JP7255480B2 - Curable composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a curable composition, preferably to an active energy ray-curable composition. The cured film of the composition of the present invention has excellent adhesion to plastic substrates, and is preferably used as a coating agent for the purpose of preventing fogging of plastic surfaces (anti-fog coating agent) and preventing adhesion of dust to plastics. and belong to these technical fields.
In the present specification, acrylate and / or methacrylate is represented as (meth) acrylate, acryloyl group and / or methacryloyl group is represented as (meth) acryloyl group, acrylic acid and / or methacrylic acid is represented as (meth) acrylic acid and an allyl group and/or a methallyl group is represented as a (meth)allyl group.

Active energy ray-curable compositions can be cured by irradiating them with active energy rays such as ultraviolet rays, visible rays, and electron beams for a very short time, and are widely used as inks and coatings for various substrates because of their high productivity. It is
The surface of plastic substrates such as plastic plates and plastic films is protected with a hard coating agent for the purpose of preventing scratches on the surface, and active energy ray-curable compositions are also used for this purpose.

Because plastic substrates are highly transparent, they are used for protective eyewear, goggles, bathroom interior walls, headlamp covers and rear lamp covers for automobiles and motorcycles, etc. However, they are used in hot and humid locations or where temperature and humidity differences are large. When it is used in a place, it may become cloudy and lose its transparency due to condensation on its surface.
In order to solve these problems, conventionally, a method of coating the substrate surface with an antifogging composition comprising a non-reactive surfactant has been used. Although the anti-fogging effect is exhibited at the initial stage, once the treated surface is wiped off, the anti-fogging property deteriorates, that is, the anti-fogging durability is lacking.
There is also a method of applying an antifogging composition comprising a hydrophilic polymer diluted with an organic solvent to the substrate surface, but the cured film hardness is insufficient and the solvent resistance is insufficient. In addition, the antifogging property was not satisfactory.

In order to solve the above problems, in recent years, antifogging compositions that are cured by active energy rays such as ultraviolet rays and electron beams have been proposed. Specifically, anti-fogging compositions (Patent Document 1) composed of a hydrophilic group-containing UV-curable resin and a hydrophilic group-free UV-curable resin, hydrophilic polymers and various hydrophilic (meth)acrylates. An antifogging composition consisting of has been proposed (Patent Document 2).
However, these compositions have the problem that they do not exhibit antifogging properties in high humidity environments.

An anti-fogging composition comprising a hydrophilic monomer and a non-reactive surfactant has also been proposed (Patent Document 3). The anti-fogging durability was lacking.

Furthermore, it has been proposed that a composition obtained by combining a specific (meth)acrylate and a surfactant reactive with the (meth)acrylate has excellent surface hardness and excellent anti-fogging durability (Patent Document 4. ).

However, since the (meth)acrylate used in the composition is an oligomer with a relatively large molecular weight, the surface hardness is insufficient because the mole fraction of (meth)acryloyl groups in the entire molecule is relatively low. In addition, the hydrophilicity of (meth)acrylate is insufficient, and improvement in antifogging properties is required. Moreover, in order to obtain good anti-fogging properties from the composition, the amount of the surfactant to be blended must be increased, making it difficult to achieve compatibility with hard coat properties.

JP-A-55-69678 JP-A-3-31369 JP-A-3-215589 JP-A-11-140109

The present inventors have found that the resulting cured film has excellent adhesion to substrates, particularly adhesion to plastic substrates, has good surface hardness, can be preferably used as a hard coating agent, and has good properties even under high humidity. In order to find a curable composition that has anti-fogging properties and that sufficiently maintains the anti-fogging properties even after wiping off the surface of the cured film, extensive studies have been conducted.

In order to solve the above problems, the present inventors have proposed an ethylenically unsaturated compound such as an alcohol solvent containing a compound having an ethylenically unsaturated group and an ionic group and a compound having a hydrophilic ethylenically unsaturated group. The inventors have found that a composition containing almost no hydroxyl group-containing compounds having no saturated groups can form a cured film having excellent surface hardness, anti-fogging properties and durability, and thus completed the present invention.
The present invention will be described in detail below.

According to the composition of the present invention, the cured film formed has good adhesion to plastic substrates, high surface hardness, and exhibits good anti-fogging durability.
Therefore, the composition of the present invention can be preferably applied to coatings such as protective eyeglasses and goggles, and coating agents for headlamps and rear lamp covers of automobiles and motorcycles, etc., where these performances are required for the cured film.

The present invention includes the following components (A), (B) and (C),
In the total 100% by weight of components (A) to (C) below, 1 to 30% by weight of component (A), 10 to 97% by weight of component (B), and 2 to 60% by weight of component (C) % including
Curing type that does not contain the following component (D) or contains the following component (D) in a proportion of 3 parts by weight or less with respect to the total 100 parts by weight of the components (A), (B) and (C) It relates to a composition (hereinafter sometimes simply referred to as "composition").
Component (A): a compound having an ethylenically unsaturated group and an ionic group, the compound containing the following component (A-1) Component (A-1): a cation having an ethylenically unsaturated group in one molecule Compound (B): a compound having a hydrophilic group and an ethylenically unsaturated group (C): Component (A) and a compound having two or more ethylenically unsaturated groups other than component (B) Component (D): a hydroxyl group-containing compound having no ethylenically unsaturated group Hereinafter, components (A) to (C), which are essential components , the (D) component that may be contained in a small amount, other components, and the method of use.

1. (A) Component (A) is a compound having an ethylenically unsaturated group and an ionic group.
Component (A) is a component that, by curing the composition, imparts a cured film with good antifogging properties and low surface resistance necessary for dust adhesion prevention.
Component (A) maintains excellent antifogging properties even when the surface of the cured film is wetted or wiped by chemically bonding the ionic groups into the cured film through the reaction of the ethylenically unsaturated groups. It can be made excellent in repeated anti-fogging properties.

Various compounds can be used as component (A) as long as they are compounds having an ethylenically unsaturated group and an ionic group.
Examples of ethylenically unsaturated groups include (meth)acryloyl, (meth)allyl, vinyl and styryl groups.
Examples of the ethylenically unsaturated group of component (A) include components (B) and (C) described later, and a compound (G) having one ethylenically unsaturated group other than components (A) and (B) A (meth)acryloyl group is preferred, and an acryloyl group is more preferred, because of its good reactivity with "(G) component" hereinafter) and excellent curability.

Since component (A) has an ionic group, it is possible to obtain anti-fogging properties and low surface resistance without impairing the original hard coat properties of the cured film of the composition, and the content of component (A) is smaller. However, the effect can be obtained.
In component (A), ionic groups include salts of strong acids, specifically sulfonates such as ammonium sulfonate, sodium sulfonate and potassium sulfonate, ammonium alkylsulfate, sodium alkylsulfate and potassium alkylsulfate. and carboxylates such as ammonium carboxylate, sodium carboxylate and potassium carboxylate.

As the ionic group of component (A), a salt of sulfonic acid group and a salt of alkyl sulfate group are preferable because the desired effect can be obtained even when the content of component (A) is reduced. .
Further, counter cations constituting the sulfonate include secondary ammonium ions, tertiary ammonium ions and quaternary ammonium ions.
Specifically, secondary ammonium ions include dimethylamine, diethylamine, di-1-propylamine, di-2-propylamine, di-n-butylamine, di-2-butylamine, and di-1-pentylamine. , di-2-pentylamine, di-3-pentylamine, dineopentylamine, dicyclopentylamine, di-1-hexylamine, di-2-hexylamine, di-3-hexylamine, dicyclohexylamine, methyl ethanol Protonated ions of amine and ethylethanolamine, respectively, and the like are included.
Tertiary ammonium ions include trimethylamine, triethylamine, tri-1-propylamine, tri-2-propylamine, tri-n-butylamine, tri-2-butylamine, tri-1-pentylamine, and tri-2-pentyl. Amine, tri-3-pentylamine, trineopentylamine, tricyclopentylamine, tri-1-hexylamine, tri-2-hexylamine, tri-3-hexylamine, tricyclohexylamine, dimethylethanolamine, ethylmethylethanol Examples include protonated ions of amine, diethylethanolamine, lauryldiethanolamine and bis(2-methoxyethyl)methylamine, respectively.
Among these, methylethanolamine, ethylethanolamine, dimethylethanolamine, diethylethanolamine, or lauryldiethanolamine is preferably a protonated ion, and methylethanolamine, ethylethanolamine, or lauryldiethanolamine is each a protonated ion. More preferably, the protonated ion is methylethanolamine, dimethylethanolamine or ethylethanolamine, respectively, and especially ethylethanolamine is the protonated ion. preferable.

The ionic group of component (A) is preferably bonded to the ethylenically unsaturated group via an alkyl group, an alkylbenzene group, an alkylene oxide group, or the like.

As the component (A), the following components (A-1) and (A-2) can be exemplified, both of which can be used , and the component (A-1) is essential .
Component (A-1): a compound consisting of a cation having an ethylenically unsaturated group in one molecule and an anion Component (A-2): an anion having an ethylenically unsaturated group in one molecule and a cation the compound that becomes

Component (A-1) is a compound consisting of a cation having an ethylenically unsaturated group in one molecule and an anion.
Cationic groups in cations having an ethylenically unsaturated group in one molecule include, for example, ammonium ions, imidazolium ions, pyridinium ions, pyrrolidinium ions, pyrrolinium ions, piperidinium ions, pyrazinium ions, and pyrimidinium ions. , triazolium ion, triazinium ion, quinolinium ion, isoquinolinium ion, indolinium ion, quinoxalinium ion, piperazinium ion, oxazolinium ion, thiazolinium ion, and morpholinium ion At least one selected from the group consisting of can be exemplified.

