JP5873376B2 - Polymerizable composition - Google Patents

Description

The present invention relates to a polymerizable composition that can be used as a raw material for a polymerized / cured product, a curable material, etc. in various industrial applications, a method for polymerizing / curing the same, and a polymerized / cured product thereof.

Fine particle-containing compositions such as resin compositions and curable compositions containing various functional fine particles are used in various situations depending on the function of the fine particles. Colored paints that have been used for a long time are resin compositions containing micron-order inorganic and organic fine particles, or curable compositions. In recent years, nano-order fine particles have been studied extensively, and many fine particle-containing compositions having functions unique to nano-order fine particles (transparency, UV / IR cut, refractive index control, light wavelength conversion, etc.) have been developed. ing. Thus, the fine particle-containing composition is a useful and important technology that has been widely used for a long time and is still developing.

An anion is a substance having a negative charge, and is present in an electrolyte solution or an ionic substance (so-called salt), and various inorganic and organic anions exist. Among them, the polymerizable unsaturated carboxylate anion, which is an organic anion, can be polymerized in an electrolyte solution such as an aqueous solution, and is often polymerized and cured in the form of an aqueous solution of a salt with a metal cation or an organic cation. The polymerized / cured product is mainly applied in water-based applications. As such polymerizable unsaturated carboxylate anions, anions of (meth) acrylic acid, maleic acid, and itaconic acid are known. In particular, anions of (meth) acrylic acid are highly polymerizable anions. As an ion, it is also important industrially.

A so-called “salt” is an ionic substance that is composed of an anion and a counter cation and is electrically neutral (electrically neutralized) as a whole. Salts can be roughly classified into two types: inorganic salts consisting only of inorganic substances and organic salts containing organic substances. One of the industrially important organic salts is a polymerizable unsaturated carboxylic acid metal salt composed of a polymerizable unsaturated carboxylic acid anion and a metal cation. By having an unsaturated bond and a metal salt structure, while exhibiting properties as a reactive compound that can be used for polymerization and curing, the polymerization / cured product has an ionic bond between a carboxylate anion and a metal cation, and It is a compound that can impart 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.

On the other hand, as the polymerizable unsaturated carboxylic acid compound, like (meth) acrylic acid ester, α-allyloxymethyl as a polymerizable compound having a double bond activated by conjugation with an adjacent carbonyl group is used. Compounds in which an allyloxymethyl group is introduced at the α-position of an acrylate ester, such as ethyl acrylate and α-allyloxymethyl acrylate, are disclosed (for example, see Non-Patent Document 1 and Non-Patent Document 2). It is disclosed that this compound undergoes cyclopolymerization by a radical addition polymerization mechanism to produce a soluble polymer.

Robert D. Thompson, two others, “Macromolecules”, 1992, 25, p. 6455-6459 Michio Urushizaki, 4 others, “Macromolecules”, 1999, vol. 32, p. 322-327

However, the conventional polymerizable unsaturated carboxylate anions and salts thereof are hardly soluble in an organic medium having low polarity and are often powdery or crystalline solids at room temperature. It was difficult to form a coating film by coating with a diluent, resin, or dissolution. In some cases, the polymerizability was not sufficient. Therefore, the usage, usage method and usage amount are remarkably limited. For example, a usage method in which the coating is dissolved in a general-purpose organic solvent or a reactive diluent and cured by heat, UV or the like is difficult. Therefore, even if there is a polymerizable composition containing fine particles in addition to the conventional polymerizable unsaturated carboxylate anion and a salt thereof, it is considered that the use, the usage method and the amount used are also significantly limited. It is done.

On the other hand, regarding the polymerizable unsaturated carboxylic acid compound, the compound in which an allyloxymethyl group is introduced at the α-position of an acrylate ester such as ethyl α-allyloxymethylacrylate and methyl α-allyloxymethylacrylate is described above. In the prior art documents, addition polymerization properties based on a radical or anion mechanism are disclosed, but nothing is described about α-allyloxymethyl acrylate anion and salts thereof. In addition, there is no mention of what kind of problem a compound having an allyloxymethyl group introduced at the α-position of an acrylate ester has as a polymerizable compound.

The present invention has been made in view of the above problems, and has a film forming property and a polymerization property, including a diene-based carboxylate anion or a salt thereof and fine particles, which have not been studied so far. An object is to provide an excellent polymerizable composition. Further, it provides a polymerization / curing method for the polymerizable composition, and further provides a polymerized / cured product obtained by the polymerization / curing method, that is, hardness, scratch resistance, fingerprint resistance, gas barrier property, Water vapor barrier property, oxygen absorption property, ultraviolet ray cut, infrared ray cut, color development / coloring, high refractive index, adhesion, various catalytic ability, fluorescence / luminescence ability, light amplification, dispersibility, antistatic, polymerization and cured products It is another object of the present invention to provide a polymerized / cured product having excellent characteristics expressed by introducing an ionic bond, particularly metal, and also having various characteristics derived from fine particles.

The present inventor made various investigations focusing on 1,6-diene-2-carboxylic acid compounds and 1,5-diene-2-carboxylic acid compounds, and found that 1,6-diene-2-carboxylic acid, Anion of 1,5-diene-2-carboxylic acid and its salt are new substances, and allyloxymethyl group is introduced at α-position of conventional polymerizable unsaturated carboxylate anion and its salt and acrylic ester It has been found that it has different properties from the unsaturated carboxylic acid ester-based compounds and can exhibit more useful properties. That is, the diene carboxylate anion and its salt have extremely excellent polymerizability, are easily soluble in various liquid media and resins ranging from water to general-purpose organic solvents, and have remarkable uses and usage methods. Without being limited, since it has been found that the composition can be excellent in coating properties and is excellent in film-forming properties, it is polymerizable including a diene carboxylate anion or a salt thereof and fine particles. The composition is also found to have excellent coating properties and excellent film-forming properties and polymerizability without being significantly limited in use and usage, and has the above problems. The idea is that this can be solved.

Furthermore, the polymerized / cured product has hardness, scratch resistance, fingerprint resistance, gas barrier property, water vapor barrier property, oxygen absorption property, ultraviolet ray cut, infrared ray cut, coloring / coloring, high refractive index, adhesion, various catalysts. Coating material, because it has excellent properties that are manifested by introducing ionic bonds and metal ions into the polymerized / cured product. , Ionomer resin, adhesive, sealant, adhesive, paint, pigment dispersion, reactive emulsifier, reactive surfactant, metal / metal oxide fine particle dispersion, ink, resist, MOD material, molding material, gas barrier material , Water vapor barrier material, oxygen absorbing material, lens, dental material, antibacterial agent, rubber, tire, lighting, solar cell, wiring material, electrode material, plating undercoat, optical fiber, optical waveguide, superconductivity From the materials, semiconductor chips, magnetic materials, memories, capacitors, and piezoelectric bodies, the present invention has been reached with the idea that it can be widely applied in various fields such as information technology (IT), automobiles, architecture, medical care, daily necessities, etc. Is.

That is, the present invention is a polymerizable composition comprising a diene carboxylate anion represented by the following general formula (1) or general formula (2) and fine particles.

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 the dotted line and the 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.

In the present invention, a polymerizable composition comprising α- (meth) allyloxymethylacrylate anion represented by the following general formula (3) and fine particles is preferable.

In the formula, R represents a hydrogen atom or a methyl group. The bond of oxygen atom-carbon atom-oxygen atom represented by the dotted line and the 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.

Further, the present invention is a method for polymerizing or curing the polymerizable composition, wherein the polymerization or curing method is selected from the group consisting of heating, irradiation with active energy rays, and exposure to an atmosphere containing oxygen. It is also a method for polymerizing or curing the polymerizable composition, comprising the step of applying at least one method.
Furthermore, the present invention is also a polymer or a cured product obtained by the above polymerization or curing method.

The present invention is described in detail below.
In this specification, “(meth) acrylic acid” represents acrylic acid or methacrylic acid. “(Meth) allyloxymethylacrylic acid” represents allyloxymethylacrylic acid or methallyloxymethylacrylic acid.

Regarding the constitution of the present invention, first, regarding the diene carboxylate anion and its salt, which are essential components of the polymerizable composition of the present invention, (1) the basic chemical structure of the diene carboxylate anion and its salt, ( 2) Performance derived from a diene carboxylate anion moiety, a preferred diene carboxylate anion structure, (3) Performance derived from a counter cation moiety, and a preferred counter cation structure, (4) Specific examples of diene carboxylates, (5) diene carboxylate anions and methods for producing salts thereof will be described. Next, the polymerizable composition, the polymerization / curing method thereof, and the polymerization / cured product thereof will be described.

<Diene carboxylate anion and its salt>
(1) The basic chemical structure of the diene carboxylate anion and its salt will be described.
The diene carboxylate anion in the present invention has a monovalent anion as a whole of an oxygen atom-carbon atom-oxygen atom bond as shown in the general formula (1) or (2). In the case of a highly polar solvent such as water, as in a normal carboxylate anion, it is solvated with a solvent molecule and ionized (so-called electrolyte solution), a low polarity solvent or In a poor solvent or substantially in the absence of a solvent, it exists in the state of an ionic substance (so-called salt) bound to a counter cation by an ionic bond. In the present specification, “substantially solvent-free” means a form that does not contain a solvent and a form that contains a solvent but contains a trace amount so that the solvent effect is not exhibited. Yes.

In order to confirm that the diene carboxylate anion in the present invention exists in the “anion” state, it can be confirmed by the same method as that applied to the identification of a normal carboxylate anion. This will be described in detail below.
As shown in the following general formula (4), the carboxylate anion (COO) ⁻ is equivalent to two carbon atom-oxygen atom bonds contained in the bond of oxygen atom-carbon atom-oxygen atom. It is generally known that the strength is intermediate between a C═O double bond and a C—O single bond, and the entire bond of oxygen atom-carbon atom-oxygen atom is a monovalent anion (for example, , Identification method by spectrum of organic compound (4th edition) / Tokyo Chemical Dojin, p117).

On the other hand, as shown in the following general formula (5), in the carboxylic acid or carboxylic acid ester, the two carbon atom-oxygen atom bonds contained in the bond of oxygen atom-carbon atom-oxygen atom are not equivalent.

In the formula, R represents a hydrogen atom or a hydrocarbon group.

Such a difference in bond equivalence and bonding force appears prominently in the infrared spectrum, and carboxylic acids and carboxylic acid esters have a strong absorption band derived from C═O stretching vibration in the vicinity of 1700 to 1750 cm ⁻¹ and 1200 cm. while causing absorption band derived from C-O stretching vibration in the vicinity of ^-1, the carboxylate anion, the region between the C = O stretching vibration and C-O stretching vibration (COO) ^- antisymmetric and symmetric Absorption bands derived from stretching vibrations are generated. In general, the anti-symmetric stretching absorption band near 1600 cm ^-1, symmetric stretching absorption band near 1400 cm ^-1 is evidence that a carboxylate anion structure (e.g., the identification method according to the spectrum of the organic compound (a 4th edition) / Tokyo Chemical Doujin, p118).

The diene carboxylate anion in the present invention is similar to a normal carboxylate anion, although it varies to some extent depending on the sample concentration, the type of solvent, and the type of counter cation coexisting in the electrolyte solution or ionic substance. , in the infrared spectrum, resulting opposite symmetric stretching absorption band near 1600 cm ^-1, the symmetric stretching absorption band near 1400 cm ^-1. That is, the reverse symmetric stretch absorption band of the diene carboxylate anion is generated in a region having a frequency lower than the C═O stretch vibration of the corresponding diene carboxylic acid or diene carboxylate ester, and is usually 1500 to 1650 cm ^−1. Observed between. In addition, the symmetric stretch absorption band of the diene carboxylate anion is generated in a region having a higher frequency than the C—O stretch vibration of the corresponding diene carboxylic acid or diene carboxylate, and is usually 1300 to 1500 cm ⁻¹ . Observed between. Note that in the infrared spectrum of a sample containing a diene carboxylate anion, the C═O stretching vibration of the carboxylic acid may disappear almost completely, or significant intensity absorption may be observed. Depending on the synthesis conditions, the raw material carboxylic acid added excessively may remain, and the remaining protic neutral low molecular weight compounds such as water and alcohol and the diene carboxylic acid anion. This is because proton exchange may occur, and depending on the analysis conditions, absorption due to the strong C═O stretching vibration of carboxylic acid may be observed.

The unique phenomenon that can be attributed to the carboxylate anion structure can also be observed in the ¹³ C-NMR spectrum. For example, in general, the absorption of the central carbon atom of the carboxylate anion is often shifted to the lower magnetic field side than the absorption of the carbonyl carbon atom of the corresponding carboxylic acid or carboxylate ester. The same phenomenon is often observed in the diene carboxylate anion in the present invention.

Further, the diene carboxylate anion, due to the presence of the double bond of the hydrogen atom H _a and H _b in the vicinity of the carboxylate anion structure as shown in following general formula (6), ^{1 H-NMR} absorption of these H _a and H _b in the spectrum becomes a good indicator for confirming that you have a carboxylate anion structure. Specifically, in comparison with the double bond hydrogen atom of the corresponding diene carboxylic acid or carboxylic acid ester, a phenomenon in which the chemical shift values of H _a and H _b shift to a higher magnetic field side is often observed. .

The absolute value of the chemical shift value and the shift width of the characteristic absorption in the NMR spectrum vary depending on the sample concentration, the type of solvent, the type of counter cation coexisting in the electrolyte solution or ionic substance, and the like. In addition, depending on the type of counter cation, the peak may be broadened due to the formation of a polymeric stable complex, the influence of paramagnetism, etc., and fine assignment may be difficult. For example, it is considered that the peak is broadened when oxygen in the air, which is a paramagnetic substance, is easily combined with a counter cation to form a stable radical, or when the counter cation itself is a paramagnetic substance. Such peak broadening is often seen when the counter cation contains a transition metal.

