, or silicon nitride; a thin film such as a metal compound formed on the surface of a plastic film by vapor deposition, sputtering, or ion plating. it can. The surface of the plastic film used as the substrate may be printed. The plastic film may be a multilayer film made of a plurality of plastic films or a laminated film with other materials such as paper.

In order to apply the curable composition of the present invention onto a substrate, any coating method such as a spray method, a dipping method, a coating method using a coater, or a printing method using a printing machine is applied to one or both surfaces of the substrate. Can be used. When coating using a coater or printing machine, for example, gravure coaters such as direct gravure method, reverse gravure method, kiss reverse gravure method, offset gravure method; reverse roll coater, micro gravure coater, air knife coater, dip coater, Various systems such as a bar coater, comma coater, and die coater can be employed.
In the present invention, after coating the composition on a substrate to form a coating film, the coating film is dried, and then the coating film is irradiated with ionizing radiation, heated, or these By performing both treatments, each carboxylic acid compound (metal salt) is polymerized and cured.

As described above, the coating film formed from the curable composition is polymerized by irradiation with ionizing radiation and / or heat treatment to produce a polycarboxylic acid (salt) polymer. At the same time, the resulting polycarboxylic acid (salt) polymer is ionically crosslinked by polyvalent metal ions. The ion-crosslinked polycarboxylic acid (salt) polymer forms a cured film. Since the cured film is a cured film of a polycarboxylic acid (salt) polymer ionically crosslinked with polyvalent metal ions, it exhibits good hard coat properties. The thickness of the cured film is usually adjusted to be in the range of 0.001 μm to 1 mm, preferably 0.01 to 100 μm, more preferably 0.1 to 10 μm. The coating amount of the composition (coating liquid), depending on the content or solid content of the water, preferably 0.01 to 1000 g / ^{m 2,} preferably from 0.1 to 100 g / ^{m 2,} more preferably 1 ˜80 g / m ² .
As the ionizing radiation, ultraviolet rays, electron beams (beta rays), gamma rays and alpha rays are preferable, and ultraviolet rays and electron beams are more preferable. In order to irradiate ionizing radiation, an apparatus that generates each radiation source is used. In order to irradiate an electron beam, an accelerated electron beam extracted from an electron beam accelerator of 20 to 2000 kV is usually used. The irradiation dose of the accelerated electron beam is usually 1 to 300 kGy, preferably 5 to 200 kGy. The penetration depth of the electron beam into the irradiated object varies depending on the acceleration voltage. The higher the acceleration voltage, the deeper the electron beam penetrates. When an electron beam is used, the adhesiveness between a base material and a cured film can be improved by the grafting reaction of the carboxylic acid compound (metal salt) which has a polymerizable unsaturated group with respect to base materials, such as a plastic film.
To irradiate ultraviolet rays, using UV irradiation devices such as germicidal lamps, fluorescent lamps for ultraviolet rays, carbon arc, xenon lamps, low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, electrodeless lamps, Irradiate light including a wavelength region of 200 to 400 nm. The lamp output of the UV irradiation device is displayed as an output wattage (W / cm) per 1 cm of emission length. As the wattage per unit length increases, the ultraviolet intensity generated increases. The lamp output is usually selected from the range of 30 to 300 W / cm. The light emission length is usually selected from the range of 40 to 2500 mm.
In order to heat the wet coating film to form a cured film, the wet coating film is usually heated to a temperature of 50 to 250 ° C, preferably 60 to 220 ° C, more preferably 70 to 200 ° C. Examples of the heating means include a method of heating the coating film using a heater, and a method of passing the coating film through a heating furnace whose temperature is controlled. The heating time is usually 1 to 120 minutes, preferably 3 to 60 minutes, more preferably 5 to 30 minutes. The lower the heating temperature, the longer the heating time, and the higher the heating temperature, the shorter the heating time is preferable from the viewpoint of hard coat properties of the cured film.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.
1. Preparation of carboxylic acid compound Zn salt-solution (Preparation Example 1)
In a reactor containing a stirrer, 1.5 g (20.8 mmol) of AA (acrylic acid), 0.49 g (4.2 mmol) of succinic acid, 0.59 g of AOMA-A (α-allyloxymethylacrylic acid) ( 4.2 mmol) and 8.17 g of ultrapure water were added and dissolved by stirring with a magnetic stirrer. While cooling in a water bath, 1.37 g of zinc oxide (ZnO) was added to carry out a neutralization reaction. After stirring until the solution is colorless and transparent, excess ZnO is filtered off (filter: membrane filter manufactured by ADVANTEC (polytetrafluoroethylene, pore size 0.20 μm)) to obtain a carboxylic acid compound Zn salt-water solution. Was made.
As for the synthesis of AOMA-A, according to the previous reports (Japanese Patent Laid-Open Nos. 10-226669 and 2012-107208), a hydrolysis step using an aqueous sodium hydroxide solution using Me-AMA as a starting material, and an aqueous solution containing sulfuric acid. It was synthesized through a summing step and an extraction / separation step using an organic solvent.