Specific examples of cations having an ethylenically unsaturated group in one molecule include dimethylmono(meth)acrylate ethylammonium ion [quaternary ammonium ion of dimethylaminoethyl(meth)acrylate], and diethylmono(meth)acryl dialkylmono(meth)acrylate alkylammonium ions such as acid ethylammonium ion [quaternary ammonium ion of diethylaminoethyl(meth)acrylate], and 1,2,2,6,6-pentamethyl-4-(meth)acrylate pipette Preferred examples include lysinium ions.
In the above ammonium ions, descriptions such as "N-" and "N, N-" indicating substituents on nitrogen atoms are omitted.

Examples of anions constituting component (A-1) include halogen anions such as sulfonic acid derivatives, bromide ions and triflates, boron anions such as tetraphenylborate, and phosphorus anions such as hexafluorophosphate.
As the anion, a sulfonic acid derivative is preferable. Specific examples of sulfonic acid derivatives include anions of sulfonic acids having polyoxyalkylene units such as anions of alkoxypolyethylene glycol sulfonic acids, and anions of alkyl group-containing aromatic sulfonic acids such as anions of isopropylbenzenesulfonic acids. be done.

Component (A-1) is preferably a compound composed of a dialkylmono(meth)acrylate alkylammonium ion and a sulfonic acid anion. Furthermore, as the anion of sulfonic acid, an anion of sulfonic acid having a polyoxyalkylene unit is preferable.
As the component (A-1) , a compound represented by the following formula (1) is essential .

In the above formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an optionally branched alkylene group having 1 to 12 carbon atoms, and R ³ and R ⁴ are each independently represents an optionally branched alkyl group having 1 to 10 carbon atoms, and X ^- is an alkyl sulfate ion, polyoxyalkylene alkyl ether sulfate ion, polyoxyalkylene alkylphenyl ether sulfate ion, alkyl sulfonate ion or Represents an alkylbenzenesulfonate ion.

R ³ and R ⁴ are optionally branched alkylene groups having 1 to 12 carbon atoms. Specific examples thereof include a methylene group, an ethylene group, a propylene group and a butylene group.
R ³ and R ⁴ are each independently an optionally branched alkyl group having 1 to 10 carbon atoms. Specific examples include methyl group, ethyl group, propyl group and butyl group.

X ⁻ is an alkyl sulfate ion, polyoxyalkylene alkyl ether sulfate ion, polyoxyalkylene alkylphenyl ether sulfate ion, alkyl sulfonate ion or alkylbenzene sulfonate ion.
In order to exhibit good anti-fogging properties, the component (A) must be present near the surface of the cured film. It's easy to do. Therefore, the alkyl group in these groups is preferably an alkyl group having 6 or more carbon atoms, more preferably an alkyl group having 6 to 20 carbon atoms, so as to increase the hydrophobicity.
Examples of polyoxyalkylene units in these groups include polyoxyethylene units, polyoxypropylene units, polyoxytetramethylene units, and the like.

A commercially available product can be used as the component (A-1).
For example, compounds having a cation containing a (meth)acryloyl group and an ammonium ion in the molecule and an anion include trade names "IL-MA1", "IL-MA2" and "IL- MA3";
Examples of compounds having a cation containing an acryloyl group and an ammonium ion and an anion include trade names "JI-62C01" and "JI-63F01" manufactured by Nippon Nyukazai Co., Ltd.; and a cation containing a methacryloyl group and an ammonium ion and an anion. Examples of compounds having an alkyl sulfuric acid as a compound include Nippon Nyukazai Co., Ltd. trade name “JNA-04006” and the like.

Component (A-2) is a compound consisting of an anion having an ethylenically unsaturated group in one molecule and a cation.
Specific examples of the component (A-2) in which the anionic group is a sulfonate ion include the following examples.
That is, polyoxyethylene-1-(allyloxymethyl)alkyl ether sulfate ammonium salt, polyoxyethylene nonylpropenylphenyl ether sulfate ammonium salt, α-sulfo-ω-(1-(alkoxy ) methyl-2-(2-propenyloxy)ethoxy)-poly(oxy-1,2-ethanediyl) ammonium salt, bis(polyoxyethylene polycyclic phenyl ether) methacrylate sulfate ester ammonium salt,
2-sodium sulfoethyl methacrylate, alkylallylsulfosuccinate sodium salt, (meth)acryloylpolyoxyalkylene sulfate sodium salt, and bis(polyoxyethylene polycyclic phenyl ether) methacrylate sulfate ester sodium salt, etc., in which the cation is a sodium ion can be mentioned.

A commercially available product can be used as the component (A-2).
Specific examples thereof include polyoxyethylene-1-(allyloxymethyl)alkyl ether sulfate ester ammonium salts, trade names "Aqualon KH-10" and "Aqualon KH-1025" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. , "Aquaron KH-05";
Examples of polyoxyethylene nonylpropenyl phenyl ether ammonium sulfate include trade names "Aquaron HS-10", "Aquaron HS-1025", "Aquaron BC-0515" and "Aquaron BC-10" manufactured by Daiichi Kogyo Seiyaku Co., Ltd. , "Aqualon BC-1025" and "Aqualon BC-20" and "Aqualon BC-2020";
As α-sulfo-ω-(1-(alkoxy)methyl-2-(2-propenyloxy)ethoxy)-poly(oxy-1,2-ethanediyl)ammonium salt, manufactured by ADEKA Corporation under the trade name “ADEKA Rear Soap SR-10", "Adekari Soap SR-20", "Adekari Soap SR-1025" and "Adekari Soap SR-3025";
As the bis(polyoxyethylene polycyclic phenyl ether) methacrylate sulfate, trade name "Antox MS-60" manufactured by Nippon Nyukazai Co., Ltd.;
As the sodium alkyl/allylsuccinate sulfonate, trade name "Antox SAD" manufactured by Nippon Nyukazai Co., Ltd.;
2-sodium sulfoethyl methacrylate, trade name "Antox MS-2N" manufactured by Nippon Nyukazai Co., Ltd.;
Alkylallyl sulfosuccinic acid sodium salt, Sanyo Chemical Industries Co., Ltd. trade name "Eleminol JS-20";-3000" and the like.

Among components (A), components (A-1) and (A-2) may be selected depending on the purpose.
As the component (A), the component (A-1) is preferred because it is more excellent in anti-fogging durability than the component (A-2).
Although the details of the reason why component (A-1) is more excellent in anti-fogging persistence are unknown, it is likely that when the cations that are the counter ions constituting component (A-2) are metal cations such as sodium and potassium, hydrophilic It is considered that these are easily eluted from the cured film when it comes into contact with water because of its extremely high resistance, and the antifogging property is difficult to maintain. If non-metallic cations such as ammonium ions are used as cations, the hydrophilicity will be slightly lowered and improvement in anti-fogging durability is expected, but generally available compounds are limited to those with relatively low molecular weights. It is considered that the elution over time cannot be sufficiently prevented and the anti-fogging durability becomes insufficient.
On the other hand, the anions (for example, alkylsulfonate ions, alkylbenzenesulfonate ions, alkylnaphthalenesulfonate ions, and polyoxyethylene alkylsulfate ions) that are counterions constituting component (A-1) are slightly hydrophobic. Therefore, it is assumed that the elution due to moisture on the surface of the cured film is reduced. In addition, when these anions have a polyoxyalkylene ether structure, a chemical bond is formed with the cured film by the action of the radicals generated on the ether group during the radical polymerization process, so that the antifogging durability is further improved. Conceivable.
Furthermore, when the amount of ultraviolet irradiation increases, it is preferable to use components (A-1) and (A-2) in combination from the viewpoint of anti-fogging properties. This suppresses an increase in the crosslink density on the surface of the cured film when the UV irradiation dose increases, and moderately maintains the motility of components exhibiting antifogging performance, resulting in better antifogging performance. In order to exhibit stable anti-fogging properties, the copolymerization properties of the component (B), the component (C) and the component (G) are largely different, and the concentration of the component (A) is designed to be locally high. Specifically, this object can be achieved by using the components (A-1) and (A-2) in combination.

Component (A) is often solid at room temperature, and is preferably diluted with an organic solvent or reactive diluent in view of handling problems such as ease of incorporation into the composition.
As the organic solvent, it is necessary to use a compound other than the component (D) described later, and examples thereof include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and ester solvents such as ethyl acetate and butyl acetate.
Examples of reactive diluents include components (B), (C) and (G) described later.

As described above, component (A) is often a solid compound, and is usually a hydroxyl group-containing compound having no ethylenically unsaturated groups, such as an alcoholic solvent, in order to facilitate the handling of compounding and mixing. [Component (D)] is often included as an organic solvent.
According to the studies of the present inventors, it has been found that when the composition contains components (A) and (D), there is a problem that the antifogging performance of the cured film is not maintained for a long period of time. As a result of earnestly examining the cause of this, the inventors presumed that it is as follows.
That is, since the acid component constituting the ionic group of component (A) has a high acidity, the balance of component (A) is biased toward the acidic side.
When the ionic group of component (A) is, for example, alkyl sulfuric acid or sulfonic acid, the alkyl sulfuric acid or sulfonic acid generated from component (A) serves as an acidic catalyst, and the ethylenically unsaturated group of component (A) and (D ) accelerates the addition reaction (Michael addition reaction) with the hydroxyl group of the component. Therefore, if component (D) such as an alcohol-based solvent is used as the organic solvent for component (A), component (A) becomes a compound having almost no ethylenically unsaturated bonds (hereinafter referred to as "by-product A -D”).