The diene carboxylate anion in the present invention can be analyzed by various chromatographic techniques. For example, if an electrolyte solution containing a diene carboxylate anion or a salt containing a diene carboxylate anion is pretreated with a strong acid to obtain a diene carboxylate, it can be analyzed by gas chromatography or liquid chromatography. Examples of such strong acids include sulfuric acid, hydrochloric acid, nitric acid, organic sulfonic acid, phosphoric acid, and the like, and may be appropriately selected depending on the sample and the apparatus. In liquid chromatography, the same effect can be obtained by mixing a strong acid with the elution solvent. If ion chromatography or capillary electrophoresis is used, it can be directly analyzed as ions.

The diene carboxylate according to the present invention is an ionic substance in which an equivalent anion and a counter cation are ion-bonded to be electrically neutral as a whole (electrically neutralized), A diene carboxylate in which at least one of the anions is a diene carboxylate anion.

The diene carboxylate according to the present invention may have the same chemical formula depending on the structure and type of counter cation, solvent, sample concentration, temperature, etc. Even if the ratio of the ion to the counter cation is the same), the coordination structure may take a plurality of different structures. In addition, these different coordination structures can be easily and reversibly converted to each other, and as a result, it is not uncommon for them to be a mixture of multiple coordination structures. These multiple coordination structures are isolated or identified.・ It is not easy to quantify.
Such a phenomenon may occur when the counter cation can take a plurality of coordination numbers, and is particularly likely to occur when the counter cation is a metal atom or an atomic group composed of a metal atom. Taking a salt represented by chemical formula (RCOO) ₂ M (RCOO: carboxylate anion, M: metal cation) as an example, a plurality of coordination structures can be taken as shown in FIG. In addition, what was shown in FIG. 1 is some examples, and does not show all the coordination structure examples.
In this way, the counter cation can take multiple coordination numbers, and the carboxylate anion can also take multiple coordination ways, so even with salts of the same chemical formula, they can take different coordination structures. Can do.

In general, the carboxylate anion is often monodentate (ligidentate), bidentate (brident), bridging, etc. It is known (for example, Non-Patent Document 3, Non-Patent Document 4, Non-Patent Document 5 below).
Non-Patent Document 3: BASIC INORGANIC CHEMISTRY (SECOND EDITION) / John Wiley & Sons, p143
Non-Patent Document 4: Principles and Applications of Organotransition Metal Chemistry / UNIVERSITY SCIENCE BOOKS, p59
Non-Patent Document 5: ADVANCED INORGANIC CHEMISTRY (FIFTH EDITION) / John Wiley & Sons, p483

As described above, there are many examples of anions other than carboxylate anions in which the actual coordination structure does not match the chemical formula. For example, titanium tetraalkoxide composed of alkoxide ions (RO ⁻ ) and titanium, usually expressed as Ti (OR) ₄ , is known to be a polymer having a tetramer structure as shown in FIG. (For example, BASIC INORGANIC CHEMISTRY (SECOND EDITION) / John Wiley & Sons, p142).
Therefore, the diene carboxylate in the present invention is not a concept indicating a single coordination structure, but is a salt represented by the same chemical formula (that is, the ratio of diene carboxylate anion to counter cation is A concept that includes a plurality of different coordination structures. In other words, if the chemical formulas are the same, it is a concept that treats different coordination structures (either a single coordination structure or a mixture of multiple coordination structures) as the same. .

In the diene carboxylate according to the present invention, at least one valence of the counter cation may be occupied by the diene carboxylate anion according to the present invention, and the remaining valence is diene carboxylate anion. It may be occupied by anions (anionic ligands) other than ions. In addition to the diene carboxylate anion and other anions, a neutral molecule (neutral molecular ligand) that can donate an electron may be coordinated to the counter cation. Examples of such anions (anionic ligands) include oxide ions (O ²⁻ ), halogen ions, hydroxide ions, alkoxide ions, and carboxylate anions other than diene carboxylate anions. Acetylacetonate ion, carbonate ion, bicarbonate ion, nitrate ion, nitrite ion, sulfate ion, sulfite ion, hydrogen sulfite ion, phosphate ion, silicate ion, borate ion and the like. Examples of the neutral molecular ligand include water, alcohols, ammonia, amines, phosphines, β-ketoesters, cyclopentadiene, and the like. In addition, a large number of anions (anionic ligands) and neutral molecular ligands are known. For example, inorganic chemistry and organic metals listed as Non-Patent Documents 3 to 5 above It is mentioned everywhere in chemistry books. The diene carboxylate according to the present invention contains only one kind of such an anionic ligand or neutral molecular ligand depending on the valence of the counter cation and the possible coordination number. You can also have multiple types of different types.

From the above, the diene carboxylate in the present invention is represented by a chemical formula comprising at least a chemical formula representing a diene carboxylate anion and a chemical formula representing a counter cation. In some cases, it is represented by a chemical formula including a chemical formula representing an anion (anionic ligand) other than the diene carboxylate anion and a neutral molecular ligand. The ratio of these diene carboxylate anions, counter cations, anions other than diene carboxylate anions (anionic ligands), and neutral molecular ligands is expressed by the smallest integer ratio. It is. If the diene carboxylate anion is RCOO, the anion other than the diene carboxylate anion (anionic ligand) is X, the neutral molecular ligand is L, and the counter cation is M. In the present invention, the diene carboxylic acid is “(RCOO) _a (X) _b (L) _c (M) _d ” (a, b, c, d is the minimum integer ratio, and a, d is 1 or more. And b and c are integers of 0 or more). However, for the neutral molecular ligand L, it may be difficult to distinguish between a salt with L and a mixture of L and a salt as impurities.

(2) Performances derived from the diene carboxylate anion moiety and matters relating to a preferred diene carboxylate anion structure will be described.
The diene carboxylate anion in the present invention has extremely excellent polymerization and curability, and is solvated and ionized with a solvent molecule such as in a highly polar solvent such as water (so-called electrolyte solution). In an ionic substance (so-called salt state) bound to a counter cation by an ionic bond, such as in a low-polar solvent or a poor solvent, or substantially in the absence of a solvent.
This is because the diene carboxylate anion can be cyclopolymerized by the mechanism shown in FIG. 3, and the α-position of the double bond conjugated with the carbonyl group is sterically crowded. Nevertheless, it is considered to exhibit high polymerization / curability.

Among these, (i) in FIG. 3, which produces a polymer having a 5-membered ring or 6-membered ring structure in the main chain via a stable 5-membered ring or 6-membered ring structure from the viewpoint of polymerization activity. This mechanism is preferable. That is, the diene carboxylate anion in the present invention is preferably a 1,6-diene-2-carboxylate anion represented by the general formula (1). More preferably, when X ¹ = Z ¹ = methylene group, Y ¹ = oxygen atom, sulfur atom, imino group, more preferably X ¹ = Z ¹ = methylene group, and Y ¹ = oxygen atom, In this case, the diene carboxylate anion is an anion of α- (meth) allyloxymethylacrylic acid.

The diene carboxylate in the present invention is easily soluble in various general-purpose organic solvents, reactive diluents, and resins, and may be liquid at room temperature depending on the structure. This is because the diene carboxylate anion contains many organic groups. In particular, the diene carboxylate anion has a structure represented by the general formula (1), and X ¹ and Z ¹ are the same or different and a methylene group or a hydrogen atom is substituted with a methyl group, Y ¹ = When it is an oxygen atom, or when it is a structure represented by the general formula (2) and X ² is a methylene group or a hydrogen atom substituted with a methyl group, and Y ² is an oxygen atom, a carbon atom Since it has a large number and contains an ether structure, it exhibits excellent solubility and compatibility in various general-purpose organic solvents, reactive diluents, and resins, from low polarity to high polarity. Depending on the case, it becomes liquid at room temperature.

When the diene carboxylate anion in the present invention is such that Z ¹ in the general formula (1) or Y ² in the general formula (2) is a methylene group, that is, a (meth) allyl group is included in the structure In the presence of active oxygen, polymerization / curing based on a so-called oxygen curing (also referred to as oxidation polymerization) mechanism is possible. As a typical compound that polymerizes and cures based on the oxygen curing mechanism, there is a polyfunctional alkyl allyl ether compound. The curing mechanism is shown in FIG. 4 (FIG. 4 is a simplified conceptual diagram). The actual oxygen curing mechanism is quite complex). When Z ¹ in the general formula (1) or Y ² in the general formula (2) is a methylene group, polymerization and curing can be performed by the same mechanism as that shown in FIG.

Therefore, a preferable structure as the diene carboxylate anion is a structure represented by the general formula (1), and R is a hydrogen atom or a methyl group, When X ¹ = Z ¹ = methylene group, Y ¹ = oxygen atom, sulfur atom, imino group, R is more preferably a hydrogen atom or methyl group, X ¹ = Z ¹ = methylene group, Y ¹ = oxygen atom This is the case.

(3) A description will be given of the performance that is derived from the counter cation moiety and the preferable counter cation structure.
The counter cation affects the solubility, film-forming property, curability, and various physical properties of the cured product of the diene carboxylate. What is necessary is just to select suitably according to the objective and a use.

The counter cation can be classified into a cation that is a metal element (metal atom) or an atomic group containing a metal atom, and a cation that is an atomic group composed of a non-metal atom. Examples of the former cation include sodium ion and potassium ion. Examples of the latter include alkali ions such as quaternized ions of group 15 elements (ammonium ions, phosphonium ions, etc.), and ions obtained by cationizing typical nonmetallic elements such as onium ions (also referred to as onium ions). It is done.

When the counter cation is an atomic group containing a metal atom and an atomic group containing both a metal atom and a non-metal atom, the entire atomic group containing a metal atom and a non-metal atom is conventionally used as 1 In some cases (for example, [ZrO] ²⁺ , [(C ₂ H ₅ O) Al] ²⁺ , [(n-C ₄ H ₉ ) ₂ Sn-O-Sn (n-C ₄ H ₉ ) ₂ ] ²⁺ ) etc.). In this case, from the viewpoint of the difference in electronegativity, there is a way of thinking that an atomic group consisting of only a metal atom or a metal atom is a cation and the other part is an anion ([ZrO] ²⁺ is Zr ⁴⁺ and O ²⁻ , [(C ₂ H ₅ O) Al] ²⁺ are Al ³⁺ and C ₂ H ₅ O ⁻ , [(n—C ₄ H ₉ ) ₂ Sn—O—Sn (n—C ₄ H ₉ ) _2] ^{2+ Sn 4+} 2 pieces and ^{O 2-} and _n-C 4 _{H 9} ^- 2 pieces). The diene carboxylate according to the present invention contains the diene carboxylate anion according to the present invention as an essential anion. If the salt is electrically neutral as a whole, the counter cation is a metal atom. And the whole atomic group containing non-metallic atoms may be regarded as one cation, or the atomic group consisting only of metal atoms or metal atoms strictly is a cation, and the other part is regarded as an anion. Also good.

In particular, when the counter cation is a cation which is a metal atom or an atomic group containing a metal atom, the polymer / cured product of a composition containing a diene carboxylate has not only a characteristic derived from ionic bonds but also a metal itself. Since the derived characteristics can be imparted, the utility value is very high. That is, the diene carboxylate in the present invention is a diene carboxylate whose counter cation is a cation that is a metal atom or an atomic group containing a metal atom (hereinafter also simply referred to as a diene carboxylate metal salt). More preferred).

The metal atom (metal element) is a typical metal element or a transition metal element. Typical metals are usually alkali metals (metals consisting of elements other than hydrogen in the periodic table group 1), alkaline earth metals (metals consisting of elements of the periodic table group 2), metals consisting of elements of the periodic table group 12 A metal consisting of an element other than boron in the periodic table group 13, a metal consisting of an element excluding carbon and silicon in the group 14 of the periodic table, a metal consisting of an element excluding nitrogen, phosphorus and arsenic in the group 15 of the periodic table, In Table 16, it refers to a metal composed of elements other than oxygen, sulfur, selenium, and tellurium, but in the present invention, it may be classified as a semimetal such as boron, silicon, arsenic, selenium, or tellurium. Elements can also be included as metal atoms. A transition metal refers to a metal composed of elements of Groups 3 to 11 of the periodic table.

Hereinafter, the diene carboxylic acid according to the present invention will be described in detail mainly with respect to the case where the counter cation is a metal atom or a cation that is an atomic group containing a metal atom (hereinafter sometimes simply referred to as a metal ion). The counter cation of the salt is not limited to the following examples, and does not exclude a cation (hereinafter sometimes referred to as an organic cation) which is an atomic group composed of nonmetallic atoms.

When a diene carboxylate containing a metal ion as a counter cation is polymerized / cured and a metal is introduced into the polymerized / cured product, so-called hard coat properties such as surface hardness and scratch resistance may be improved. 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, the metal contained in the counter cation is preferably a 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. . Considering 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 , Iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, aluminum, gallium, indium, silicon, germanium, tin, lead, antimony, bismuth and the like.
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 transition metals such as yttrium and lanthanum, and group 4 transition metals such as titanium and zirconium can be particularly preferably used.

When a diene carboxylate containing a metal ion as a counter cation is polymerized / cured and a metal is introduced into the polymerized / cured product, the refractive index may be increased by introducing the metal into the polymerized / cured product. Yes, it can be preferably used for optical materials such as lenses, optical films and optical fibers. In addition, when used as an optical material, it is often advantageous that the coloring is light or colorless. From this viewpoint, the metals contained in the counter cation include magnesium, calcium, strontium, barium, zinc, and aluminum. Typical metals such as gallium, indium, germanium, tin, lead, 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.

When a diene carboxylate containing a metal ion as a counter cation is polymerized / cured and a metal is introduced into the polymerized / cured product, electromagnetic waves in a specific wavelength range may be absorbed depending on the type of the metal. That is, since it can be utilized as a light-cutting agent or a polymerizable colorant for coloring, it can be used for ultraviolet-cutting, infrared-cutting, X-ray blocking, coloring filters, and the like. For example, in the case of a colorless to light color light filter, magnesium, calcium, strontium, barium, zinc, aluminum, gallium, indium, germanium, tin, lead, antimony, bismuth and other typical metals, yttrium, lanthanum and the like 3 Group 4 transition metals such as Group, Titanium, and Zirconium are particularly preferably used.