Preparation Examples 2 to 14 were also produced in the same manner as Preparation Example 1 so that the blending ratios shown in Tables 1 and 2 were obtained.
2. Preparation of curable composition Carboxylic acid compound Zn salt—To the carboxylic acid compound Zn salt in the aqueous solution, 3 parts by weight of photopolymerization initiator Irgacure 2959 and 0.8 part by weight of surface conditioner 215M were added, and magnetic. Stir with a stirrer to dissolve. The mixture was filtered through a polytetrafluoroethylene membrane filter (ADVANTEC, pore size 0.20 μm) to obtain a curable composition.
3. Evaluation of compatibility Immediately after the above "1. Preparation of carboxylic acid compound Zn salt-solution" and after standing for 1 week, the appearance of the solution was observed and evaluated according to the following criteria.
◯: No change in appearance ×: Liquid is cloudy or precipitate (precipitate) is generated Tables 1 and 2 show the evaluation results. In addition, the ratio of each compound is molar ratio, and a solvent is contained 70 mass% of a composition. Further, zinc (Zn) was used as a metal salt, and a metal salt of a carboxylic acid compound having a neutralization degree of 100% was used except for a part thereof.

表１及び表２の結果から本発明の効果を確認できた。

From the results of Tables 1 and 2, the effect of the present invention was confirmed.

  By comparison between Preparation Examples 1 to 3 and Preparation Examples 4 to 8, (A) a zinc salt of a polycarboxylic acid compound (succinic acid) and (B) a zinc salt of a monocarboxylic acid compound (acrylic acid) are contained. In the composition, it was found that (B) the monocarboxylic acid compound (acrylic acid) zinc salt contained in a specific amount or more was excellent in compatibility after standing.

  Moreover, the comparison of Preparation Example 1 and Preparation Example 9 confirmed the superiority of using water as a solvent.

  A comparison between Preparation Example 1 and Preparation Example 11 shows that (A) the composition using succinic acid having no polymerizable unsaturated group as the polyvalent carboxylic acid compound has fumaric acid having a polymerizable unsaturated group. It was found that the composition after use was superior in compatibility after standing.

  Therefore, the composition of this invention has high compatibility compared with the conventional thing, and expresses the outstanding performance when it is set as a hardened | cured material.

  The water-based curable composition of the present invention is excellent in compatibility and curability, and is suitable as a coating liquid for forming a member in the electronic field or precision machine field and a packaging material in the food field.

Claims (5)

A composition comprising (A) a metal salt of a polyvalent carboxylic acid compound and (B) a metal salt of a monocarboxylic acid compound. The composition according to claim 1, further comprising (C) a metal salt of a diene carboxylic acid compound. The content of the (B) monocarboxylic acid compound and its anion is 60 mol% or more with respect to a total of 100 mol% of the total carboxylic acid compound and its anion, according to claim 1 or 2. The composition as described. The composition according to any one of claims 1 to 3, wherein the (B) monocarboxylic acid compound is a monocarboxylic acid compound having one polymerizable unsaturated group in the molecule. Hardened | cured material formed by hardening | curing the composition in any one of Claims 1-4.