Therefore, when the composition is cured, the by-products A to D are not chemically bonded in the cured film, and although the antifogging property immediately after the cured film is formed is good, the effect of moisture adhering to the cured film surface By-products A to D are washed away by the curing process, and the ionic groups derived from component (A) disappear in the cured film.
On the other hand, the composition of the present invention does not contain the (D) component, or the (D) component is added to the total 100 parts by weight of the (A) component, (B) component and (C) component. Since it is contained at a ratio of 3 parts by weight or less, there is no such problem.

The content ratio of component (A) may be appropriately set according to the purpose. It is preferably contained in an amount of 1 to 30% by weight, more preferably 3 to 20% by weight, based on 100% by weight of the total of components (C) and (G).
By containing the component (A) in an amount of 1% by weight or more, the cured film exhibits excellent antifogging properties, and by containing the component (A) in an amount of 30% by weight or less, sufficient hydrophilicity to impart antifogging properties and long It becomes a cured film that does not swell and peel off due to water absorption even if it is exposed to high temperature and high humidity for a long time.
Hereinafter, components (A) to (C) or components (A) to (C) and (G) are referred to as "curable components".

2. (B) Component (B) is a compound having a hydrophilic group and an ethylenically unsaturated group.
As described above, when the composition contains the components (A) and (D), the ethylenically unsaturated groups in the component (A) and the hydrophilic groups in the component (D) undergo an addition reaction to form a side reaction. products A to D, and the ethylenically unsaturated groups in component (A) disappear.
On the other hand, the component (B) is a side reaction product (hereinafter referred to as “side reaction product AB”) resulting from a side reaction between the ethylenically unsaturated groups in the component (A) and the hydrophilic groups in the component (B). ), and even if the ethylenically unsaturated groups in the component (A) disappear due to the side reaction, the side reaction product AB contains the ethylenically unsaturated groups derived from the component (B). As a result, the ionic groups derived from the component (A) are incorporated into the cured film by chemical bonding, and the antifogging performance is maintained for a long period of time.

In addition, ammonium alkylsulfate and ammonium sulfonate are used as raw materials in the process of producing component (A), and the ammonia generated from these materials during the production process is added to the ethylenically unsaturated bond of component (A). and the ethylenically unsaturated groups are converted to amino groups (hereinafter referred to as "by-products A-AM"). Therefore, in the same manner as described above, the by-product A-AM is not chemically bonded in the cured film of the composition, is washed away by moisture on the surface of the cured film, and is contained in the cured film by ionic The group disappears, and the anti-fogging durability is lowered.
The ethylenically unsaturated groups of component (B) can react with the amino groups of by-products A-AM. Furthermore, even if the component (B) reacts with the by-product A-AM, since it has an ethylenically unsaturated group derived from the component (B), an ionic group derived from the component (A) is present in the cured film. can be taken in.

In the component (B), the hydrophilic group includes a hydroxyl group, a carboxyl group, a sulfone group, a phosphoric acid group, and the like, and a hydroxyl group is more preferable from the viewpoint of excellent cured film performance.
As the ethylenically unsaturated group of the component (B), a (meth)acryloyl group is preferred, and an acryloyl group is more preferred, since the composition exhibits excellent curability.

Preferred examples of component (B) include a compound having a hydroxyl group and one (meth)acryloyl group [hereinafter referred to as "hydroxyl group-containing monofunctional (meth)acrylate"], and a hydroxyl group and two or more (meth)acryloyl Group-containing compound [hereinafter referred to as "hydroxyl group-containing polyfunctional (meth)acrylate"]
Examples of hydroxyl group-containing monofunctional (meth)acrylates include hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate and hydroxybutyl (meth)acrylate;
Polyol mono(meth)acrylates such as trimethylolpropane mono(meth)acrylate, glycerol mono(meth)acrylate, pentaerythritol mono(meth)acrylate, ditrimethylolpropane mono(meth)acrylate and dipentaerythritol mono(meth)acrylate acrylates; and mono(meth)acrylates of these polyol alkylene oxide adducts.
Examples of hydroxyl group-containing polyfunctional (meth)acrylates include trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di- or tri(meth)acrylate, di-trimethylolpropane di- or tri(meth)acrylate. Poly(meth)acrylates of acrylates and di-, tri-, tetra- or penta(meth)acrylate polyols of dipentaerythritol;
Poly(meth)acrylates of these polyol alkylene oxide adducts;
di(meth)acrylates of isocyanuric acid; and di(meth)acrylates of alkylene oxide adducts of isocyanuric acid.
In this case, examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide and tetramethylene oxide.

Among these compounds, a hydroxyl group-containing polyfunctional (meth)acrylate is preferable because the cured film is excellent in repeated anti-fogging properties and excellent in surface hardness. Specific examples are as described above.
Further, as the hydroxyl group-containing polyfunctional (meth)acrylate, glycerin di(meth)acrylate, di- or tri(meth)acrylate of pentaerythritol, and di(meth)acrylate of an alkylene oxide adduct of isocyanuric acid are preferred.

The content of component (B) may be appropriately set according to the purpose, and is preferably 10 to 97% by weight, more preferably 40 to 80% by weight based on 100% by weight of the total curable components.
When the proportion of component (B) is 10% by weight or more, excellent adhesion to plastics is obtained, and when it is 97% by weight or less, excellent antifogging properties are obtained.

3. (C) Component (C) is a compound having two or more ethylenically unsaturated groups other than the components (A) and (B).
Component (C) is a component necessary for improving the curability and surface hardness of the composition.
In addition, as described above, component (A) contains by-products A-AM.
The ethylenically unsaturated bond of component (C) reacts with the amino group of the by-product A-AM, and since the reactant has an ethylenically unsaturated group, it originates from component (A) in the cured film. It can incorporate ionic groups.

As the ethylenically unsaturated group of the component (C), a (meth)acryloyl group is preferable, and an acryloyl group is more preferable, because the curability of the composition is excellent.

The (C) component includes a compound having two (meth)acryloyl groups (hereinafter referred to as "bifunctional (meth)acrylate") and a compound having three or more (meth)acryloyl groups (hereinafter referred to as "3 functional or higher (meth)acrylate”), and the like.
Specific examples of bifunctional (meth)acrylates include di(meth)acrylate of alkylene oxide adduct of bisphenol A, di(meth)acrylate of alkylene oxide adduct of bisphenol F, butanediol di(meth)acrylate, diol di(meth)acrylates such as hexanediol di(meth)acrylate and nonanediol di(meth)acrylate;
Di(meth)acrylates of these polyol alkylene oxide adducts can be mentioned.
In this case, examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide and tetramethylene oxide.

Specific examples of trifunctional or higher (meth)acrylates include glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and di poly(meth)acrylates of polyols such as pentaerythritol hexa(meth)acrylate;
Di(meth)acrylates of these polyol alkylene oxide adducts;
tris(2-(meth)acryloyloxyethyl)isocyanurate; and tri(meth)acrylate of isocyanuric acid alkylene oxide adduct.
In this case, examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide and tetramethylene oxide.

Among these compounds, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and isocyanuric acid alkylene oxide adduct tri(meth)acrylate are preferred. These compounds are relatively highly hydrophilic among tri- or more functional (meth)acrylates, and are preferable in that the coating film hardness and curability can be improved without adversely affecting the antifogging properties by blending these components.

The content of component (C) may be appropriately set according to the purpose, and is preferably 2 to 60% by weight, more preferably 10 to 40% by weight, based on 100% by weight of the total curable components.
By containing the component (C) in an amount of 2% by weight or more, the cured film exhibits excellent hard coat properties, and by containing the component (C) in an amount of 40% by weight or less, an excellent antifogging property is obtained.

4. Component (D) In the composition of the present invention, 3 hydroxy group-containing compounds having no ethylenically unsaturated groups as component (D) are added to a total of 100 parts by weight of components (A), (B) and (C). It is contained in a ratio of parts by weight or less. Component (D) is preferably contained in a proportion of 2 parts by weight or less, and more preferably does not contain component (D).
A composition containing component (D) in an amount exceeding 3 parts by weight is repeatedly degraded in antifogging properties.
As described above, when the composition contains components (A) and (D), the ethylenically unsaturated groups in component (A) and the hydroxyl groups in component (D) undergo a Michael addition reaction. This is due to the production of side reactants AD and the disappearance of the ethylenically unsaturated groups in component (A).

Specific examples of component (D) include alcohol compounds such as methanol, ethanol, isopropanol and butanol; alkylene glycol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; and acetone alcohols such as diacetone alcohol. .
In addition, water is not contained in the (D) component. Since water does not cause the Michael addition reaction that causes repeated deterioration of the antifogging property, it may be contained in the composition in an amount of several percent, preferably 5% by weight or less in the composition.

5. Curable composition The composition of the present invention contains the components (A), (B) and (C) as essential components and does not contain the component (D) or contains the components (A) and (B). ) and (C) in a proportion of 3 parts by weight or less of the component (D) with respect to a total of 100 parts by weight of the component (D).
As a method for producing the composition of the present invention, the essential components (A) to (C) and, if necessary, other components described later may be stirred and mixed.
Other components described later may contain component (D) as an organic solvent, and in the present invention, the composition does not contain component (D) brought in from other components, It should be 3 parts by weight or less per 100 parts by weight of components (B) and (C) combined.
When mixing the components (A) to (C) and, if necessary, other components described later, the mixture may be heated and stirred as necessary. The temperature for stirring and mixing with heating is preferably in the range of 40 to 90°C. However, when a thermal polymerization initiator described later is blended, it is preferable to carry out at 30° C. or less in order to prevent polymerization during production of the composition.