On the other hand, when used as a coloring filter (coloring agent), transition metals belonging to Group 5-11 such as vanadium, chromium, manganese, iron, cobalt, nickel, copper, etc. can be preferably used. Furthermore, particularly when used as a colorant, by combining a plurality of metal species or an organic cation such as an ammonium salt or a phosphonium salt, light absorption characteristics that cannot be produced with a single metal ion may be exhibited. Is possible. As such a combination of cations, any combination of cations is possible, but a combination including a transition metal is particularly preferable. For example, by combining copper and lanthanum, light absorption characteristics exhibiting a bright blue color that cannot be obtained with copper alone can be developed. Moreover, in order to change the light absorption characteristics, not only the adjustment of the counter cation moiety but also the combination of anions other than the diene carboxylate anion in the present invention, or the combination of neutral ligands such as amines and phosphines. It is also effective to do.

When a diene carboxylate containing a metal ion containing a rare earth metal element as a counter cation is polymerized / cured, and the rare earth element is introduced into the polymerized / cured product, it may be able to impart fluorescence / light emission capability, It can be applied to display devices, solar cells, optical fibers, etc. For example, when europium is introduced, red fluorescence can be developed, and when erbium is introduced, application to an optical fiber utilizing light amplification is possible. Similarly to the case of using as a colorant, fluorescence and luminescence can be obtained by combining a plurality of kinds of cations, anions other than the diene carboxylate anion in the present invention, or neutral ligands such as amines and phosphines. It is also possible to adjust the characteristics. The rare earth element refers to 17 elements including lanthanides from lanthanum to lutetium and scandium and yttrium.

When a diene carboxylate containing a metal ion as a counter cation is polymerized / cured and a metal is introduced into the polymerized / cured product, the polymerized / cured product may exhibit catalytic ability depending on the introduced metal. That is, it can be used as a solid catalyst. Since the diene carboxylic acid metal salt in the present invention is easily soluble in many organic solvents, reactive diluents and resins, it can be easily processed into various forms, for example, film-like, thin-film-like, particulate-like, It is possible to obtain a solid catalyst in a preferable form suitable for the method of use. The metal may be selected according to the intended reaction, but considering the types of reactions that can be handled, typical metals of Groups 12-16 of the periodic table and transition metals of Groups 3-11 of the periodic table are preferred. Specifically, for example, titanium, zirconium, zinc, aluminum, tin, lead and bismuth are catalysts for various organic reactions such as urethanization catalysts and transesterification catalysts, and vanadium, chromium, manganese, cobalt, cerium and the like are oxidized. It can be preferably used as a catalyst. Moreover, what polymerized and hardened the diene-type carboxylate in this invention which consists of a cation containing ammonium salt and phosphonium salt as a counter cation can also be used as a catalyst.

When diene carboxylates containing metal ions as counter cations are polymerized and cured, and when metal is introduced into the polymerized / cured product, antibacterial, bactericidal, antifungal and antibiotic adhesion can be imparted Therefore, it can be applied to antibacterial coating, sterilization coating, anti-mold coating, ship bottom coating and the like. As such a metal, zinc, copper, silver and the like are particularly preferable. In addition, a polymer obtained by polymerizing and curing the diene carboxylate according to the present invention, which includes a cation containing an onium ion such as an ammonium salt or a phosphonium salt as a counter cation, may exhibit the same effect.

A polymer obtained by polymerizing and curing a diene carboxylate may be capable of imparting antistatic ability. Examples of such counter cations include organic cations such as metal ions having high affinity with water such as magnesium, calcium, and barium, and quaternized ions of group 15 elements such as ammonium ions and phosphonium ions. .

A polymer obtained by polymerizing and curing a diene carboxylate can be applied as an adhesive or a primer because it exhibits good adhesion to both an inorganic material and a resin material. The type of counter cation may be a metal ion or an organic cation, and may be appropriately selected according to the type of adherend.

The shape of the adherend may be a block shape or a plate shape, and may be selected according to the purpose and application.
As a suitable plate-shaped adherend, inorganic substrates include: glass substrate; ceramic substrate; inorganic substrate such as calcium silicate plate, asbestos slate plate, cement slate plate; aluminum plate, copper plate, stainless steel plate, Although metal base materials, such as a plated steel plate, are mentioned, this invention is not limited only to this illustration.

Examples of suitable plate-shaped adherends include resin-based (meth) acrylic resins such as polymethyl methacrylate; polystyrene, polyvinyltoluene, polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile. Copolymer, acrylonitrile-butadiene-styrene block copolymer, styrene resin such as poly (p-methylstyrene); polycarbonate; polyarylate; polyethersulfone; polyolefin resin such as polyethylene, polypropylene, ethylene-propylene; norbornene Cyclic olefin resins such as resins; halogen-containing resins such as vinyl chloride resins and chlorinated vinyl resins; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexane dimeta Polyester resins such as nylon terephthalate; polyamides such as nylon 6, nylon 66 and nylon 610; cellulose resins such as cellulose triacetate, cellulose acetate propionate and cellulose acetate butyrate; polyacetal resins; polyvinyl fluoride, polyfluoride Fluorine resins such as vinylidene, polychlorotrifluoroethylene, polyethylenetetrafluoroethylene, polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer; polyphenylene oxide; polyphenylene sulfide Polyetheretherketone, polyethernitrile, polysulfone, polyethersulfone, polyoxybenzile ; Polyamide-imide; silicone resin, resin base material and the like, the present invention is not limited only to those exemplified. Among these resins, (meth) acrylic resins, polyolefin-based resins, cyclic olefin-based resins, polyester-based resins, polyamides are versatile and adherent to those obtained by polymerizing and curing diene carboxylates. Cellulose resins and fluororesins are preferred, and (meth) acrylic resins, cyclic olefin resins, polyester resins, and cellulose resins are more preferred.

Although the thickness of the resin base material is not particularly limited, it is usually preferably about 10 to 800 μm.
In addition to the above-mentioned base materials, woody base materials such as plywood, MDF (medium density fiberboard), and particle board can also be used.

The diene carboxylate can be used as an undercoat agent when the resin is metal-plated. Usually, the types of resins that can be easily metal-plated are limited, and complicated pretreatments such as the treatment of unevenness on the surface of the resin to improve plating adhesion, treatment with a plating activator or a plating catalyst, etc. Although necessary, if a diene carboxylate is used as an undercoat agent, a part or most of the complicated pretreatment may be omitted. Such a counter cation may be a metal ion or an organic cation, and may be appropriately selected according to the type of resin or plating. A counter cation containing a transition metal is preferable, and in particular, noble metals such as silver, gold, and platinum are used. When it is included, it is possible to form metal nanoparticles at the same time as being cured by UV irradiation, and to perform electroless plating using the generated metal nanoparticles as a nucleus, or in some cases, electrolytic plating. When combined with microfabrication technology using photocuring such as photolithography and UV nanoimprint technology, fine conductive wiring and black matrix can be formed on a resin film without high-temperature heat treatment.

In addition, it is generally known that metal fine particles having a carboxylic acid moiety on the surface can be obtained from a carboxylic acid metal salt as a raw material by hydrolysis, oxidation treatment, reduction treatment, energy ray irradiation, etc. In the same manner, diene carboxylic acid metal salts containing metal ions can be made into fine particles. That is, polymerizable metal fine particles having a diene carboxylic acid moiety on the surface of the metal fine particles can also be obtained.

Diene carboxylates containing metal ions as counter cations are useful as raw materials for composites containing metal nanoparticles or metal oxide nanoparticles. In particular, when a metal (such as silver or gold) that has the property of being reduced from an ion to a metal by UV irradiation is included, the metal nanoparticles are generated at a very high concentration by being cured by UV irradiation and simultaneously generating metal nanoparticles. Thus, a uniformly dispersed composite can be easily prepared. If the particle diameter is controlled to be about several nm to 100 nm, a material having plasmon absorption peculiar to metal nanoparticles can be obtained, and it can be applied to a color material, a sensor or the like using plasmon absorption. Depending on the diameter and concentration of the metal particles, it can also be used as a conductive material. In addition, when combined with microfabrication technology using photocuring such as photolithography and UV nanoimprint technology, it is also useful as a raw material for producing fine wiring and metamaterials.

The diene carboxylate according to the present invention containing a metal ion as a counter cation can be used as a radical curable MOD (Metal Organic Decomposition) material. A conventional MOD material is a film-forming composition comprising a non-polymerizable organic solvent-soluble long-chain carboxylic acid metal salt or an organic solvent-soluble metal alkoxide, which is applied to a substrate and dried. The obtained coating film is a metal or metal oxide film (hereinafter sometimes simply referred to as a metal thin film) decomposed at high temperature, and then fired at high temperature to be densified and crystallized metal. It is a material for obtaining a thin film. However, in order to obtain a finely processed metal thin film using a conventional MOD material, the metal thin film is etched using a positive resist after the metal thin film is formed, or a high output energy beam such as an electron beam is dried. A complicated process such as irradiating the coating film to fire and crystallize only the irradiated part and an expensive apparatus are required. Since the diene carboxylic acid metal salt in the present invention has high radical curability, inexpensive energy rays such as a plate making process (photolithography) using a photomask and UV light, ultraviolet curable nanoimprint, visible light laser and infrared laser, etc. A simpler plate-making process such as direct drawing by thermosetting or thermosetting nanoimprinting can be employed.

Although a preferable metal changes according to the composition of the target metal thin film, a preferable metal species is particularly preferable for a semiconductor chip, a superconducting material, a magnetic material, a memory, a capacitor, and a piezoelectric body. Specifically, strontium, barium, scandium, yttrium, lanthanoid, titanium, zirconium, hafnium, niobium, thallium, chromium, molybdenum, manganese, iron, cobalt, nickel, copper, silver, zinc, aluminum, gallium, indium, silicon , Germanium, tin, lead, arsenic, antimony, bismuth, selenium, tellurium and the like. Also, diene carboxylate and conventional non-polymerizable metal salt can be mixed with diene carboxylate and conventional non-polymerizable metal salt. Even in the form of complex chlorination, both high radical curability and film forming properties can be achieved, and it can be suitably used as a MOD material.

In the diene carboxylic acid metal salt, when an alkali metal or alkaline earth metal is used as a metal, it is possible to obtain a polymer that is soluble or swells in an organic solvent or water, and such a polymer is dispersed. It can be used for agents, water-absorbing resins, materials for ion secondary batteries such as lithium ion batteries, and the like. Further, as will be described later, diene carboxylic acid alkali metal salts, especially sodium salts and potassium salts are also useful as intermediate raw materials for producing metal salts other than sodium salts and potassium salts.

As described above, the diene carboxylate in the present invention will exhibit various different properties depending on the type of counter cation to be combined, and is preferable as a metal atom or non-metal atom serving as a counter cation or an atomic group composed of these. Things will depend on the application of the diene carboxylate. Further, by combining an anion other than the diene carboxylic acid in the present invention, various performances can be adjusted according to the application while retaining the characteristics of the diene carboxylic acid in the present invention.
The diene carboxylate anion in the present invention can be combined with various metal atoms, nonmetal atoms, or atomic groups comprising these, and diene carboxylates that can be suitably used for various applications. It has a great technical significance in that it is an anion that can be formed.

(4) A specific example of a diene carboxylate will be described.
As described above, the diene carboxylate in the present invention is not a concept indicating a single coordination structure, but a concept including a plurality of different coordination structures as long as it is a salt represented by the same chemical formula. . In other words, if the chemical formulas are the same, it is a concept that treats different coordination structures (either a single coordination structure or a mixture of multiple coordination structures) as the same. .
When the chemical formula of the diene carboxylate is generalized, it is represented by the following general formula (7).

In the formula, A ¹ , A ² , A ³ ... Are diene carboxylate anions in the present invention and represent different types, and a1, a2, a3. Represents. X ¹ , X ² , X ³ ... Are anions (anionic ligands) other than the diene carboxylate anion in the present invention, and represent different types, b1, b2, b3 ... represents an integer of 0 or more. L ¹ , L ² , L ³ ... Are electron donating neutral molecular ligands and represent different types, and c1, c2, c3. Represent. M ¹ , M ² , M ³ ... Are counter cations composed of atoms or atomic groups and represent different types, and d 1, d 2, d 3. Represent. .., b1, b2, b3..., c1, c2, c3..., d1, d2, d3.

In the following, some specific examples will be given, and the diene carboxylate in the present invention will be explained by a chemical formula. It is not intended to be limited to these specific examples.
First, for convenience, the diene carboxylate anion is enumerated only when it contains only α-allyloxymethyl acrylate anion (AMA ion), but when it contains other diene carboxylate anions, The case where a plurality of diene carboxylate anions are included is not denied.

First, as the simplest example, an example consisting of an AMA ion and only one kind of counter cation will be shown below. The AMA ion is represented as “AMA”. (CH ₃ ) ₄ N represents a tetramethylammonium ion, and (Ph) ₄ P represents a tetraphenylphosphonium ion. In addition, the sign of each ion and the valence are omitted.
_{Li (AMA), Na (AMA} ), K (AMA), (CH 3) 4 N (AMA), (Ph) 4 P (AMA), Mg (AMA) 2, Ca (AMA) 2, Sr (AMA) ₂ , Ba (AMA) ₂ , Y (AMA) ₃ , La (AMA) ₃ , Ti (AMA) ₄ , Zr (AMA) ₄ , Cr (AMA) ₃ , Mn (AMA) ₂ , Fe (AMA) ₃ , Co (AMA) ₂ , Ni (AMA) ₂ , Cu (AMA) ₂ , Ag (AMA), Zn (AMA) ₂ , Al (AMA) ₃ , In (AMA) ₃ , Bi (AMA) ₃

An example in which an anion is combined with an oxide anion in addition to the AMA ion is shown below.
Zr (O) (AMA) ₂ , V (O) (AMA) ₂
These can also be expressed as a salt of AMA ions and a counter cation that is an atomic group composed of a metal element and a nonmetal element. _{That, Zr (O) (AMA)} 2 is AMA ions and salts of ZrO ion _{ZrO (AMA) 2, V (} O) (AMA) 2 be represented as salt VO _{(AMA) 2} of the AMA ion and VO ion You can also.