The viscosity of the composition may be appropriately set according to the application and purpose of use. A preferable viscosity is 5 to 10,000 mPa·s, more preferably 10 to 1,000 mPa·s. If the viscosity is high, it is difficult to obtain a cured film that is thin and has excellent surface smoothness.
Viscosity in the present invention means a value measured at 25° C. with an E-type viscometer.

The present invention also provides a method for storing a curable composition containing the components (A), (B) and (C), wherein the curable composition does not contain the component (D). Alternatively, storage of a curable composition stored in a state containing 3 parts by weight or less of component (D) with respect to a total of 100 parts by weight of components (A), (B) and (C). It also relates to methods.
Thereby, it is possible to prevent deterioration of the antifogging durability of the cured film of the composition due to Michael addition of the component (D) to the component (A).

The composition of the present invention can be used as an active energy ray-curable composition or as a thermosetting composition, but is preferably used as an active energy ray-curable composition.
The composition of the present invention contains the components (A) to (C) as essential components, but various components can be blended depending on the purpose.
Other components include, specifically, a photopolymerization initiator [hereinafter referred to as "(E) component"], a thermal polymerization initiator [hereinafter referred to as "(F) component"] and (G) component [(A) compounds having one ethylenically unsaturated group other than the component and the component (B)] and the like.
These components are described below.
As for the other components described later, only one kind of the exemplified compounds may be used, or two or more kinds thereof may be used in combination.

1) Component (E) When the composition of the present invention is used as an active energy ray-curable composition and further used as an electron beam-curable composition, the component (E) (photopolymerization initiator) is not included. , electron beam curing is also possible.
When the composition of the present invention is used as an active energy ray-curable composition, particularly when ultraviolet rays and visible light are used as active energy rays, from the viewpoint of ease of curing and cost, component (E) is further added. It is preferable to contain.
When used as an electron beam curable composition, component (E) does not necessarily have to be contained, but a small amount may be blended as necessary to improve curability.

Various known photopolymerization initiators can be used as the component (E) in the present invention. Further, the component (E) is preferably a radical photopolymerization initiator.
Specific examples of component (E) include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenylketone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one. , 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopro pan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, diethoxyacetophenone, oligo{2-hydroxy-2-methyl-1-[4-( Acetophenone compounds such as 1-methylvinyl)phenyl]propanone} and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one ;
Benzophenone compounds such as benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone and 4-benzoyl-4'-methyldiphenylsulfide;
α-keto ester compounds such as methylbenzoyl formate, 2-(2-oxo-2-phenylacetoxyethoxy)ethyl ester of oxyphenylacetic acid and 2-(2-hydroxyethoxy)ethyl ester of oxyphenylacetic acid;
2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide Phosphine oxide compounds such as;
Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; titanocene compounds; 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4 - acetophenone/benzophenone hybrid photoinitiators such as methylphenylsulfinyl)propan-1-one;
oxime ester photopolymerization initiators such as 2-(O-benzoyloxime)-1-[4-(phenylthio)]-1,2-octanedione; and camphorquinone.

Among these, acetophenone-based compounds, benzophenone-based compounds, and phosphine oxide-based compounds are preferred, and even when the cured film is coated as a thin film of several μm or less, good curability can be easily obtained under air. Acetophenone-based compounds are particularly preferred because they can be used.

The content of component (E) is preferably 0.01 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, with respect to 100 parts by weight of the total amount of curable components. ~5 parts by weight is particularly preferred. Within the above range, the curability of the composition is excellent, and the scratch resistance of the resulting cured film is excellent.

2) Component (F) Component (F) is a thermal polymerization initiator, and when the composition is used as a thermosetting composition, component (F) can be blended.
The composition of the present invention can be mixed with a thermal polymerization initiator and cured by heating.
Various compounds can be used as the thermal polymerization initiator, and organic peroxides and azo initiators are preferred.

Specific examples of organic peroxides include 1,1-bis(t-butylperoxy) 2-methylcyclohexane, 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)cyclohexane, 2 , 2-bis(4,4-di-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluoylperoxy)hexane, t-butylperoxy oxyisopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl peroxyacetate, 2, 2-bis(t-butylperoxy)butane, t-butylperoxybenzoate, n-butyl-4,4-bis(t-butylperoxy)valerate, di-t-butylperoxyisophthalate, α, α '-Bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl Peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3 , 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide and the like.

Specific examples of azo compounds include 1,1′-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile , azodi-t-octane, azodi-t-butane and the like.
These may be used alone or in combination of two or more. Also, the organic peroxide can be combined with a reducing agent to cause a redox reaction.

The content of component (F) is preferably 10 parts by weight or less per 100 parts by weight of the total amount of curable components.
When the thermal polymerization initiator is used alone, it may be carried out according to the conventional means of normal radical thermal polymerization. Heat curing can also be performed for the purpose of improving the

3) Component (G) Component (G) is a compound having one ethylenically unsaturated group other than components (A) and (B).
Component (G) is an arbitrary component used to adjust the viscosity and other physical properties of the composition, and various components can be used.
Examples of the component (G) include (meth)acrylates having one (meth)acryloyl group [hereinafter referred to as "monofunctional (meth)acrylates"], and (meth)acryloyl groups having one (meth)acryloyl group. ) acrylamide compounds [hereinafter referred to as “monofunctional (meth)acrylamide”] and the like.

Specific examples of monofunctional (meth)acrylates include
Methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, lauryl ( Alkyl (meth)acrylates such as meth)acrylate and stearyl (meth)acrylate;
Cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, etc. A monofunctional (meth)acrylate having an alicyclic group of;
glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclohexanespiro-2-(1,3-dioxolane -4-yl)methyl (meth)acrylate, monofunctional (meth)acrylates having a cyclic ether group such as 3-ethyl-3-oxetanylmethyl (meth)acrylate;
aromatic monofunctional (meth)acrylates such as benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, o-phenylphenoxy (meth)acrylate and p-cumylphenolethylene (meth)acrylate;
Monofunctional (meth)acrylates having a maleimide group such as (meth)acrylolyloxyethylhexahydrophthalimide;
(meth)acryloylmorpholine;
Examples include monofunctional (meth)acrylates having an alkoxyalkyl group, such as alkylcarbitol (meth)acrylates such as ethyl carbitol (meth)acrylate and 2-ethylhexyl carbitol (meth)acrylate.

Specific examples of monofunctional (meth)acrylamides include N-methyl (meth)acrylamide, Nn-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, Nn-butyl (meth)acrylamide, N-alkyl (meth)acrylamides such as N-sec-butyl (meth)acrylamide, Nt-butyl (meth)acrylamide, Nn-hexyl (meth)acrylamide; N such as N-hydroxyethyl (meth)acrylamide - hydroxyalkyl (meth)acrylamide; and N,N-dimethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide ) acrylamide, N,N-di-n-propyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, N,N-di-n-butyl(meth)acrylamide and N,N-dihexyl(meth)acrylamide and N,N-dialkyl (meth)acrylamide of.

The content of component (G) is preferably 1 to 30 parts by weight, more preferably 5 to 25 parts by weight, and 10 to 20 parts by weight with respect to 100 parts by weight of the total amount of the curable components. is more preferable. Within the above range, the physical properties can be adjusted without impairing the excellent adhesion to the substrate, which is a feature of the composition of the present invention.

4) Other components other than those mentioned above As other components other than those mentioned above, known additives can be used. Examples include antioxidants, surface modifiers, hydrophilic polymers, fillers, silane coupling agents, acid generators, pigments, dyes, tackifiers and polymerization inhibitors.
Among these other components, organic solvents, antifog modifiers, ultraviolet absorbers, light stabilizers, acidic substances, antioxidants, surface modifiers, hydrophilic polymers, and fillers are described below.

<Organic solvent>
Although the composition of the present invention can be used without solvent, various organic solvents can be used for the purpose of adjusting coating viscosity and film thickness.
When using an organic solvent, it must be a compound that does not correspond to component (D). Specifically, aromatic compounds such as benzene, toluene and xylene; propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, etc. ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ether compounds such as dibutyl ether; and N-methylpyrrolidone.

Incidentally, the component (D) can also be blended immediately before the composition is applied.
Specific examples in this case include the compounds described above.

The content of the organic solvent is preferably 0.01 to 200 parts by weight, more preferably 10 to 150 parts by weight, more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the total amount of the curable components. Parts by weight are more preferred.

<Anti-fogging modifier>
In the composition of the present invention, the cured film is excellent in repeated anti-fogging properties. A substance can be added.
Anti-fogging modifiers include ionic surfactants having no ethylenically unsaturated groups.
Known ionic surfactants having no ethylenically unsaturated group can be used, and examples thereof include anionic surfactants, cationic surfactants and zwitterionic surfactants. .

Examples of anionic surfactants include dialkyl sulfosuccinates such as di(2-ethylhexyl) sodium sulfosuccinate and di(2-ethylhexyl) ammonium sulfosuccinate; fatty acid salts such as sodium oleate and potassium oleate; lauryl higher alcohol sulfates such as sodium sulfate and ammonium lauryl sulfate; alkylbenzenesulfonates such as sodium dodecylbenzenesulfonate; alkylnaphthalenesulfonates of sodium alkylnaphthalenesulfonate; naphthalenesulfonic acid formalin condensates; Polyoxyethylene sulfate salts such as ethylene alkylphenyl ether sodium sulfate and the like are used.
Among these compounds, dialkyl sulfosuccinates are preferred from the viewpoint of superior initial anti-fogging properties.
Dialkyl sulfosuccinates are commercially available, and commercial products can be used. As di(2-ethylhexyl) sulfosuccinate sodium salt, Shin Nippon Rika Co., Ltd. Likasurf P-10 (solution of the same compound), M-30 (solution of the same compound) and G-30 (propylene glycol of the same compound / water mixed solution), and RAPISOL A30, A70, A80 and A90 manufactured by NOF Corporation. Examples of the di(2-ethylhexyl)ammonium sulfosuccinate include Likasurf G-600 (propylene glycol/water mixed solution of the same compound manufactured by Shin Nippon Rika Co., Ltd.).