Examples of anions that are combined with carboxylate anions in addition to AMA ions are shown below. Ac represents an acetate anion, AA represents an acrylic acid anion, and MAA represents a methacrylic acid anion.
Ca (AMA) ₁ (Ac) ₁ , Ba (AMA) ₁ (AA) ₁ , Zr (AMA) ₂ (MAA) ₂ , Zn (AMA) ₁ (AA) ₁ , In (AMA) ₂ (MAA) ₁

An example in which the anion is combined with a carbon anion in addition to the AMA ion is shown. N-C ₄ H ₉ represents an n-butyl anion.
_{(N-C 4 H 9)} 2 Sn (AMA) 2, (n-C 4 H 9) 2 Pb (AMA) 2
These may be interpreted as a salt of AMA ion and (n-C ₄ H ₉ ) ₂ Sn ion, or a salt of AMA ion and (n-C ₄ H ₉ ) ₂ Pb ion.

An example in which an anion is combined with an oxide anion and a carbon anion in addition to the AMA ion will be shown.
(CH ₃ ) ₄ Sn ₂ (O) (AMA) ₂
These may be interpreted as a salt of AMA ion and (CH ₃ ) ₂ Sn—O—Sn (CH ₃ ) ₂ ion.

An example in which multiple types are combined as counter cations is shown below.
(La) ₁ (Cu) ₂ (AMA) ₇ , ((C ₂ H ₅ ) ₃ NH) ₁ (Ag) ₁ (AMA) ₂
As an example in which an anionic ligand other than carboxylic acid is included, an example in which a hydroxide ion, an alkoxide ion, or a halogen ion is included is shown.
(Ph) ₂ Sn (OH) ₁ (AMA) ₁ , (n-C ₄ H ₉ O) ₂ Ti (AMA) ₂ , Y (Cl) (AMA) ₂
As an example in which a neutral molecular ligand is included, an example in which water, methanol, and 2,2′-bipyridine are coordinated is shown. 2,2'-bipyridine is represented by bpy.
(H ₂ O) ₂ Zn (AMA) ₂ , (H ₂ O) ₁ (CH ₃ OH) ₁ Zn (AMA) ₂ , (bpy) ₂ Sm (AMA) ₃
In addition, what can generally be used as a solvent such as water, methanol, diethyl ether, tetrahydrofuran or the like is contained in the salt as a neutral molecular ligand, or is simply a mixture of a salt and a residual solvent. Is often difficult to distinguish.

Thus, the diene carboxylate according to the present invention is represented by a chemical formula representing a diene carboxylate anion, a chemical formula representing another anion and a neutral molecular ligand, and a chemical formula representing a counter cation. Is done.
The anions other than the diene carboxylate anion in the above specific examples, neutral molecular ligands, and counter cations are only examples, and are not limited thereto. Those described in Patent Documents 3 to 5 can be applied.

(5) A method for producing a diene carboxylate anion and a salt thereof will be described.
Examples of the method for producing a diene carboxylate anion and a salt thereof in the present invention include (i) a method of reacting a diene carboxylic acid or an anhydride of a diene carboxylic acid with a basic substance or a latent basic substance, ii) A diene carboxylate or diene carboxylate nitrile is hydrolyzed with a basic substance or a latent basic substance to form a diene carboxylate, and then exchanged with another cation as required. There are two major methods.

Method (i) is a kind of neutralization reaction and is also called a direct method. In some cases, method (ii) means two steps. In particular, the process of exchanging the cation at the second step for another cation is sometimes referred to as a metathesis method. If these methods are performed in an electrolyte solution, an ionized diene carboxylate anion can be obtained. Moreover, after performing these methods in a non-electrolyte solution, or performing it in an electrolyte solution, it can also be set as the state of a diene carboxylate by performing operations, such as solvent removal, solvent exchange, and extraction.
The basic substance or latent basic substance is a substance capable of generating hydroxide ions by reacting with water (which may be heated), and various organic bases such as ammonia and amines, And a simple metal, a metal oxide, a metal hydroxide, a metal alkoxide, and the like (hereinafter sometimes simply referred to as a base).
Therefore, in order to obtain a diene carboxylate anion, any one of a diene carboxylate, an anhydride of a diene carboxylate, a diene carboxylate, and a diene carboxylate nitrile is used as a raw material.

However, it is industrially disadvantageous to obtain the diene acyl group structure shown in FIG. 5 by a method other than the method of converting the α-position of acrylate ester or acrylonitrile. That is, as shown in FIG. 6, industrially, first, acrylic acid ester or acrylonitrile is used as a raw material, and then converted to diene carboxylic acid ester or diene carboxylic nitrile, followed by hydrolysis with a base to diene carboxylic acid. Diene carboxylic acid is obtained by hydrolysis with a salt or acid. When a salt of another cation is used, a direct method or a metathesis method is used. The hydrolysis of the diene carboxylic acid ester or the diene carboxylic acid nitrile is more preferably hydrolyzed with a base from the viewpoint that side reactions hardly occur and corrosion of the reaction apparatus hardly occurs. When a trace amount of alkali metal is not desired to be mixed, it may be preferable to hydrolyze with an acid using a corrosion-resistant reactor.
That is, a method for producing a diene carboxylate anion and a salt thereof, wherein 1,6-diene-2-carboxylic acid ester or nitrile, or 1,5-diene-2-carboxylic acid ester or nitrile is converted into a base. The method for producing a diene carboxylate anion and a salt thereof including a step of hydrolysis with an acidic substance or a latent basic substance or a hydrolysis with an acid is preferable as a method for producing a diene carboxylate anion and a salt thereof. This is one of the embodiments.

In the following, the industrially advantageous production method of the diene carboxylate anion and its salt in the present invention will be described in detail. As a representative example of the diene carboxylate anion and its salt, α-allyloxymethylacrylic acid An anion (AMA ion) and its salt (AMA salt) are taken up. First, a method for producing AMA ions and AMA salts of α-allyloxymethyl acrylate ester (AMA ester) or α-allyloxymethyl acrylate nitrile (AMA nitrile) by hydrolysis with a base will be described in detail. . Next, a metathesis method for converting an AMA salt obtained by hydrolysis with a base into a salt of another cation will be described in detail. Furthermore, although the AMA salt obtained by hydrolysis with a base is converted into α-allyloxymethylacrylic acid (AMA carboxylic acid), a method for producing a salt of another cation by a direct method is described in detail. The method for producing a diene carboxylate anion and a salt thereof in the present invention is not limited to these.

First, a method for producing AMA ions and AMA salts by hydrolysis of AMA ester or AMA nitrile with a base will be described.
This method is a method in which a reaction is allowed to proceed by stirring a basic substance or a latent basic substance with an AMA ester or AMA nitrile, preferably in the presence of water.
As a raw material, AMA ester is more preferable from the viewpoint of safety to living bodies.
As the AMA ester, a lower ester is preferable because of easy hydrolysis, and an ester having 1 to 5 carbon atoms such as methyl, ethyl, propyl, butyl, glycidyl, and tetrahydrofurfuryl is particularly preferable.

As the basic substance or the latent basic substance, an alkali metal or alkaline earth metal hydroxide is preferable in view of availability and reactivity. Most AMA esters are separated from alkali metal / alkaline earth metal hydroxides or their aqueous solutions, so they are suspended at the beginning of the reaction, but emulsify as the reaction progresses, and finally they are uniformly transparent. In many cases, it becomes liquid and it is easy to confirm the progress of the reaction.
As alkali metals and alkaline earth metals, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, hydroxide are available in terms of availability and ease of reaction. Barium is preferable, and sodium hydroxide and potassium hydroxide are particularly preferable.
When these alkali metal / alkaline earth metal hydroxides are used as an aqueous solution, the concentration may be appropriately selected according to the type of AMA ester, reaction temperature, etc., but preferably 0.1 to 60% by mass. 1 to 50% is more preferable, and 3 to 40% by mass is most preferable.
The reaction temperature may be appropriately selected depending on the alkali hydroxide concentration and the type of AMA ester, but is preferably -20 to 120 ° C, more preferably -10 to 100 ° C, and 0 to 80 ° C. Most preferred.

Next, a method for producing by the double decomposition method will be described.
This method includes the AMA salt comprising the cation _M ^{a +} (expressed as _{"M a} salt of AMA"), and a raw material salt composed of a cation _M ^{b +} (simply referred to as "raw material _{M b} salt"), both In some cases, the cation is exchanged by mixing in the presence of a catalyst in the presence of a catalyst to produce an AMA salt composed of the cation M _b ⁺ (expressed as “AMA M _b salt”).
The solvent is as long as it can dissolve any part of both the M _a salt and the raw material M _b salt of AMA, water, preferably an alcohol, water is most preferred.
The M _a salt of AMA, alkali metal, or alkaline earth metal salts are preferred, availability, in terms of progression easiness of the reaction, in particular sodium salts, potassium salts are preferred.

Material M _b alkali metal or alkaline earth metal other than the metal salts as salts or ammonium salts, although phosphonium salts are preferred, when using sodium or potassium as M _a, M _b sodium or alkali metal or non-potassium as Alkaline earth metals can also be used. As the raw material _Mb salt, salts with various acids soluble in a solvent can be used, and a water-soluble salt is particularly preferable. Such a salt may be appropriately selected according to the target metal, but sulfate, nitrate, hydrochloride, sulfonate, phosphate, perchlorate, hydrobromide, carbonate, Examples thereof include acetates, and sulfates, nitrates, and hydrochlorides (metal chlorides) are particularly preferable from the standpoints of availability, water solubility, stability, and ease of metal exchange.
The reaction temperature may be appropriately selected according to the type of each cation (M _a ⁺ , M _b ⁺ ), preferably −20 to 120 ° C., more preferably −10 to 100 ° C., and more preferably 0 to 80 ° C is most preferred.
M _b salt object of AMA may or may be separated without particular operation, suitable organic solvents (e.g., diethyl ether, toluene, chloroform and the like) extracted with, it may be separated.

Furthermore, a method for converting an AMA salt obtained by hydrolysis with a base into α-allyloxymethylacrylic acid (AMA carboxylic acid) and subsequently producing a salt of another cation by a direct method is described.
This process is divided into a step of obtaining an AMA carboxylic acid (previous step) and a step of converting it to a salt of another cation by a direct method performed subsequently (post step).
The preceding step is a step of treating the AMA salt with an acid (preferably a strong acid) in the presence of water, and it is simple and most preferable to mix the aqueous solution of the AMA salt and the strong acid. Preferred examples of the acid include sulfuric acid, nitric acid, hydrochloric acid, organic sulfonic acid (p-toluenesulfonic acid and the like), trifluoroacetic acid, phosphoric acid, and acidic ion exchange resins (particularly sulfonic acid type are preferable).
The reaction temperature is preferably −20 to 120 ° C., more preferably −10 to 100 ° C., and most preferably 0 to 80 ° C.
If necessary, the AMA carboxylic acid may be isolated and purified before the subsequent step. Although it does not specifically limit as an isolation / purification method, For example, the method of extracting and isolate | separating with a suitable organic solvent (For example, diethyl ether, toluene, chloroform etc.) is mentioned.

The post-stage process is a kind of neutralization reaction, and the AMA carboxylic acid obtained in the pre-stage process may be mixed with a base corresponding to the target cation. The reaction temperature is preferably −20 to 120 ° C., more preferably −10 to 100 ° C., and most preferably 0 to 80 ° C.
In the direct method, the target AMA salt is hydrolyzable and difficult to synthesize in an aqueous solution, or the AMA salt is water-soluble and difficult to extract, or the base (for example, metal hydroxide) , Amine, phosphine, etc.) are particularly effective when readily available.

The diene carboxylate in the present invention can contain an anion other than the diene carboxylate anion and a neutral molecular ligand. Such a salt can be easily obtained, for example, by hydrolysis with the above-mentioned base, metathesis method or direct method. To obtain a salt containing other carboxylate anions, e.g., in the hydrolysis step with a base or an acid, it is sufficient to coexist other carboxylic acid ester or carboxylic acid nitriles, also in double decomposition method, AMA of M _a What is necessary is just to make the Ma salt of other carboxylic acid coexist with _a salt. Further, in the direct method, other carboxylic acids may coexist. Other anions X ^- (e.g. sulfate ion, nitrate ion, halogen ion, etc.) in order to obtain a salt containing, for example, in double decomposition method, M _b salt as an anion X ^- and the multivalent M _b ions using a salt (e.g. divalent salt _M b _{(X) 2),} the amount of _{M a} salt of AMA to use (i.e. the amount of AMA ions), may be less than the equivalent of valence of _{M b.} In order to coordinate the neutral molecular ligand, the target neutral molecular ligand may be present in the reaction solution. For example, in the hydrolysis method, metathesis method or direct method, A neutral molecular ligand may be used as a solvent or added to the reaction solution.
Further, as a method for obtaining a diene carboxylate, a method of mixing two or more kinds of salts is also preferable, and a complex type salt is particularly easily obtained. For example, it is possible to obtain a composite M _a salt alone, acrylic acid -AMA carboxylic acid corresponding to the mixing ratio for mixing the M _a salt and AMA M _a salt of acrylic acid. Similarly, _M a -M _b composite salt of AMA carboxylic acid is obtained if you mixed with _{M a} salt and AMA _{M b} salt of the AMA.

<Polymerizable composition of the present invention>
The present invention is a polymerizable composition comprising the diene carboxylate anion represented by the general formula (1) or the general formula (2) and fine particles.

The diene carboxylate anion and its salt are as described above.
The total amount of diene carboxylate anion in the polymerizable composition is preferably 0.001 from the viewpoint of film forming property, curability, and fine particle content with respect to 100% by mass of the total amount of the polymerizable composition. It is -95 mass%, More preferably, it is 0.01-90 mass%.
The solid content (nonvolatile content) in the polymerizable composition is preferably 1 to 100% by mass, more preferably 5 to 100% by mass, from the viewpoint of applicability. When the diene carboxylate in the polymerizable composition has high fluidity at room temperature, it may be usable without adding a volatile component.