Cationic surfactants include ethanolamines, amine salts such as laurylamine acetate, triethanolamine monoformate, stearamideethyldiethylamine acetate, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and dilauryldimethylammonium chloride. , quaternary ammonium salts such as distearyldimethylammonium chloride, lauryldimethylbenzylammonium chloride and stearyldimethylbenzylammonium chloride.

Examples of the zwitterionic surfactant include fatty acid type zwitterionic surfactants such as dimethylalkyllaurylbetaine and dimethylalkylstearylbetaine, sulfonic acid type zwitterionic surfactants such as dimethylalkylsulfobetaine, and alkylglycine. mentioned.

Among these ionic surfactants having no ethylenically unsaturated groups, anionic surfactants are preferred from the viewpoint of superior initial antifogging properties, and dialkyl sulfosuccinates are more preferred as described above.

The content of the antifogging modifier is preferably 0.1 to 10% by weight per 100% by weight of the total amount of the composition of the present invention. When the content of the anti-fogging modifier is within the above range, the initial anti-fogging property of the cured film can be excellent without impairing the repeated anti-fogging property.

<Ultraviolet absorber>
Specific examples of UV absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)- 1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1, 3,5-triazine, 2-[4-[(2-hydroxy-3-(2-ethylhexyloxy)propyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyroxyphenyl)-6-(2,4-bisbutyroxyphenyl)-1,3,5-triazine, 2-( Triazine UV absorbers such as 2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine; 2-(2H-benzo triazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy Benzotriazole UV absorbers such as -5-(2-(meth)acryloyloxyethyl)phenyl]-2H-benzotriazole; benzophenone UV absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone; cyanoacrylate UV absorbers such as ethyl-2-cyano-3,3-diphenyl acrylate and octyl-2-cyano-3,3-diphenyl acrylate; UV rays such as titanium oxide particles, zinc oxide particles and tin oxide particles; and inorganic particles that absorb
Among the above compounds, benzotriazole-based UV absorbers are particularly preferred.

UV absorbers are used for the purpose of suppressing the discoloration of plastic substrates, which tend to turn yellow due to exposure to active energy rays, and are also used to protect articles with a cured coating film from sunlight when used outdoors. Used to prevent deterioration.
The content of the ultraviolet absorber is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and 0.05 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable components. More preferably 1 to 2 parts by weight.

<Light stabilizer>
As the light stabilizer, known light stabilizers can be used, and among them, hindered amine light stabilizers (HALS) are preferred.
Specific examples of hindered amine light stabilizers include bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate , 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3 ,5-triazine, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester and the like.
Commercially available hindered amine light stabilizers include TINUVIN 111FDL, TINUVIN123, TINUVIN 144, TINUVIN 152, TINUVIN 292, and TINUVIN 5100 manufactured by BASF.

The content of the light stabilizer is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, more preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the total amount of the curable components. More preferably 1 to 1 part by weight.

<Acidic substances>
The composition of the present invention is excellent in adhesion to substrates such as plastics, and the adhesion can be further improved by adding an acidic substance.
Examples of acidic substances include photoacid generators, inorganic acids, and organic acids that generate acids upon exposure to active energy rays. Inorganic acids include sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, and the like. Organic acids include organic sulfonic acid compounds such as p-toluenesulfonic acid and methanesulfonic acid.
Among these, an inorganic acid or an organic acid is preferable, an organic sulfonic acid compound which is an organic acid is more preferable, an aromatic sulfonic acid compound is more preferable, and p-toluenesulfonic acid is particularly preferable.
The content of the acidic substance is preferably 0.0001 to 5 parts by weight, more preferably 0.0001 to 1 part by weight, and more preferably 0.0005 parts by weight with respect to 100 parts by weight of the total amount of the curable components. More preferably ~0.5 parts by weight. When the content of the acidic substance is within the above range, the cured film has excellent adhesion to the substrate, and problems such as corrosion of the substrate and decomposition of other components can be prevented.

<Antioxidant>
The composition of the present invention may further contain an antioxidant for the purpose of improving the heat resistance and weather resistance of the cured film.
Examples of antioxidants used in the present invention include phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like.
Preferable examples of phenolic antioxidants include hindered phenols such as di-t-butylhydroxytoluene. Commercially available products include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70 and AO-80 manufactured by Adeka Corporation.
Preferable examples of phosphorus-based antioxidants include phosphines such as trialkylphosphine and triarylphosphine, and trialkyl phosphite and triaryl phosphite. Commercially available products of these derivatives include, for example, Adekastab PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A and 3010 manufactured by Adeka Co., Ltd. etc.
Examples of sulfur-based antioxidants include thioether-based compounds, and commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation.

The antioxidant content is preferably 0.01 to 5% by weight, more preferably 0.1 to 1% by weight, based on 100% by weight of the total composition of the present invention. When the content of the antioxidant is within the above range, the composition has excellent stability and good curability and adhesion.

<Surface modifier>
A surface modifier may be added to the composition of the present invention for the purpose of improving the leveling property during application, or for the purpose of improving the slipperiness of the cured film to improve the scratch resistance.
Surface modifiers include surface modifiers, surfactants other than those mentioned above, leveling agents, antifoaming agents, agents for imparting smoothness and agents for imparting antifouling properties, and known surface modifiers can be used. can be done.
Among them, silicone-based surface modifiers and fluorine-based surface modifiers are preferred. Specific examples include silicone-based polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone-based polymers and oligomers having a silicone chain and a polyester chain, and fluorine-based polymers having a perfluoroalkyl group and a polyalkylene oxide chain. and oligomers, and fluorine-based polymers and oligomers having perfluoroalkyl ether chains and polyalkylene oxide chains.
A surface modifier having an ethylenically unsaturated group, preferably a (meth)acryloyl group, in the molecule may also be used for the purpose of increasing the durability of the lubricity.

The content of the surface modifier is preferably 0.01 to 1.0% by weight based on 100% by weight of the total amount of the composition of the present invention. When the content of the surface modifier is within the above range, the surface smoothness of the cured film is excellent.

<Hydrophilic polymer>
When the curable composition of the present invention is applied to a substrate, repelling or the like may occur in the coating film after the composition has been applied to the substrate and dried, depending on the type of substrate to be applied and the coating method. , the appearance of the finally obtained cured film may be poor.
In this case, it is preferable to add a hydrophilic polymer to the curable composition for the purpose of preventing repelling of the coating film.

Hydrophilic polymers include polymers having hydrophilic groups.
Examples of hydrophilic groups include acidic groups and hydroxyl groups, with acidic groups being preferred. The acidic group includes a carboxyl group, a sulfonic acid group, a phosphoric acid group, and the like, preferably a carboxyl group or a sulfonic acid group, and more preferably a carboxyl group.
As a hydrophilic polymer having an acidic group (hereinafter referred to as an "acidic group-containing polymer"), a neutralized salt obtained by neutralizing a part or all of the acidic groups is preferable. As a method for producing the neutralized salt of the acidic group-containing polymer, there is a method in which a neutralized salt is used as a raw material vinyl-based monomer, and a method in which an acidic group-containing polymer is produced and then neutralized. A manufacturing method and the like can be mentioned.

As the hydrophilic polymer, a polymer having a vinyl-based monomer having a hydrophilic group as an essential constituent monomer unit is preferable. Examples of vinyl-based monomers having a hydrophilic group include vinyl-based monomers having an acidic group and vinyl-based monomers having a hydroxyl group.

Examples of vinyl-based monomers having an acidic group include ethylenically unsaturated compounds having a carboxyl group, ethylenically unsaturated compounds having a sulfonic acid group, and ethylenically unsaturated compounds having a phosphoric acid group.
Ethylenically unsaturated compounds having a carboxyl group include (meth)acrylic acid, maleic acid, itaconic acid, crotonic acid, and salts of these compounds. Ethylenically unsaturated compounds having a sulfonic acid group include acrylamide 2-methylpropanesulfonic acid, styrenesulfonic acid, and (meth)allylsulfonic acid. Examples of ethylenically unsaturated compounds having a phosphoric acid group include phosphoric acid group-containing (meth)acrylates such as esters of phosphoric acid and (meth)acrylic acid.
When the acidic group-containing polymer is a neutralized salt in which some or all of the acidic groups are neutralized, it is preferable to use a neutralized salt as the vinyl-based monomer having an acidic group.
Alkaline compounds for forming neutralized salts of vinyl monomers having an acidic group include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; ammonia; and triethylamine and triethanol. Examples include amine compounds such as amines.

Vinyl monomers having a hydroxyl group include hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate and hydroxybutyl (meth)acrylate.

As the hydrophilic polymer, copolymers of vinyl-based monomers other than vinyl-based monomers having a hydrophilic group (hereinafter referred to as "other monomers") may be used.
Other monomers include alkyl (meth)acrylate, alkylaminoalkyl (meth)acrylate, styrene, alkyl vinyl ether, vinylidene chloride, (meth)acrylamide, N-vinylformamide, N-vinylacetamide, vinyl acetate, vinylpyrrolidone, (meth)acrylonitrile, (meth)acryloylmorpholine, and the like.
Alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, ) acrylate and decyl (meth)acrylate.
Dialkylaminoalkyl (meth)acrylates include dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.