The polymerizable composition of the present invention contains the diene carboxylate anion and fine particles as essential components, and may contain a liquid medium and various additives as necessary.
The diene carboxylate anion, which is an essential component of the polymerizable composition of the present invention, forms a salt by ion-bonding with various cations, and the salt exhibits excellent film-forming properties at room temperature alone. However, when the counter cation is a metal ion, the fluidity tends to be lacking so that it can be applied. preferable. Therefore, the form which contains a liquid medium further as a preferable form of the polymeric composition of this invention is mentioned. Even if the diene carboxylate anion salt is fluid enough to be applied at room temperature and alone (when the counter cation is an organic cation such as an ammonium ion) In the case of a use that has a viscosity that can be molded, it is not necessary to dilute with a liquid medium.

Although it does not specifically limit as an additive, A hardening accelerator, a stabilizer, a leveling agent, a monofunctional or polyfunctional polymerizable monomer, binder resin, a coloring material, a dispersing agent, etc. are mentioned. Among these, a curing accelerator such as a radical initiator or a dryer is a component that is preferably added because it can further bring out the performance of the polymerizable composition of the present invention. A preferable form of the polymerizable composition of the present invention further includes a form containing a radical initiator and / or a dryer.

Below, (A) microparticles | fine-particles which are essential components other than the said diene carboxylate anion and its salt are demonstrated first.
Next, the (B) liquid medium contained as necessary will be described, and the additives will be described separately for (C) radical initiator, (D) dryer, (E) and other additives.

(A) Fine particles Fine particles that are essential components of the polymerizable composition of the present invention are colored, UV cut, IR cut, increased hardness, imparted rubber elasticity, improved scratch resistance, improved wear resistance, increased refractive index, Organic or inorganic fine particles used for the purpose of imparting various functions derived from the fine particles themselves such as lowering the refractive index and imparting antibacterial properties to the polymerized / cured product or improving the performance.

The particle size of the fine particles is preferably in the submicron order of about 100 nm or less when transparency is required, and preferably in the micron order of about 1 to 100 μm when hiding is required, and can be appropriately selected according to the purpose and application. Good.
The method for measuring the particle diameter may be appropriately selected according to the type of particle and the particle diameter. For example, it can be measured using an optical microscope or an electron microscope. In the case of being dispersed in a liquid medium, it can be measured by a dynamic light scattering method or the like. In the present specification, the particle diameter means an average primary particle diameter expressed as an arithmetic average value by observation with an electron microscope.

The type of fine particles may be appropriately selected according to the function desired to be imparted or improved, for example, various organic pigments or inorganic pigments for coloring, UV absorbing inorganic fine particles such as zinc oxide for UV cutting, Use high-hardness inorganic fine particles such as zirconia and silica to improve hardness and scratch resistance, polymer fine particles to give rubber elasticity, and high-refractive index fine particles such as titania and zirconia to increase the refractive index. be able to. The kind of fine particles contained in the polymerizable composition of the present invention may be only one kind or two or more kinds, or only organic fine particles, inorganic fine particles, or a mixture thereof. The fine particles may be subjected to surface treatment by a known method.

The polymerizable composition of the present invention is preferably in a state in which fine particles are dispersed. Examples of a method for producing such a state include (i) a diene carboxylate anion and a salt thereof, and a diluent. A method in which a fine particle is crushed and dispersed, preferably by adding a dispersing agent in a state containing a medium and fine particles, (ii) a diene carboxylate anion diluted with a liquid medium and its salt, and a separately prepared fine particle dispersion (Iii) A method of microparticulating a fine particle precursor by a method such as hydrolysis, oxidation, reduction, etc. in a state containing a diene carboxylate anion and its salt, a diluent medium, and a fine particle precursor. Various methods known as a method for preparing a fine particle dispersion such as. Methods (i) and (ii) can be suitably applied to both organic fine particles and inorganic fine particles, and method (iii) can be particularly suitably applied to inorganic fine particles.

Hereinafter, specific functions of the function desired to be imparted or improved and fine particles preferably selected according to the function will be described, but the present invention is not limited thereto.
When the function desired to be imparted or improved is one that emphasizes transparency, hardness, scratch resistance, and wear resistance, and the method for producing a state in which fine particles are dispersed is the method (ii) above, Examples of such a separately prepared fine particle dispersion include water of silica fine particles or an organic solvent dispersion. Specifically, for example, ST-30, ST-O, ST-N, ST-C, ST-AK, ST-AK-A, IPA-ST, MEK-ST, TOL-ST (above, Nissan Chemical Co., Ltd.) Manufactured) and the like.

When the function to be imparted or improved is focused on transparency and high refractive index, and the method of creating a state in which fine particles are dispersed is the method (ii), such a separate preparation is required. Examples of the fine particle dispersion to be prepared include water or organic solvent dispersion of zirconia fine particles. Specifically, for example, nano-use OZ, ZR, SZ (manufactured by Nissan Chemical Co., Ltd.), SZR-W, SZR-CW, SZR-M, SZR-K (manufactured by Sakai Chemical Industry Co., Ltd.), NANON5 ZR-010 (manufactured by Solar Corporation) and the like can be mentioned.

When the function to be imparted or improved is focused on UV absorption and the method for creating a state in which fine particles are dispersed is the method (ii), such fine particle dispersion prepared separately Examples of the liquid include water or an organic solvent dispersion of cerium oxide and zinc oxide fine particles. Specifically, nanouse CE, CE-T, OC-T (above, the product made by Nissan Chemical Co., Ltd.), NANON5 ZN-502, the same ZN-004 (made by the solar company) etc. are mentioned, for example.

When the function to be imparted or improved is focused on antistatic and the method for creating a state in which fine particles are dispersed is the method (ii), such fine particle dispersion prepared separately Examples of the liquid include water or an organic solvent dispersion of conductive composite inorganic oxide fine particles. Examples of such conductive composite inorganic oxides include tin-containing indium oxide (ITO), antimony-containing tin oxide (ATO), and tin oxide. Specific examples of such a fine particle dispersion include Specifically, for example, Celnax CX-Z, CX-S (manufactured by Nissan Chemical Co., Ltd.) and the like can be mentioned.

If the function to be imparted or improved is colored, fine particles of various organic or inorganic pigments can be used as the fine particles. Organic pigments include azo pigments, phthalocyanine pigments, polycyclic pigments (quinacridone, perylene, perinone, isoindolinone, isoindoline, dioxazine, thioindigo, anthraquinone, quinophthalone, metal complex System, diketopyrrolopyrrole, etc.), dye lake pigments, etc. can be used. Inorganic pigments include white and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.) and chromatic pigments (yellow lead, cadmium, chrome vermilion, nickel titanium, chrome titanium) , Yellow iron oxide, bengara, zinc chromate, red lead, ultramarine, bitumen, cobalt blue, chromium green, chromium oxide, bismuth vanadate, etc.), black pigment (carbon black, bone black, graphite, iron black, titanium black, etc.) Bright pigments (pearl pigments, aluminum pigments, bronze pigments, etc.) and fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.) can be used. As the dye, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like can be used. As a method for producing a state in which these pigments are dispersed, the above method (i) or (ii) can be publicly applied.
In this manner, the type of fine particles may be selected as appropriate according to the function desired to be imparted or improved.

The total amount of the fine particles added may be appropriately set in consideration of the above functionality according to the purpose and application, and is not particularly limited. However, the total amount of the fine particles is 0.1% with respect to 100% by mass of the total amount of the diene carboxylate anion. It is preferable to set it as 1-1000 mass%. More preferably, it is 0.5-500 mass%, More preferably, it is 1-200 mass%. Functions such as coloring and antibacterial effects may be obtained with a very small addition amount, and when adding functions such as high hardness, improved wear resistance and refractive index adjustment, the addition amount was relatively large. May be more effective.

(B) Liquid medium As mentioned above, the preferable form of the polymerizable composition of the present invention includes a form diluted with some liquid medium to a viscosity that can be applied at the temperature to be used.
The preferred viscosity of the polymerizable composition of the present invention may vary depending on the coating method, the thickness of the coating layer, etc., but is preferably 0.1 to 100,000 mPa · s, more preferably 0.5 to 50000 mPa · s, and still more preferably 1. 10000 mPa · s.
The viscosity can be measured using a commonly used viscometer such as a capillary viscometer, a falling ball viscometer, a rotational viscometer, etc., and a rotational viscometer is preferable in terms of simplicity of measurement and a wide range of application. In the present specification, the viscosity is a value at 25 ° C., and a value measured by a cone plate type rotational viscometer (E type viscometer) is used.

The liquid medium used for dilution may be a substance that is liquid at room temperature, such as low-viscosity low-molecular compounds such as water, organic solvents, and reactive diluents; and liquid oligomers and polymers having a certain degree of viscosity. Can be mentioned.

Examples of the organic solvent include those described below, but the present invention is not limited to such examples.
Monoalcohols such as methanol, ethanol, isopropanol, n-butanol, s-butanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol monoethers such as glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 3-methoxybutanol; ethylene glycol dimethyl ether, ethylene glycol Jie Glycol ethers such as ether ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono Butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, B propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, esters of glycol ethers such as 3-methoxybutyl acetate.

Methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Alkyl esters such as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl acetoacetate, ethyl acetoacetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; benzene, toluene, xylene, ethylbenzene, etc. Aromatic hydrocarbons; Aliphatic hydrocarbons such as hexane, cyclohexane, and octane; Amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; Triethylamine, dibutylamine Tributylamine, trioctylamine, amines such as pyridine.
These may be used alone or in combination of two or more, and may be appropriately selected depending on the purpose and application.

As the reactive diluent, for example, a monofunctional or polyfunctional polymerizable monomer described later can be used at room temperature.
Examples of the liquid oligomer / polymer include those having a structure in which repeating units are bonded, such as a polyether skeleton, a polysiloxane skeleton, and a polybutadiene skeleton.

The total addition amount of the liquid medium may be appropriately set according to the purpose and application, and is not particularly limited. Is preferred. More preferably, it is 0-1500 mass%, More preferably, it is 0-1000 mass%.
The liquid medium is not an essential component of the polymerizable composition of the present invention, and may not be added depending on the application, curing conditions, and the like.

(C) Radical initiator The diene carboxylate anion and its salt in the present invention can be polymerized and cured by initiating radical polymerization by heating and / or irradiation with active energy rays such as electromagnetic waves and electron beams. By using a radical initiator in combination, it can be cured more effectively.
Examples of the radical initiator include a thermal radical initiator that generates radicals by heating and a photo radical initiator that generates radicals by irradiation of active energy rays, and one or two of those usually used as radical initiators. More than seeds can be used.
Moreover, it is also preferable to add 1 type (s) or 2 or more types of the radical polymerization accelerator, photosensitizer, etc. which are used normally as needed.

As the thermal radical initiator, organic peroxide initiators and azo initiators are suitable, and specific examples include the following.
Methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetyl acetate peroxide, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1- Bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 1,1-bis (t-butylperoxy) butane, 2,2-bis (4 , 4-Di-t-butylperoxycyclohexyl) propane p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α, α '-Bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl Peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide , Stearoylpa Oxide, succinic acid peroxide, m-toluoylbenzoyl peroxide, benzoyl peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di 2-ethoxyethyl peroxydicarbonate, di-2-ethoxyhexyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-s-butyl peroxydicarbonate, di (3-methyl-3- Methoxybutyl) peroxydicarbonate, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate 1- Rohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, , 1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexanoate, 1-cyclohexyl-1-methylethyl Peroxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxy Isobutyrate, t-butyl peroxymalate, t-butyl peroxy 3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-butyl peroxyacetate, t-butyl Peroxy-m-toluylbenzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, 2,5-dimethyl-2,5-bis (m-toluylperoxy) hexane, t-hexylper Oxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyallyl monocarbonate, t-butyltrimethylsilyl peroxide, 3,3 ', 4,4'-tetra (t -Butylperoxycarbonyl) benzophenone, 2 Organic peroxide initiators such as 1,3-dimethyl-2,3-diphenylbutane.

2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl) azo] formamide, 1,1′-azobis (cyclohexane-1-carbonitrile), 2, 2'-azobis (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2, 4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2 '-Azobis [N- (4-chlorophenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [N- (4-H Rophenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [2-methyl-N- (phenylmethyl) propionamidine] dihydrochloride, 2,2'-azobis [2-methyl-N- (2 -Propenyl) propionamidine] dihydrochloride, 2,2'-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [2- (5-methyl-2- Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (4,5,6, 7-tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- 3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane ] Dihydrochloride, 2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2'-azobis [2- (2-imidazoline- 2-yl) propane], 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'-azobis {2-methyl -N- [1,1-bis (hydroxymethyl) ethyl] propionamide}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] 2,2'-azobis (2-methylpropionamide), 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), dimethyl-2,2 -Azo initiators such as azobis (2-methylpropionate), 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis [2- (hydroxymethyl) propionitrile].

The radical polymerization accelerator that can be used together with the thermal radical initiator is not particularly limited as long as it promotes the decomposition (generation of initiation radicals) of the thermal radical initiator, and those that are usually used can be used. is not. For example, organic salts, inorganic salts, oxides or metal complexes of metals such as cobalt, copper, tin, zinc, manganese, iron, zirconium, chromium, vanadium, calcium, potassium, cerium, samarium; Tertiary amine compounds; quaternary ammonium salts; thiourea compounds; ketone compounds and the like. Specifically, for example, cobalt octylate, cobalt naphthenate, zinc octylate, zinc naphthenate, zirconium octylate, zirconium naphthenate, copper octylate, copper naphthenate, manganese octylate, manganese naphthenate, dimethylaniline, Examples include triethanolamine, triethylbenzylammonium chloride, di (2-hydroxyethyl) p-toluidine, ethylenethiourea, acetylacetone, and methyl acetoacetate. Further, the diene carboxylate itself in the present invention can be such a radical polymerization accelerator.

Examples of the photo radical initiator include alkylphenone compounds, benzophenone compounds, benzoin compounds, thioxanthone compounds, halomethylated triazine compounds, halomethylated oxadiazole compounds, biimidazole compounds, oxime ester compounds, and titanocene. A compound, a benzoic acid ester compound, an acridine compound and the like are preferable, and specific examples thereof include the following.