The weight average molecular weight (hereinafter referred to as “Mw”) of the hydrophilic polymer is preferably 5,000 to 100,000, more preferably 7,000 to 30,000.
In the present invention, the Mw of the hydrophilic polymer means a value determined by gel permeation chromatography (hereinafter referred to as "GPC") using standard polystyrene as a calibration curve, and carboxylic acid etc. as an acid component. is the value measured before neutralizing the acidic groups of In addition, since GPC measurement cannot be performed when amine monomers are included as other monomers, ordinary alkyl (meth) acrylates are used instead of these components, and the same polymerization temperature, initiator concentration, monomer It means a value estimated from the results of GPC measurement of a polymer polymerized under the same conditions such as concentration and solvent concentration.

As the hydrophilic polymer, those produced by conventional polymerization using the above-mentioned monomers can be used.
For example, a radical polymerization method, a living anion polymerization method, a living radical polymerization method, and the like can be mentioned.
Examples of the form of polymerization include solution polymerization, emulsion polymerization, suspension polymerization and bulk polymerization.
When attempting to produce the aforementioned low-molecular weight polymer by a normal polymerization method, it is usually necessary to increase the amount of chain transfer agent and polymerization initiator. When a polymer containing a large amount of a chain transfer agent is used, the cured film tends to be colored by irradiation with active energy rays. tends to decrease.
Therefore, a polymer produced by high-temperature polymerization that does not require a large amount of chain transfer agent or polymerization initiator is preferred.
The temperature for high-temperature polymerization is preferably 160 to 350°C, more preferably 180 to 300°C.

The form of the hydrophilic polymer may be selected according to the purpose, and examples thereof include hydrophilic polymer solutions, hydrophilic polymer dispersions, powders, and the like.
Specific examples include an organic solvent solution of a hydrophilic polymer, an aqueous solution or dispersion of a hydrophilic polymer, a mixed solution or aqueous dispersion of an organic solvent and water of a hydrophilic polymer, and powders. Among these, an aqueous solution or aqueous dispersion of the hydrophilic polymer, an organic solvent solution, and a mixed solution or aqueous dispersion of the hydrophilic polymer in an organic solvent and water are preferred because of their excellent solubility in the composition.
The solid content of the hydrophilic polymer solution or dispersion is preferably 3 to 70% by weight.
The viscosity of the hydrophilic polymer solution or dispersion is preferably 5 to 20,000 mPa·s.

The content of the hydrophilic polymer is preferably 0.5 to 50 parts by weight based on the solid content in either an aqueous solution or an aqueous dispersion with respect to 100 parts by weight of the total amount of the composition. , more preferably 2 to 30 parts by weight.
By setting the content of the hydrophilic polymer to 0.5 parts by weight or more, it is possible to prevent repelling of the cured film, improve adhesion to various substrates, and improve adhesion to thin substrates such as films. It is possible to prevent deformation and warping of the substrate when the composition of the present invention is applied and cured. can be prevented.

<Filler>
When the composition of the present invention contains an organic solvent, if the component (B) and/or component (C) have a low viscosity, the organic When the solvent evaporates, the composition may repel on the substrate, resulting in poor coating film appearance.
When a composition containing an organic solvent is used in the coating method as described above, it is preferable to add a filler to the composition to increase the viscosity, since repelling after drying can be prevented.
As the filler, both inorganic fillers and organic fillers can be used, and organic fillers are preferred.
Examples of inorganic fillers include inorganic compounds such as silica and alumina.
Examples of organic fillers include hydrophobic polymers such as polyurethane, poly(meth)acrylate, polyamide, polyurea, nylon, polystyrene, polyethylene and polypropylene, with poly(meth)acrylate being preferred.
As the hydrophobic polymer, one having a high average molecular weight is preferable because it can reduce the number of parts to be added for thickening and can prevent deterioration of the antifogging property of the composition. However, it preferably has a high molecular weight within a range that does not impair compatibility with the composition, and the weight average molecular weight is preferably 10,000 to 5,000,000, more preferably 100,000 to 2,000,000.
The filler is preferably in the form of particles, and its average particle size is preferably 1 to 15 μm, more preferably 4 to 12 μm.
The average particle size in the present invention means a value measured at a wavelength of 680 nm by a laser diffraction method.
Considering the effect on the anti-fogging property, the content of the filler is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the total composition excluding the organic solvent. is preferred, and 0.5 to 5 parts by weight is more preferred.

6. Method of use The composition of the present invention may be used in accordance with conventional methods.
For example, there is a method in which the composition is applied to the substrate to which it is applied by a conventional coating method, and then cured by irradiation with active energy rays or by heating.
As for the irradiation method of the active energy ray, a general method known as a conventional curing method may be adopted.
In addition, the component (E) (photopolymerization initiator) and the component (F) (thermal polymerization initiator) are used together in the composition, and after irradiating with active energy rays, the composition is heated and cured to improve adhesion to the substrate. A method for improving the property can also be adopted.

In the case where the curable composition is an active energy ray-curable composition, if there is a heating step after the irradiation with the active energy ray, long-term heating may reduce the antifogging property.
In this case, a method of supplying an inert gas such as nitrogen gas and heating after irradiating with active energy rays in an inert gas atmosphere is preferable because deterioration of the anti-fogging property can be prevented.

Substrates to which the composition of the present invention can be applied include various materials such as inorganic materials, plastics, and paper.
Examples of inorganic materials include glass, metals, mortar, concrete, and stone materials. Examples of metals include steel plates, metals such as aluminum and chromium, and metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO). mentioned.
Specific examples of plastics include polyolefins such as polyethylene and polypropylene, ABS resins, polyvinyl alcohol, cellulose acetate resins such as triacetyl cellulose and diacetyl cellulose, acrylic resins, polyethylene terephthalate, polycarbonates, polyarylates, polyether sulfones, norbornene, and the like. cyclic polyolefin resins, polyvinyl chloride, epoxy resins, polyurethane resins and the like, which use cyclic olefins of the above as monomers.

Among these substrates, the composition of the present invention has excellent adhesion to plastics, and therefore can be preferably applied to plastics. Furthermore, as inorganic materials, glass and metal can be preferably applied, and as plastics, polyethylene terephthalate, polycarbonate, poly(methyl) methacrylate, and copolymers containing these as main components can be preferably applied.

The method of applying the composition of the present invention to a substrate may be appropriately set according to the purpose, and may be a bar coater, an applicator, a doctor blade, a dip coater, a roll coater, a spin coater, a flow coater, a knife coater, a comma A coating method using a coater, a reverse roll coater, a die coater, a lip coater, a spray coater, a gravure coater, a micro gravure coater, or the like can be mentioned.

The film thickness of the composition-cured film with respect to the substrate may be appropriately set according to the purpose. The thickness of the cured film may be selected depending on the substrate to be used and the application of the substrate having the cured film produced, but is preferably 1 to 100 μm, more preferably 2 to 40 μm. .

When the composition contains an organic solvent, it is preferable to heat and dry the composition after applying it to the substrate to evaporate the organic solvent.
The drying temperature is not particularly limited as long as it is not higher than the temperature at which problems such as deformation of the applied base material do not occur. A preferable heating temperature is 40 to 100°C. The drying time may be appropriately set depending on the substrate to be applied and the heating temperature, preferably 0.5 to 20 minutes.

When the composition of the present invention is used as an active energy ray-curable composition, examples of the active energy ray for curing include electron beams, ultraviolet rays and visible rays, but ultraviolet rays or visible rays are preferred, and ultraviolet rays are preferred. Especially preferred. Ultraviolet irradiation devices include high-pressure mercury lamps, metal halide lamps, ultraviolet (UV) electrodeless lamps, light emitting diodes (LEDs), and the like.
The irradiation energy should be appropriately set according to the type of active energy ray and composition, but if a high-pressure mercury lamp is used as an example, the irradiation energy in the UV-A region is 100 to 8,000 mJ/. cm ² is preferred, and 200-3,000 mJ/cm ² is more preferred. When the irradiation energy is 1,000 mJ/cm ² or more, it is preferable to incorporate the antifogging modifier described above from the viewpoint of the antifogging performance of the cured film.

When the composition of the present invention is used as a thermosetting composition, a cured film can be obtained by allowing the cured film to stand still in a heatable dryer or the like.
The heating temperature may be appropriately set according to the substrate to be used and the purpose, and is preferably 40 to 180°C. When the base material is plastic, the base material may be deformed if the temperature is too high, so the temperature is preferably 120° C. or less.
The heating time may be appropriately set depending on the substrate to be applied and the heating temperature, preferably 0.5 to 60 minutes.

7. Uses The composition of the present invention can be used for various purposes, and specific examples thereof include anti-fog coating agents and anti-dust adhesion coating agents for plastic substrates and floors.

Specific examples of coating agents include protective glasses, goggles, bathroom interior walls, kitchen surroundings, headlamp covers for automobiles and motorcycles, rear lamp covers, etc. Anti-fogging coating agents for glass and plastic, plastic substrates and floor surfaces. A dust-adhesion prevention coating agent for preventing dust adhesion, and the like are included.

EXAMPLES Examples and comparative examples are shown below to describe the present invention more specifically. It should be noted that the present invention is not limited by these examples.
Further, hereinafter, unless otherwise specified, "parts" means parts by weight, and "%" means % by weight.

1. Manufacturing example
1-1) Production Example 1 [Production of acrylate containing component (B) and component (C)]
Glycerin (purified glycerin (trade name) manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was added to a 3-liter flask equipped with a stirrer, a thermometer, a gas inlet tube, a rectifying column and a cooling tube. Hereinafter, it will be referred to as "GLY". ] 302.75 parts (3.29 mol), 2-methoxyethyl acrylate (hereinafter referred to as “MCA”) 2312.84 parts (17.77 mol), catalyst X DABCO (triethylenediamine) 6.51 parts (0.06 mol), 24.07 parts (0.12 mol) of zinc acrylate as catalyst Y, 1.19 parts (0.01 mol) of hydroquinone monomethyl ether (hereinafter referred to as "MEHQ"), phenothiazine 0.21 part (0.002 mol) of was charged, and an oxygen-containing gas (5% by volume of oxygen and 95% by volume of nitrogen) was bubbled into the liquid.
While heating and stirring the reaction liquid temperature in the range of 100 to 130 ° C., the pressure in the reaction system was adjusted in the range of 110 to 760 mmHg, and 2-methoxyethanol (hereinafter referred to as "MEL") was withdrawn from the reaction system through the rectifying column and the cooling pipe. In addition, MCA was added to the reaction system in the same weight part as the liquid withdrawn. After 18 hours from the start of heating and stirring, the pressure in the reaction system was returned to normal pressure to complete the extraction.
The acrylated rate of the hydroxyl groups of GLY was found to be 58 mol % from the amount of MEL produced.
After the reaction solution was cooled to room temperature and the precipitate was separated by filtration, aluminum silicate [Kyoward 700 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd.] was added to adsorb and remove catalyst X and catalyst Y contained in the filtrate. 58.7 parts of was added and stirred, and further heated and stirred in the range of 70 to 100° C. for 1 hour. After the aluminum silicate after the adsorption treatment is separated by filtration, the filtrate is placed in a flask connected to a stirrer, a thermometer, a gas inlet tube, a condenser tube for distillation, and a tube for pressure reduction, and the temperature is 70 to 100 ° C. and the pressure is Vacuum distillation was performed for 10 hours while bubbling dry air in the range of 0.001 to 100 mmHg to separate a distillate containing unreacted MCA. 5.0 parts of diatomaceous earth [Radiolite (trade name) manufactured by Showa Kagaku Kogyo Co., Ltd.] was added to the pot liquid, pressure filtration was performed, and the obtained filtrate was used in Examples. Yield was 651 parts. This is called BC-1.
When all 302.75 parts of GLY charged were converted to glycerin diacrylate (hereinafter also referred to as "GLY-DA"), the yield was 658 parts. 99%.
Using HPLC equipped with a UV detector, the purity of each component contained in BC-1 was calculated from the following formula (1). TA”) was 33%, and glycerin monoacrylate (hereinafter referred to as “GLY-MA”) was 5%.
The resulting BC-1 had a viscosity of 43 mPa·s (25° C.) and a hydroxyl value of 238 mgKOH/g. Mw was 314 by GPC measurement.

HPLC, viscosity, hydroxyl value, GPC and GC were measured under the following conditions.
HPLC measurement conditions/apparatus: ACQUITY UPLC manufactured by Waters Co., Ltd.
・ Detector: UV detector ・ Detection wavelength: 210 nm
Column: ACQUITY UPLC BEH C18 (Part No. 186002350, column inner diameter 2.1 mm, column length 50 mm, manufactured by Waters Co., Ltd.)
・Column temperature: 40°C
・Composition of eluent: mixed solution of 0.03% by weight trifluoroacetic acid aqueous solution and methanol ・Flow rate of eluent: 0.3 mL/min

◆ Purity calculation method of GLY-DA contained in BC-1 Purity of GLY-DA (%)
= [(D x 1.27)/(M x 1.74 + D x 1.27 + T)] x 100 (1)
D, M, and T in formula (1) mean the following values obtained by analyzing BC-1 using HPLC equipped with an ultraviolet (UV) detector.
・D: Peak area of GLY-DA at 210 nm ・M: Peak area of GLY-MA at 210 nm ・T: Peak area of GLY-TA at 210 nm

◆Viscosity measurement conditions An E-type viscometer was used to measure the viscosity at 25°C.

◆Hydroxyl value measurement conditions An acetylation reagent is added to the sample and heat-treated in a hot bath at 92°C for 1 hour. After standing to cool, a small amount of water is added and heat treatment is performed in a hot bath at 92°C for 10 minutes. After allowing to cool, the acid was titrated with a potassium hydroxide ethanol solution using the phenolphthalein solution as an indicator to determine the hydroxyl value.

◆GPC measurement conditions/equipment: Waters Co., Ltd. GPC system name 1515 2414 717P RI
・Detector: Differential refractive index (RI) detector ・Column: Guard column Shodex KFG (8 μm 4.6 × 10 mm) manufactured by Showa Denko K.K., two types of this column Waters styragel HR 4E THF (7. 8 x 300mm) + styragel HR 1THF (7.8 x 300mm)
・Column temperature: 40°C
- Eluent composition: THF (containing 0.03% sulfur as an internal standard), flow rate 0.75 mL/min - Calibration curve: A calibration curve was created using standard polystyrene.
- Among the detection peaks derived from BC-1, detection peaks derived from monofunctional (meth) acrylates, solvents, and detection peaks with retention times slower than peaks derived from water are not considered in the calculation of Mw, The Mw was calculated by considering the other multiple detected peaks as one peak.

1-2) Production Example 2 [Production of acrylate containing component (B) and component (C)]
302.71 parts (3.29 mol) of GLY and 2312.76 parts (17.77 mol) of MCA were placed in a 3-liter flask equipped with a stirrer, thermometer, gas inlet tube, rectifying column and condenser. , 9.76 parts (0.087 mol) of DABCO as catalyst X, 36.10 parts (0.17 mol) of zinc acrylate as catalyst Y, 1.60 parts of MEHQ, 4-hydroxy-2,2, 0.074 parts of 6,6-tetramethylpiperidine-1-oxyl (hereinafter referred to as "TEMPOL") and 5.00 parts (0.28 mol) of pure water were charged, and an oxygen-containing gas (5% by volume of oxygen, 95% by volume of nitrogen) was bubbled into the liquid. While heating and stirring the reaction liquid temperature in the range of 105 to 130° C., the pressure in the reaction system is adjusted in the range of 150 to 760 mmHg, and the mixed liquid of MCA and MEL produced as a by-product along with the progress of the transesterification reaction is rectified. It was withdrawn from the reaction system via a tower and condenser. In addition, MCA was added to the reaction system in the same weight part as the liquid withdrawn. Also, MCA containing MEHQ and TEMPOL was added as needed to the reaction system via the rectification column. After 40 hours from the start of heating and stirring, the pressure in the reaction system was returned to normal pressure, and the extraction was completed.
The acrylated rate of the hydroxyl groups of GLY was found to be 91 mol % from the amount of MEL produced.
The resulting reaction product was cooled to room temperature and the precipitate was separated by pressure filtration. 14 parts of aluminum silicate [Kyowa Kagaku Kogyo Co., Ltd. Kyoward 700 (trade name)] was added to the filtrate, and after contact treatment by heating and stirring at an internal temperature of 80 to 105 ° C. under normal pressure for 1 hour, 27 parts of calcium hydroxide was added at a temperature of 20 to 40° C. and stirred for 1 hour under normal pressure.
After separating the insoluble matter by pressure filtration, vacuum distillation is performed for 16 hours at a temperature of 70 to 98 ° C. and a pressure of 0.001 to 100 mmHg while bubbling dry air through the filtrate to contain unreacted MCA. The distillate was separated.
The resulting pot liquid was cooled to room temperature, 0.16 part (0.0018 mol) of N,N-diethylhydroxylamine was added, and the mixture was stirred under normal pressure for 1 hour. After that, 8.0 parts of activated carbon (Taiko S (trade name) manufactured by Futamura Chemical Co., Ltd.) was added and stirred at room temperature for 1 hour for contact treatment, and then the solid matter containing activated carbon was separated by pressure filtration to obtain the filtrate. is called BC-2.
Using HPLC equipped with a UV detector, the purity of each component contained in BC-2 was calculated from the above formula (1), and as a result, GLY-DA was 8% and GLY-TA was 92%. .
The obtained BC-2 had a viscosity of 26 mPa·s (25° C.) and a hydroxyl value of 16 mgKOH/g. Mw was 338 by GPC measurement.