2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2 -Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl}- 2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) Nyl] -1-butanone and other alkylphenone compounds; benzophenone, 4,4′-bis (dimethylamino) benzophenone, benzophenone compounds such as 2-carboxybenzophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin Benzoin compounds such as isobutyl ether; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone; 2- (4-methoxy Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( Halomethylated triazine compounds such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine; 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl )]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole, and other halomethylated oxadiazole compounds; 2,2′-bis (2- Chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-teto Biphenyls such as phenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, etc. Imidazole compounds; 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]-1,2-octanedione, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl]-, 1- (O-acetyloxime) ethanone and other oxime ester compounds; bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- ( 1H-pyrrol-1-yl) -phenyl) titanium compounds such as titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; Acridine-based compounds such as gin.

Sensitivity and curability can be improved by using a photosensitizer and a radical polymerization accelerator together with the photo radical initiator. As such a photosensitizer and a radical polymerization accelerator, those usually used can be used and are not particularly limited. Dye-based compounds, dialkylaminobenzene-based compounds, mercaptan-based hydrogen donors, and the like are suitable. For example, xanthene dyes, coumarin dyes, 3-ketocoumarin-based compounds, pyromethene dyes and other dye-based compounds; ethyl 4-dimethylaminobenzoate And dialkylaminobenzene compounds such as 2-ethylhexyl 4-dimethylaminobenzoate; mercaptan hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and 2-mercaptobenzimidazole.

When adding the radical initiator, the total amount added may be appropriately set according to the purpose and application, and is not particularly limited, but from the viewpoint of balance between polymerization / curability, adverse effects of decomposition products, and economic efficiency. The diene carboxylate anion or salt thereof is preferably 0.01 to 30% by mass with respect to 100% by mass. More preferably, it is 0.05-20 mass%, More preferably, it is 0.1-15 mass%.

In the case of adding the radical polymerization accelerator and photosensitizer, the total amount added may be appropriately set according to the purpose and application, and is not particularly limited, but from the balance of polymerization / curability, economy, etc. The diene carboxylate anion or a salt thereof is preferably 0.001 to 20% by mass with respect to 100% by mass. More preferably, it is 0.005-10 mass%, More preferably, it is 0.01-10 mass%.

(D) A dryer dryer is a compound having an action of promoting the decomposition of peroxides, that is, a compound that decomposes peroxides by redox action to generate oxide radicals or peroxide radicals, and is usually used as a dryer. 1 type or 2 types or more can be used.
Examples of such a dryer include, but are not limited to, for example, cobalt, copper, tin, zinc, manganese, iron, zirconium, chromium, vanadium, calcium, potassium, cerium, samarium, and other metal organic salts, inorganic salts, and oxidation. Products, or metal complexes; primary, secondary, tertiary amine compounds; quaternary ammonium salts; thiourea compounds; ketone compounds. Specifically, for example, cobalt octylate, cobalt naphthenate, copper octylate, copper naphthenate, manganese octylate, manganese naphthenate, vanadium octylate, vanadium naphthenate, dimethylaniline, triethanolamine, triethylbenzylammonium chloride , Di (2-hydroxyethyl) p-toluidine, ethylenethiourea, acetylacetone, methyl acetoacetate and the like. In addition, the diene carboxylate itself can be such a dryer.

When the above dryer is added, the total amount added may be appropriately set according to the purpose and application, and is not particularly limited. However, from the balance of curability and economy, the diene carboxylate anion or a salt thereof It is preferable to set it as 0.001-20 mass% with respect to 100 mass%. More preferably, it is 0.005-10 mass%, More preferably, it is 0.01-10 mass%.

(E) Other additives The additives other than the above (C) radical initiator and (D) dryer are not particularly limited. For example, curing accelerators other than radical initiators and dryers, stabilizers, leveling agents, Functional or polyfunctional polymerizable monomers, binder resins, dispersants, fillers, adhesion improvers, mold release agents, plasticizers, ultraviolet absorbers, infrared absorbers, matting agents, antifoaming agents, antistatic agents Agents, slip agents, surface modifiers, acid generators and the like. The main items are explained below.

<Hardening accelerator other than radical initiator and dryer>
Examples of the curing accelerator other than the radical initiator and the dryer include polyfunctional thiols. The polyfunctional thiol can act as a polyfunctional chain transfer agent in radical curing, and when the diene carboxylate in the present invention is an α- (meth) allyloxymethylcarboxylate, a (meth) allyl ether group Therefore, the curability of the diene carboxylate according to the present invention can be improved. Such a polyfunctional thiol is not particularly limited as long as it is a compound having two or more mercapto groups in the same molecule. For example, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3 -Mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3 , 5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione and the like. These may be used alone or in combination of two or more.

The total amount of the curing accelerator other than the radical initiator and the dryer may be appropriately set depending on the purpose and application, and is not particularly limited, but is 100% by mass of the diene carboxylate anion or a salt thereof. It is preferable to set it as 0-150 mass%. More preferably, it is 0-100 mass%, More preferably, it is 0-80 mass%.
The curing accelerator other than the radical initiator and the dryer is not an essential component of the polymerizable composition of the present invention, and may not be added depending on the use, curing conditions, and the like. Also good.

<Stabilizer>
Stabilizers are compounds that have the function of preventing radical polymerization and oxidative polymerization in order to improve handling and storage stability. One or more polymerization inhibitors and antioxidants that are usually used can be used. There is no particular limitation.
Examples of such compounds include phenolic compounds, organic acid copper salts, phenothiazines, phosphites, phosphines, thioethers, hindered amine compounds, ascorbic acids, thiocyanates, thiourea derivatives, nitrites, sulfites. Examples thereof include salts, thiosulfates, and hydroxylamine derivatives. Among these, phenolic compounds are preferable in terms of coloring and compatibility. Specifically, hydroquinone, methylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, p-methoxyphenol, 6-t-butyl-2, 4-xylenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methoxyphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), and the like. . In addition, it is more preferable to use these phenolic compounds in combination with stabilizers classified as so-called secondary antioxidants typified by phosphites and thioethers because the polymerization prevention property and the coloration prevention property are further enhanced.

When the stabilizer is added, the total amount added may be appropriately set according to the purpose and application, and is not particularly limited. However, from the balance of curability and economy, the diene carboxylate anion or its It is preferable to set it as 0.001-20 mass% with respect to 100 mass% of salt. More preferably, it is 0.005-10 mass%, More preferably, it is 0.01-5 mass%. In addition, depending on the type of metal, storage conditions, and the structure and use conditions of the diene carboxylate anion and its salt, the diene carboxylate anion and its salt are stable, and the addition amount of the stabilizer is 0 mass. %.

<Leveling agent>
The leveling agent is a compound having a lipophilic part and a hydrophilic part, which has a function of improving the coating property by lowering the surface tension and is usually classified as a leveling agent or a surfactant. The polymerizable composition of the present invention may have a sufficiently low surface tension even without a leveling agent, but a leveling agent may be added as necessary.

Such leveling agents include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoroalkyl ethylene oxide derivatives. And various ionic or nonionic compounds such as polyethylene glycol derivatives, alkylammonium salts, fluoroalkylammonium salts, silicone derivatives and the like, and fluorine-based and silicone derivatives are particularly preferable.

When the leveling agent is added, the total amount added may be appropriately set according to the purpose and application, and is not particularly limited, but from the balance of leveling properties, adhesion, economy, etc., the polymerizable property of the present invention. It is preferable to set it as 0.001-5 mass% in a composition. More preferably, it is 0.005-1 mass%, More preferably, it is 0.01-0.5 mass%. Further, depending on the type and amount of anions and cations contained in the composition, or other additives, the surface tension may be sufficiently low without including a leveling agent, and the addition amount of the leveling agent is 0 mass. %.

<Monofunctional or polyfunctional polymerizable monomer>
The polymerizable composition of the present invention is a monofunctional or polyfunctional polymerizable monomer (low molecular compound having a polymerizable group that can be polymerized by heating or irradiation with active energy rays) depending on the purpose and application. May be included. Of these, those that are liquid and low-viscosity at room temperature are sometimes classified as reactive diluents because they also have a viscosity adjusting function. Examples of the polymerizable group include a radical polymerizable group such as a carbon-carbon unsaturated bond, and a cationic polymerizable group such as an epoxy group, an oxetanyl group, and a vinyl ether group. One of these polymerizable groups is included in the same molecule. May have only (monofunctional), or two or more (polyfunctional). When two or more are present, the same polymerizable group or two or more different groups may be used.
Since the diene carboxylate anion in the present invention has radical polymerizability, a polymerizable monomer having a radical polymerizable group that can be cured by the same mechanism is preferable because a synergistic effect can be easily obtained.

Specific examples of the monofunctional radically polymerizable monomer include those described below.
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, T-butyl (meth) acrylate, n-amyl (meth) acrylate, s-amyl (meth) acrylate, t-amyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) acrylic acid 2-ethylhexyl, isodecyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, (meth) Stearyl acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isovo (meth) acrylate Nyl, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, ( 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, ( Phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, (meth) acrylic acid (3 , 4-epoxycyclohexyl) methyl, (meth) acrylic acid N, - dimethylaminoethyl, alpha-hydroxymethyl acrylate methyl, (meth) acrylic acid esters such as alpha-hydroxymethyl acrylate.

(Meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, and acryloylmorpholine; Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, and vinylbenzoic acid Acids; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid; unsaturated such as mono (2-acryloyloxyethyl) succinate and mono (2-methacryloyloxyethyl) succinate Monocarboxylic acids in which the chain is extended between the carboxyl group and the unsaturated group; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; aromatics such as styrene, α-methylstyrene, vinyltoluene and methoxystyrene Vinyls: methylmaleimide, ethylmaleimide, isopropylmaleimide, cyclo N-substituted maleimides such as xylmaleimide, phenylmaleimide, benzylmaleimide and naphthylmaleimide; conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate Class: methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2- Hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, etc. N-ethers; N-vinyl compounds such as N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinyl imidazole, N-vinyl morpholine, N-vinyl acetamide; non-isocyanatoethyl (meth) acrylate, allyl isocyanate, etc. Saturated isocyanates.

Moreover, when it is a carboxylic acid or ester having the same structure as the diene carboxylate anion in the present invention, that is, a compound represented by the following general formula is also suitable as a reactive diluent.

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. R ′ represents a hydrogen atom or a monovalent organic group.
In particular, R ′ is a hydrogen atom, methyl, ethyl, propyl, butyl, 2-ethylhexyl, cyclohexyl, isobornyl, dicyclopentanyl, dicyclopentenyloxyethyl, benzyl, methoxyethyl, tetrahydrofurfuryl, etc. In the case of a monovalent organic group having a hydrocarbon skeleton that may contain 12 or less oxygen atoms, the dilutability is very high, which is preferable.

Specific examples of the polyfunctional radically polymerizable monomer include those described below.
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexanedimethanol Di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerin tri (meth) acrylate , Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Lithritol hexa (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added ditrimethylolpropane tetra (meth) acrylate, ethylene oxide-added pentaerythritol tetra (meth) acrylate, ethylene oxide-added dipentaerythritol hexa (meth) acrylate , Propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added ditrimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (meth) acrylate, propylene oxide-added dipentaerythritol hexa (meth) acrylate, ε- Caprolactone-added trimethylolpropane tri (meth) acryl And polyfunctional (meth) acrylates such as ε-caprolactone-added ditrimethylolpropane tetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (meth) acrylate, and ε-caprolactone-added dipentaerythritol hexa (meth) acrylate.

Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrile Methylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethyl Polyfunctional vinyl ethers such as ethylene propane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether; (meth) acrylic acid 2-vinyloxyethyl, (meth) acrylic acid 3-vinyloxypropyl, (meth) 1-methyl-2-vinyloxyethyl acrylate, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 5-vinyloxy (meth) acrylate Pentyl, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, p-vinyloxymethylphenylmethyl (meth) acrylate, (meth) acryl 2- (vinyloxy) ethyl, (meth) vinyl ether group-containing (meth) acrylic acid esters such as ethyl acrylic acid 2- (vinyloxy ethoxy ethoxy ethoxy).

Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, Ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethyl Polyfunctional allyl ethers such as ethylene propane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, ethylene oxide-added dipentaerythritol hexaallyl ether; allyl group-containing (meth) acrylic esters such as allyl (meth) acrylate; Multifunctional (meth) acryloyl groups such as tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri (acryloyloxyethyl) isocyanurate, alkylene oxide-added tri (methacryloyloxyethyl) isocyanurate -Containing isocyanurates; polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; tolylene diisocyanate, isophorone di Polyfunctional urethane obtained by reaction of polyfunctional isocyanates such as socyanate and xylylene diisocyanate with hydroxyl-containing (meth) acrylic esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate (Meth) acrylates; polyfunctional aromatic vinyls such as divinylbenzene;

In addition, when the ester has the same structure as the diene carboxylate anion in the present invention, that is, a compound represented by the following general formula is also suitable as the reactive diluent.

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. Z represents a divalent or higher organic group, and n represents an integer of 2 or higher.

The total amount of the polymerizable monomer added may be appropriately set depending on the purpose and application, and is not particularly limited. % Is preferable. More preferably, it is 0-1000 mass%, More preferably, it is 0-800 mass%.
The polymerizable monomer is not an essential component of the polymerizable composition of the present invention, and may not be added depending on the application, curing conditions, and the like.

<Binder resin>
The binder resin is an oligomer or polymer that acts as a filler such as imparting / improving coating film formability and preventing loss of shape. Depending on the purpose and application, the binder resin may further be alkali developability, colorant dispersibility, and heat resistance. Various functions such as adhesion are imparted. As such a binder resin, one or two or more kinds of various oligomers or polymers can be used, and the binder resin is not particularly limited.