2. Examples 1 to 6 and Comparative Example 1 (Preparation of composition)
Using BC-1 obtained in Production Example 1 and the components with the following abbreviations, the proportions shown in Table 1 were stirred and mixed at 40° C. to obtain a composition. Each composition was used after being left for 7 days after the composition was prepared.
The obtained composition was measured for viscosity at 25° C. using an E-type viscometer.
(A) component and (D) component mixture
・ JI-62C01: Propylene glycol monomethyl ether (hereinafter referred to as "PGME") 50% solution of a compound having a cation having an acryloyl group and an ammonium ion and an anion (hereinafter referred to as "A-1-1") [Japan JI-62C01 manufactured by Emulsifier Co., Ltd.]
(A) component, (B) component and (C) component mixture
· JI-64C01: 50% solution of A-1 and BC-2 [JI-64C01 manufactured by Nippon Nyukazai Co., Ltd.]. A solution in which the entire amount of PGME in JI-62C01 was replaced with BC-2 obtained in Production Example 2.
· JI-64C02: 50% solution of A-1 and BC-1 [JI-64C01 manufactured by Nippon Nyukazai Co., Ltd.]. A solution in which the entire amount of PGME in JI-62C01 was replaced with BC-1 obtained in Production Example 1.
(A) component
SR-10: A compound having an SO ₃ NH ₄ group (anionic) at one end of a polyethylene glycol (additional mole number: 10) and an alkyl group and an allyl group at the other end [Adekalia manufactured by ADEKA Co., Ltd. Soap SR-10]
(B) component and (C) component mixture
・MT-3545: A mixture product of 70 parts of dipentaerythritol pentaacrylate (hereinafter referred to as “DPET-PA”) and 30 parts of dipentaerythritol hexaacrylate (hereinafter referred to as “DPET-HA”) [manufactured by Toagosei Co., Ltd. Aronix MT-3545]
(E) component
HCPK: 1-hydroxy-cyclohexyl-phenyl-ketone [IRGACURE184 manufactured by BASF]
・TPO: (2,4,6-trimethylbenzoyl) diphenylphosphine oxide, Irgacure TPO manufactured by BASF
Other ingredients
・ G-30: Di(2-ethylhexyl) sodium sulfosuccinate in propylene glycol (hereinafter referred to as “PG”) / water mixed solution (solid content: 70%, PG: 15%, water: 15%), Shin Nippon Rika Rikasurf G-30 manufactured by Co., Ltd. In Tables 1 and 2 below, the solid content, component (D) (PG), and water are shown separately.
・ AC-AC: polymethyl methacrylate, acrylicon AC manufactured by Mitsubishi Rayon Co., Ltd. (Mw: about 1.3 million)

2. Evaluation of plastic substrates The compositions obtained in Examples 1 to 6 and Comparative Example 1 were cut using a bar coater. Polycarbonate manufactured by Mitsubishi Engineering-Plastics, Iupilon NF2000 (150 mm × 70 mm × 1 mm) with a film thickness of 10 μm. It was coated so as to be a test piece.
Then, using a high-pressure mercury lamp [H06-L41 manufactured by Eye Graphics Co., Ltd.] equipped with a conveyor, the UV-A lamp output illuminance was 80 W/cm, the irradiation intensity per pass was 250 mW/cm ² , and the irradiation energy was 400 mJ. /cm ² , the specimen was irradiated with ultraviolet rays. As an index for active energy ray curing, the number of passes until tackiness on the surface of the cured film disappeared was evaluated. A smaller number of passes indicates better curability.
The obtained cured film was used and evaluated according to the following methods. Those results are shown in Table 2.

1) Adhesion The obtained cured film was cut with a cutter knife at intervals of 1 mm in length and width to form 100 squares with a size of 1 mm × 1 mm. After pasting the cellophane tape, it was strongly peeled off. The number of remaining films after peeling was evaluated. The larger the number of remaining films, the better the adhesion.

2) Pencil Hardness The pencil hardness of the resulting cured film was measured with a load of 750 g according to JIS K5600-5-4.

3) The antifogging persisting cured film was exposed to steam at 80°C for 1 minute, and whether or not the cured film fogged was visually evaluated. After the evaluation, the anti-fogging durability was evaluated by wiping off moisture adhering to the surface of the cured film with paper, and then exposing the cured film to steam at 80°C for 1 minute, which was repeated eight times in total. In addition, A, B, and C in Table 2 represent the following meanings.
A: Not cloudy, B: Slightly cloudy, C: Cloudy

4) Water contact angle The cured film immediately after curing and the cured film after repeated evaluation of anti-fog durability five times were measured for contact angle with water using a contact angle measurement device OCA20 manufactured by Eiko Seiki Co., Ltd.
Water was dripped on the cured film using a microsyringe, and the value was read 30 seconds later.
In general, there is a correlation between anti-fogging performance and contact angle, and a cured film showing a low contact angle even after evaluation of anti-fogging persistence indicates better anti-fogging performance.

Parentheses in the formulation column of Tables 1 and 2 mean the number of parts of each component, and "-" means not contained.
In addition, in the composition column in Tables 1 and 2, the components (A) to (C) contained in JI-64C01 and JI-64C02 used as raw materials are separately described, and included in JI-62C01. (A) component and (D) component are described separately.

4. As is clear from the results of Examples 1 to 6 in Table 3 of the evaluation results , the composition of the present invention is excellent in adhesion to plastic substrates, surface hardness, antifogging properties of cured film surfaces, and durability thereof. Met.
On the other hand, the composition of Comparative Example 1 contains component (D) in excess of 3 parts by weight with respect to a total of 100 parts by weight of component (A), component (B) and component (C), so that the cured film Due to the small amount of component (A) bound and incorporated therein, the anti-fogging performance deteriorated upon repeated exposure to steam. Furthermore, in the fifth anti-fogging durability evaluation, no visual difference was observed between Examples 1 to 6 and Comparative Example 1, but the contact angle measurement result with water showed that Comparative Example 1 was larger. It's gone.
For the compositions of Examples 1 to 6, a cured film was formed in the same manner as described above, except that the specimen was irradiated with ultraviolet rays under the condition of an irradiation energy of 1000 mJ/cm ² . Persistence was evaluated. As a result, in the compositions of Examples 1 to 3, the antifogging durability of the cured film was reduced, but in the compositions of Examples 4 to 6 containing G-30, the antifogging of the cured film was There was no change in sustainability, and it was excellent.

The curable composition of the present invention can be preferably used as a curable composition, and the resulting cured film has excellent adhesion and scratch resistance to various substrates, and has antifogging properties and dust adhesion prevention. It also has excellent performance. It can be preferably used as protective glasses, goggles, bathroom interior walls, headlamp covers and rear lamp covers for automobiles and motorcycles, anti-fogging paints for security camera lenses, etc., and dust-adhesion prevention coating agents for plastic films.

Claims (13)

Including the following (A) component, (B) component and (C) component,
In the total 100% by weight of components (A) to (C) below, 1 to 30% by weight of component (A), 10 to 97% by weight of component (B), and 2 to 60% by weight of component (C) % including
Does not contain the following component (D), or contains the following component (D) in a proportion of 3 parts by weight or less with respect to a total of 100 parts by weight of components (A), (B) and (C) Composition.
Component (A): A compound having an ethylenically unsaturated group and an ionic group, the compound containing the following component (A-1) Component (A-1): a cation having an ethylenically unsaturated group in one molecule A compound consisting of a functional group and an anion, and represented by the following formula (1)

In the above formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an optionally branched alkylene group having 1 to 12 carbon atoms, and R ³ and R ⁴ are each independently represents an optionally branched alkyl group having 1 to 10 carbon atoms, and X ^- is an alkyl sulfate ion, polyoxyalkylene alkyl ether sulfate ion, polyoxyalkylene alkylphenyl ether sulfate ion, alkyl sulfonate ion or Represents an alkylbenzenesulfonate ion.
Component (B): a compound having a hydrophilic group and an ethylenically unsaturated group Component (C): a compound having two or more ethylenically unsaturated groups other than the components (A) and (B) Component (D) : A hydroxyl group-containing compound that does not have an ethylenically unsaturated group The curable composition according to claim 1, wherein the component (A) contains the component (A-1) and the component (A-2) below.
Component (A-2): a compound consisting of an anionic group having an ethylenically unsaturated group in one molecule and a cation 3. The curable composition according to claim 1, wherein the component (B) is a compound having a hydroxyl group and two or more ethylenically unsaturated groups. The curable composition according to any one of claims 1 to 3, wherein the component (B) is a compound having a (meth)acryloyl group as an ethylenically unsaturated group. The curable composition according to any one of claims 1 to 4, wherein the component (C) is a compound having a (meth)acryloyl group as an ethylenically unsaturated group. 6. The curable composition according to any one of claims 1 to 5 , further comprising an ionic surfactant having no ethylenically unsaturated groups. 7. The curable composition according to any one of claims 1 to 6 , further comprising a radical photopolymerization initiator (E). 8. The curable composition according to any one of claims 1 to 7 , further comprising a thermal radical polymerization initiator (F). An active energy ray-curable coating composition comprising the composition according to claim 7 . An active energy ray-curable antifogging coating composition comprising the composition according to claim 7 . A thermosetting coating composition comprising the composition of claim 8 . A thermosetting anti-fogging coating composition comprising the composition according to claim 8 . Including the following (A) component, (B) component and (C) component,
In the total 100% by weight of components (A) to (C) below, 1 to 30% by weight of component (A), 10 to 97% by weight of component (B), and 2 to 60% by weight of component (C) %include
A method for storing a curable composition,
The curable composition does not contain the following component (D), or 3 parts by weight of the following component (D) with respect to a total of 100 parts by weight of the components (A), (B) and (C) A method for preserving a curable composition in which the composition is preserved in a state containing the composition at a ratio of 10 parts or less.
Component (A): a compound having an ethylenically unsaturated group and an ionic group, the compound containing the following component (A-1) Component (A-1): a cation having an ethylenically unsaturated group in one molecule A compound consisting of a functional group and an anion, and represented by the following formula (1)

In the above formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an optionally branched alkylene group having 1 to 12 carbon atoms, and R ³ and R ⁴ each independently represents an optionally branched alkyl group having 1 to 10 carbon atoms, and X ^- is an alkyl sulfate ion, polyoxyalkylene alkyl ether sulfate ion, polyoxyalkylene alkylphenyl ether sulfate ion, alkyl sulfonate ion or Represents an alkylbenzenesulfonate ion.
Component (B): a compound having a hydrophilic group and an ethylenically unsaturated group Component (C): a compound having two or more ethylenically unsaturated groups other than the components (A) and (B) Component (D) : A hydroxyl group-containing compound that does not have an ethylenically unsaturated group