As the main chain skeleton of the binder resin, (meth) acrylic resin skeleton; polystyrene, polyvinyltoluene, polystyrene, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene block copolymer Styrene resin skeletons such as poly (p-methylstyrene); polycarbonate skeletons; polyarylate skeletons; polyethersulfone skeletons; polyolefin resin skeletons such as polyethylene, polypropylene and ethylene-propylene; cyclic olefins such as norbornene resins -Based resin skeleton; halogen-containing resin skeleton such as vinyl chloride resin and chlorinated vinyl resin; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexanedimethanol Polyester resin skeleton such as phthalate; Polyamide skeleton such as nylon 6, nylon 66, nylon 610; Cellulosic resin skeleton such as cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate; Polyacetal resin skeleton; Polyvinyl fluoride , Fluororesin skeletons such as polyvinylidene fluoride, polychlorotrifluoroethylene, polyethylene tetrafluoroethylene, polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer; polyphenylene Oxide skeleton; Polyphenylene sulfide skeleton; Polyetheretherketone skeleton; Polyethernitrile skeleton; Polysulfone bone ; Polyether sulfone skeleton; polyoxyethylene benzylidene alkylene skeleton; polyamideimide skeleton; silicone resin skeleton; polyurethane skeleton, and the like, but is not limited only to those exemplified.

In addition, a form having a polymerizable group at its terminal and / or side chain is also one of the preferred binder resin forms, and examples of such a polymerizable group include the polymerizable groups described above. A radically polymerizable group is preferable because it can easily obtain a synergistic effect with a diene carboxylate anion. The polymerizable group is usually bonded to the main chain skeleton via an ester bond, a urethane bond, an ether bond, an amide bond or the like.

The total addition amount of the binder resin may be appropriately set in consideration of the above functionality depending on the purpose and application, and is not particularly limited. It is preferable to set it as 0-1000 mass%. More preferably, it is 0-800 mass%, More preferably, it is 0-500 mass%.
The binder resin is not an essential component of the polymerizable composition of the present invention, and may not be added depending on the application, curing conditions, and the like.

<Polymerization / curing method of polymerizable composition of the present invention>
The polymerization or curing method for the polymerizable composition of the present invention includes a step of applying at least one method selected from the group consisting of heating, irradiation with active energy rays, and exposure to an atmosphere containing oxygen. .
As described above, since the diene carboxylate anion and the salt thereof in the present invention can have a radical polymerization mechanism and / or an oxidative polymerization mechanism, they are heated, irradiated with active energy rays, and exposed to an atmosphere containing oxygen. It can be cured by the following three methods. Of these methods, only one type may be used, or two or more types may be used in combination.
Such curing may be carried out in a state containing water and other volatile components (such as an organic solvent), and after applying and drying the polymerizable composition of the present invention, it contains almost no volatile components such as water. It may be done after, and it may be properly used according to the purpose and application.

The heating conditions in the polymerization / curing method by heating, that is, the polymerization / curing temperature, may be appropriately selected according to the type of diene carboxylate anion and its salt, the combination of other additive components, etc., but the curing accelerator When not using together, 30-400 degreeC is preferable, More preferably, it is 70-350 degreeC, More preferably, it is 100-350 degreeC. By setting it as such temperature, it can harden | cure easily without a hardening accelerator and can reduce thermal decomposition by excessive heating.
When using together a hardening accelerator, it can be made to harden | cure at lower temperature than the case where it does not use together, 0-400 degreeC is preferable, More preferably, it is 10-350 degreeC, More preferably, it is 20-350 degreeC.

Curing by heating may be performed in one step, may be performed in two or more steps, and may be performed before curing by irradiation with active energy rays and / or exposure to an atmosphere containing oxygen, It may be done later. For example, it is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and more preferably after processing such as development after being crosslinked to some extent by heating at a low temperature or irradiation with a short period of active energy rays. The step of curing at a high temperature of 200 ° C. or higher is also referred to as post-bake or post-cure, and is preferable because it can further promote the crosslinking reaction.

As the active energy ray in the polymerization / curing method by irradiation with the active energy ray, those usually used can be used, such as electromagnetic waves such as gamma rays, X-rays, ultraviolet rays, visible rays, infrared rays, electron rays, neutron rays. And particle beams such as proton beams. Among these, gamma rays, X-rays, ultraviolet rays, visible rays, and electron beams are preferable, ultraviolet rays, visible rays, and electron beams are more preferable, and ultraviolet rays are most preferable from the viewpoints of energy intensity, energy beam generator, and the like. . When a curing accelerator is not used in combination, it is preferable to use an active energy ray having strong energy such as gamma rays, X-rays, and electron beams. When a curing accelerator is used in combination, energy such as ultraviolet light and visible light is Active energy rays that are relatively weak but easy to generate and economical can be preferably used.

In the curing method by exposure to an atmosphere containing oxygen, the oxygen concentration in the atmosphere is preferably 5% by volume or more, more preferably 10% by volume or more, and most preferably 18% by volume or more. That is, the concentration is most preferably equal to or higher than the oxygen concentration in the air. Further, the curing method by exposure to an atmosphere containing oxygen may be used in combination with the polymerization / curing method by heating and / or the polymerization / curing method by irradiation with active energy rays. In particular, a polymerization / curing method in which heating and / or irradiation with active energy rays are performed in the air is a preferable curing method as a polymerization / curing method that can be easily used together.

<Polymerized / cured product of the polymerizable composition of the present invention>
The polymer or cured product of the present invention is obtained by the polymerization or curing method of the polymerizable composition.
In the polymerized / cured product of the present invention, many ionic bonds are introduced into the polymerized / cured product. In particular, when the diene carboxylate is a metal salt, a metal is also introduced. These ionic bonds and / or various properties depending on the metal will be exhibited. Examples of such properties include hardness, scratch resistance, fingerprint resistance, gas barrier property, water vapor barrier property, Various properties such as oxygen absorption, ultraviolet cut, infrared cut, color development / coloring, high refractive index, adhesion, various catalytic ability, fluorescence / luminous ability, light amplification, dispersibility, antistatic etc. The present invention can be applied to various application methods using various characteristics. Furthermore, it can be suitably used as a MOD material.

ADVANTAGE OF THE INVENTION According to this invention, the polymeric composition excellent in film forming property and polymerizability, and its polymerization and hardening method are provided. In addition, a polymerized / cured product obtained by the polymerization / curing method, that is, an ionic bond, and in some cases, a metal is also introduced into the polymerized / cured product, and these ionic bonds and / or various properties according to the metal (for example, , Hardness, scratch resistance, fingerprint resistance, gas barrier property, water vapor barrier property, oxygen absorption, ultraviolet ray cut, infrared ray cut, color development / coloring, high refractive index, adhesion, various catalytic ability, fluorescence / luminescence ability, light A polymerized / cured product exhibiting amplification, dispersibility, antistatic property and the like is provided.
Therefore, the polymerizable composition of the present invention and the polymerized / cured product thereof are coating materials, ionomer resins, adhesives, sealing materials, pressure-sensitive adhesives, paints, pigment dispersions, reactive emulsifiers, reactive surfactants, Dispersion of metal / metal oxide fine particles, ink, resist, MOD material, molding material, gas barrier material, water vapor barrier material, oxygen absorbing material, lens, dental material, antibacterial agent, rubber, tire, lighting, solar cell, wiring material, Electrode materials, plating undercoats, optical fibers, optical waveguides, superconducting materials, semiconductor chips, magnetic materials, memories, capacitors, piezoelectric bodies, etc. Widely applicable in the field.

It is a diagram showing a plurality of coordination structure of the salt represented as _{(RCOO) 2} M. It is a figure which shows the titanium tetraalkoxide which consists of an alkoxide ion (RO < ^- >) and titanium. It is a figure which shows the superposition | polymerization mechanism of a diene type carboxylate anion. It is a figure which shows the oxygen hardening mechanism of a polyfunctional alkyl allyl ether compound. It is a figure which shows a diene type acyl group structure. It is a figure which shows one example of the manufacturing method of a diene type carboxylate anion and its salt. It is a graph which shows ¹ H-NMR spectrum and attribution of methyl α-allyloxymethylacrylate. It is a graph which shows IR spectrum and attribution of methyl (alpha)-allyl oxymethyl acrylate. It is a graph which shows ¹ H-NMR spectrum and attribution of Zn (AMA) ₂ . It is a graph which shows IR spectrum and attribution of Zn (AMA) ₂ .

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.

<Synthesis of compound and preparation of aqueous solution thereof>
Hereinafter, the synthesis and analysis of an aqueous solution containing a diene carboxylate anion in the present invention will be described. The equipment and conditions used for the analysis are as follows.
[HPLC analysis]
The following high performance liquid chromatography (HPLC) apparatus and conditions were used.
By this apparatus and conditions, α-allyloxymethyl acrylate ester and α-allyloxymethyl acrylic acid can be detected. α-Allyloxymethylacrylic acid ions are detected in the form of α-allyloxymethylacrylic acid by the action of phosphoric acid contained in the elution solvent.
HPLC apparatus: DGU-20A5, LC-20AD, SIL-20A, SPD-20A, CTO-20A (all manufactured by Shimadzu Corporation) Diluting solvent: acetonitrile / methanol = 2/1 (mass ratio)
Elution solvent: 0.1 mol% phosphoric acid aqueous solution / acetonitrile / methanol mixed solvent separation column: CAPCELL PACK C18 TYPE: AQ (manufactured by Shiseido)

^[1 H-NMR spectrum measurement]
A nuclear magnetic resonance apparatus (400 MHz / Varian) was used.
[IR transmission spectrum measurement]
An infrared spectrometer (device name: NEXUS-670 / manufactured by Thermo Nicolet) was used.
[ICP emission analysis]
An ICP emission spectroscopic analyzer (device name: CIROS120 / SPECTRO) was used.
[Non-volatile content]
About 0.4 g of the sample was weighed into an aluminum cup, air-dried at room temperature for 30 minutes, and then dried at 80 ° C. for 30 minutes in a vacuum dryer. The mass after drying was weighed, and the nonvolatile content was calculated from the residual mass of the sample.

[Synthesis / Preparation Example 1-1]
Synthesis and synthesis of methyl α-allyloxymethyl acrylate: Me-AMA were performed as in Example 28 of International Publication No. 2011/148903.
The obtained colorless and transparent liquid was dissolved in deuterated dimethyl sulfoxide (d-DMSO), and ¹ H-NMR spectrum measurement was performed. The obtained NMR spectrum and attribution are shown in FIG. Further, when IR transmission spectrum measurement was performed by a liquid film method using a potassium bromide (KBr) plate, there was no absorption band attributed to the carboxylate anion, and C = O of carboxylic acid or carboxylate ester. There was an absorption band attributed to stretching vibration, and the wave number at which the absorption of the absorption band was maximum (hereinafter referred to as ν (C═O)) was 1720 cm ⁻¹ . The obtained IR spectrum and attribution are shown in FIG.

[Synthesis / Preparation Example 1-2]
Preparation of aqueous solution containing acrylate ion (AA ⁻ ) and zinc ion (Zn ²⁺ ) 30.0 parts of zinc acrylate (manufactured by Aldrich, hereinafter referred to as Zn (AA) ₂ ) in a reactor containing a stirring bar And 70.0 parts of distilled water was added, and the reactor was stirred for 30 minutes while warming in a 30-35 ° C. warm bath. Thereafter, the mixture is filtered with a 0.45 μm pore size filter, and an aqueous solution of Zn (AA) ₂ , that is, an acrylate ion (AA ⁻ ) and a zinc ion (Zn ²⁺ ) at a ratio of 2: 1 (molar ratio) as a colorless transparent liquid. An aqueous solution containing 95.0 parts was obtained. The nonvolatile content was 30.6%.

[Synthesis / Preparation Example 1-3]
Preparation of MeOH (methanol) solution containing acrylate ion (AA ⁻ ) and zinc ion (Zn ²⁺ ) In a reactor containing a stirring bar, 30.0 parts of Zn (AA) ₂ and 55.0 parts of MeOH were added and reacted. The vessel was stirred for 30 minutes while warming in a 30-35 ° C warm bath. Thereafter, the mixture is filtered with a 0.45 μm pore size filter, and a MeOH solution of Zn (AA) ₂ , that is, acrylic acid ion (AA ⁻ ) and zinc ion (Zn ²⁺ ) is 2: 1 (molar ratio) as a colorless and transparent liquid. As a result, 80.0 parts of MeOH solution was obtained. The nonvolatile content was 37.2%.

[Synthesis / Preparation Example 1-4]
Preparation of aqueous solution containing α-allyloxymethyl acrylate ion (AMA ⁻ ) and sodium ion (Na ⁺ ) In a reactor containing a stirring bar, 40.0 parts of 10% sodium hydroxide (NaOH) aqueous solution and Me-AMA15. 0 parts was charged and stirred with a magnetic stirrer while cooling in a water bath. Stirring is continued until Me-AMA disappears, and an aqueous solution containing AMA ⁻ and Na ⁺ at a 1: 1 (molar ratio), that is, sodium salt of α-allyloxymethylacrylic acid (hereinafter referred to as Na (AMA)). An aqueous solution was obtained. The disappearance of Me-AMA was confirmed by HPLC analysis.
A small amount of Na (AMA) aqueous solution was collected from the reactor, IR measurement was performed by the liquid membrane method using a KBr plate, and the difference spectrum with water was measured. As a result, the absorption attributed to the antisymmetric stretching of the carboxylate anion The wave number (hereinafter referred to as ν (COO ⁻ )) at which the absorption in the absorption band is maximum was 1554 cm ⁻¹ .

[Synthesis / Preparation Example 1-5]
Preparation of aqueous solution containing α-allyloxymethyl acrylate ion (AMA ⁻ ) and zinc ion (Zn ²⁺ ) 50 ml of diisopropyl ether (DIPE) was added to a reactor containing the Na (AMA) aqueous solution of Synthesis Example 1-4. Then, 13.5 parts of zinc sulfate heptahydrate was added and stirred for 1 hour.
The contents were transferred to a dropping funnel and extracted with DIPE and separated. After adding 0.005 part and 0.008 part of 6-t-butyl-2,4-xylenol and Adekastab AO-412 (manufactured by Adeka) to the DIPE layer, the DIPE is distilled off using an evaporator. As a colorless and transparent liquid, 46.0 parts of a DIPE solution of a salt (hereinafter referred to as Zn (AMA) ₂ ) composed of AMA ⁻ and Zn ^{2+ in} a molar ratio of 2: 1 was obtained.
A small amount of ZnPE (AMA) ₂ DIPE solution was collected from the reactor and dried using a vacuum pump. ¹ H-NMR measurement was performed on the sample dissolved by adding d-DMSO. The obtained spectrum and attribution are shown in FIG. Similarly, a solution obtained by adding dichloromethane to a small sample dried by a vacuum pump was applied to a KBr plate, and left standing at room temperature to dry, and IR measurement was performed. As a result, ν (COO ⁻ ) was 1594 cm ⁻¹ . . The obtained spectrum and attribution are shown in FIG. Further, when the collected DIPE solution of Zn (AMA) ₂ was diluted with xylene and subjected to ICP emission analysis, a strong peak attributed to zinc was confirmed.
Add 60.0 parts of distilled water to the reactor containing the DIPE solution of Zn (AMA) ₂ , remove DIPE by distilling off under reduced pressure while warming the reactor in a warm bath at 30 to 35 ° C., and remove the solvent in water. Exchanged. Filtration through a 0.45 μm pore size filter gave an aqueous solution of Zn (AMA) ₂ , that is, 66.0 parts of an aqueous solution containing AMA ⁻ and Zn ²⁺ in a 2: 1 (molar ratio). The nonvolatile content was 20.9%.

[Synthesis / Preparation Example 1-6]
Preparation of isopropanol (IPA) solution containing α-allyloxymethyl acrylate ion (AMA ⁻ ) and zinc ion (Zn ²⁺ ) In the same manner as in Synthesis / Preparation Example 1-5, a DIPE solution of Zn (AMA) ₂ was obtained. Thereafter, DIPE was distilled off almost completely using a vacuum pump, and Zn (AMA) ₂ was obtained as a colorless and transparent water-like material. Thereto, 60.0 parts of IPA was added and redissolved, and then IPA was distilled off under reduced pressure and concentrated. Filtration through a 0.45 μm pore size filter gave an IPA solution of Zn (AMA) ₂ , that is, 41.0 parts of an IPA solution containing AMA ⁻ and Zn ²⁺ in a 2: 1 (molar ratio). The nonvolatile content was 33.6%.

[Synthesis / Preparation Example 1-7]
Zn _{(AMA) 2} aqueous solution 9.0 parts obtained in Synthetic Preparation Example 1-5, and the Zn _{(AA) 2} aqueous solution 11.0 parts obtained in Synthetic Preparation Example 1-2 were mixed, ^AMA -, AA ^An aqueous solution containing Zn ²⁺ in a molar ratio of 1: 3: 2 was obtained. This corresponds to an aqueous solution containing Zn (AMA) ₂ and Zn (AA) ₂ at a molar ratio of 1: 3 and a mass ratio of 36:64. The nonvolatile content of this aqueous solution was calculated to be 26.2% from the nonvolatile content of the Zn (AMA) ₂ aqueous solution and the nonvolatile content of the Zn (AA) ₂ aqueous solution.

<Applicability of the polymerizable composition of the present invention>
[Example 1-1]
2.0 parts of the aqueous solution obtained in Synthesis / Preparation Example 1-7 was weighed into a screw tube, and 0.184 parts of an aqueous dispersion of silica fine particles was added dropwise while stirring with a stirrer. This is an amount such that the proportion of silica fine particles in the nonvolatile content is 5%.
The details of the aqueous silica fine particle dispersion used are as follows.
・ Product name: ST-AK-A (Nissan Chemical Co., Ltd.)
-Particle diameter: 10-15 nm
-Fine particle content (non-volatile content): 15.0%
Further, 0.71 part of distilled water was added so that the non-volatile content was 19.1% to obtain a transparent aqueous dispersion composition.
This aqueous dispersion composition was placed on a glass plate with No. When applied using a bar coater of No. 8, no repelling was observed, and a uniform wet coating film could be obtained. The results are shown in Table 1.

[Examples 1-2 to 1-6]
The addition amount of ST-AK-A was adjusted so that the ratio of silica fine particles in the nonvolatile content was the ratio shown in Table 1, and the addition amount of distilled water was adjusted so that the nonvolatile content was 19.1%. Except for the above, an aqueous dispersion composition was obtained in the same manner as in Example 1-1. When the applicability of the obtained aqueous dispersion composition was confirmed, no repelling was observed at all, and a uniform wet coating film could be obtained. The results are shown in Table 1.

[Comparative Example 1]
Aqueous compositions were obtained in the same manner as in Examples 1-2 to 1-6, except that ST-AK-A was not added. When the applicability of the obtained aqueous composition was confirmed, it was strongly repelled at the moment of application with a bar coater, and a wet coating film could not be obtained at all.

<Effect of dispersing silica fine particles: applicability>
From the comparison between Examples 1-1 to 1-6 and Comparative Example 1, it can be seen that the applicability is greatly improved by dispersing the silica fine particles.

<Hardness of the cured product of the present invention>
[Example 2]
2.0 parts of the IPA solution of Zn (AMA) ₂ obtained in Synthesis / Preparation Example 1-6 was weighed into a screw tube, and 0.944 parts of an IPA dispersion of silica fine particles was added dropwise while stirring with a stirrer. This is an amount such that the proportion of silica fine particles in the nonvolatile content is 30%.
The details of the silica fine particle IPA dispersion used are as follows.
・ Product name: IPA-ST (Nissan Chemical)
-Particle diameter: 10-15 nm
Fine particle content (nonvolatile content): 30.5%
Furthermore, 0.17 part of IPA was added so that the non-volatile content would be 30.8%, then 0.034 part of Darocur 1173 (manufactured by BASF) was added as a photo radical initiator, and IPA dispersion of transparent silica fine particles was performed. A composition was obtained.
No. so that the dry film thickness becomes 2 μm. This IPA dispersion composition was applied to a glass plate using a 5 bar coater.
The dry film thickness was calculated according to the following formula.
Dry film thickness [μm] = 1.3 × Bar coater No. × Non-volatile content (mass%) ÷ 100

After coating, the glass plate was dried at 80 ° C. for 10 minutes in a vacuum dryer and then cured by UV irradiation on the glass plate on which the coating film was formed in the air by a belt conveyor type UV irradiator.
The belt conveyor type UV irradiator used is as follows.
UV irradiation device: Light hammer 6
Belt conveyor device: Model LC-6B
As described above, the UV irradiation conditions manufactured by Fusion UV Systems are as follows.
Light source: Illuminance at H bulb wavelength 365 nm: 200 mW / cm ²
Best speed: 6.0m / s
Irradiation time per pass: 1 second Integrated light quantity per pass: 200 mJ / cm ²
Irradiation frequency: 20 passes When this UV cured coating film was measured for scratch hardness (pencil method) according to JIS K 5600-4, it was 5H.

[Comparative Example 2]
UV which does not contain silica fine particles was operated in the same manner as in Example 2 except that IPA-ST was not added and the amount of IPA added was changed to 0.18 parts so that the nonvolatile content was 30.8%. A cured coating was obtained. It was 3-4H when scratch hardness (pencil method) was measured about this UV hardening coating film.

<Effect of dispersing silica fine particles: hardness>
From the comparison between Example 2 and Comparative Example 2, it can be seen that the hardness of the cured product is improved by dispersing the silica fine particles.

<Film Formability of Polymerizable Composition of the Present Invention>
[Example 3]
Aqueous system containing AMA ⁻ , AA ⁻ , Zn ²⁺ in a molar ratio of 1: 3: 2 and uniform dispersion of silica fine particles in an amount of 30% in the non-volatile content by exactly the same operation as in Example 1-4. A wet film of the composition was formed.
When this was dried for 10 minutes at 80 ° C. in a vacuum dryer, a transparent and uniform dry coating film was obtained.
That is, a transparent uniform dry coating film containing AMA ⁻ , AA ⁻ and Zn ²⁺ in a molar ratio of 1: 3: 2 and 30% by mass of silica fine particles was obtained.

[Comparative Example 3]
Aqueous solution obtained in Synthesis Preparation Example 1-7 aqueous solution obtained in Synthesis Preparation Example 1-2 instead of ^{(AMA - -,} AA, the ^{Zn 2+} respectively, a molar ratio of 1: 3 2 aqueous solution containing) (AA ^- In the same manner as in Example 3 except that an aqueous solution containing Zn ²⁺ in a molar ratio of 2: 1 was used, and AA ⁻ and Zn ²⁺ were each contained in a molar ratio of 2: 1 and 30% in the nonvolatile content. An aqueous composition in which an amount of silica fine particles to be uniformly dispersed was prepared, and this was applied onto a glass plate to form a wet coating film.
When this was dried at 80 ° C. for 10 minutes in a vacuum drier, a dry coating film that was entirely whitened was formed.

<Effects using diene carboxylate anion: film-forming property>
From the comparison between Example 3 and Comparative Example 3, it can be seen that the film forming property is expressed by using a diene carboxylate anion.

<Adhesiveness of the cured product of the present invention>
[Example 4-1]
To the aqueous solution obtained in Synthesis / Preparation Example 1-7, Irgacure 2959 (manufactured by BASF) in an amount of 3% by mass with respect to the non-volatile content in the aqueous solution was further added as a photoradical initiator, and 70 to 80 ° C. The mixture was shaken while warming to make a uniform solution.
4.0 parts of this aqueous solution containing a photoradical initiator was placed in a container containing a stirrer, and 3.0 parts of ST-AK-A (3.0 parts) was added dropwise with stirring to obtain a transparent aqueous composition. . This aqueous composition contains 30% by mass of silica fine particles in the nonvolatile content. Moreover, the non volatile matter of the obtained aqueous composition was computed with 21.4%.
After filtering with a 0.45 μm pore size filter, the dry film thickness is 2 μm according to the above formula. 7 was applied to a glass plate using a bar coater and dried at 100 ° C. for 10 minutes in a vacuum dryer to obtain a dried coating film.
This dry coating film contains the same dry coating film as in Example 3 except that it contains a photoradical initiator (AMA ⁻ , AA ⁻ , Zn ²⁺ in a molar ratio of 1: 3: 2 respectively, and 30 masses of silica fine particles. % Dry film). This was UV cured in the same manner as in Example 2.
About the cured coating film formed on this glass plate, the adhesiveness with respect to a glass plate was evaluated based on JISK5600-5-6 (cross-cut method). However, the squares were 10 × 10 squares = 100 squares, and adhesion was evaluated as the number of squares remaining without peeling or breakage in 100 squares. The results are shown in Table 2.

[Examples 4-2 to 4-6]
Adhesion was evaluated in the same manner as in Example 4-1, except that the substrate used was changed to the one shown in Table 2. The results are shown in Table 2.

[Example 4-7]
0.8 parts of the IPA solution of Zn (AMA) ₂ obtained in Synthesis / Preparation Example 1-6 and 1.29 parts of the MeOH solution of Zn (AA) ₂ obtained in Synthesis / Preparation Example 1-3 were mixed, While stirring with a stirrer, 1.05 parts of IPA-ST was added dropwise. Furthermore, 0.023 parts of Irgacure 2959 (manufactured by BASF) and 0.34 parts of IPA were added so as to be 3% by mass with respect to the nonvolatile content, and then filtered through a 0.45 μm pore size filter.
According to the above calculation formula, No. is set so that the dry film thickness becomes 2 μm. 5 was applied to a glass plate using a bar coater and dried at 80 ° C. for 10 minutes in a vacuum dryer to obtain a dried coating film. This dry coating film is the same as Example 4-1.
Subsequent operation performed exactly the same operation as Example 4-1, and evaluated the adhesiveness with respect to a glass plate. The results are shown in Table 2.

[Comparative Example 4]
As a compound having good curability and film forming property, trimethylolpropane triacrylate (TMPTA) is dissolved in IPA so as to have a concentration of 30.5%, and further Irgacure 2959 so as to be 3% with respect to TMPTA. (BASF) was added and shaken well. 2.0 parts of this solution was weighed, 0.86 parts of IPA-ST was dropped while stirring with a stirrer, and then filtered through a 0.45 μm pore size filter to obtain a uniform transparent dispersion composition. This is a composition containing 30% silica fine particles in the nonvolatile content.
Subsequent operations were carried out in the same manner as in Example 4-7, and the adhesion to the glass plate was evaluated. The results are shown in Table 2.

<Effects using diene carboxylate anion: adhesion>
From the comparison between Examples 4-1 and 4-7 and Comparative Example 4, it can be seen that the adhesion is dramatically improved by using the diene carboxylate anion. Moreover, it turns out that the hardened | cured material of this invention adheres with respect to various base materials from Examples 4-1 to 4-6.

From the results of Tables 1 and 2, it was revealed that the polymerizable composition of the present invention has excellent coating properties, and the cured product has hardness, film-forming property, adhesion, and the like.
As described above, the polymerizable composition is excellent by forming the polymerizable composition comprising the specific diene carboxylate anion represented by the general formula (1) or (2) and fine particles. In addition, the polymerized and cured product has various characteristics (hardness, scratch resistance, fingerprint resistance, gas barrier property, water vapor barrier property, ionic bond and / or metal. (Oxygen absorption, UV cut, infrared cut, color development / coloring, high refractive index, adhesion, various catalytic functions, fluorescence / luminescence, light amplification, dispersibility, antistatic, etc.) It is thought that there is.
Therefore, it can be said from the results of the above-described embodiments that the present invention can be applied in the entire technical scope of the present invention and in various forms disclosed in the present specification, and can exhibit advantageous effects.

Claims (5)

A polymerizable composition comprising a diene carboxylate anion represented by the following general formula (1 ) or a salt thereof , and fine particles.

In the formula, R represents a hydrogen atom or a methyl group. X ¹ and Z ¹ represent a methylene group. Y ¹ represents an oxygen atom. The bond of oxygen atom-carbon atom-oxygen atom represented by the dotted line and the 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. The polymerizable composition according to claim 1, further comprising a liquid medium. The polymerizable composition according to claim 1, further comprising a radical initiator and / or a dryer. A method for polymerizing or curing the polymerizable composition according to claim 1,
The polymerization or curing method includes a step of applying at least one method selected from the group consisting of heating, irradiation with active energy rays, and exposure to an atmosphere containing oxygen. Method of polymerizing or curing the product. A polymer or cured product of the polymerizable composition according to claim 1.

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