KR20020031072A - Photo-curable composition and method for curing thereof - Google Patents

Abstract

PURPOSE: A photocurable emulsion composition and a method of curing the same are provided which solve problems of a conventional photocurable composition, such as VOC, productivity and labor cost, or those of a cured article consisting of a conventional photocurable emulsion composition, such as water resistance (resistance to boiling water), acid resistance, solvent resistance and a photosensitive characteristic. CONSTITUTION: The photocurable composition contains a reactive monomer and/or a reactive prepolymer, a photoinitiator, emulsion particles and a variable surfactant as an emulsifier. The method of curing the photocurable composition is characterized in that a heat treatment and/or an active energy beam irradiation treatment is implemented after coating with the photocurable composition.

Description

Photocurable composition and its hardening method {PHOTO-CURABLE COMPOSITION AND METHOD FOR CURING THEREOF}

The present invention relates to a photocurable composition. More specifically, by including the variable surfactant in the photocurable composition, the variable surfactant is thermally decomposed and / or photolyzed by, for example, thermal and / or active energy ray irradiation treatment, and the resulting cured product is water resistant (non-water resistant). The present invention relates to a photocurable composition exhibiting excellent properties such as acid resistance, solvent resistance, photosensitive properties, and the like, suitable for various uses such as paints, printing inks, surface coating agents, photoresist inks, adhesives, and the like, and a curing method thereof.

Conventionally, the photocurable composition is wide in order to solve problems such as VOC (Volatile Organic Solvent) problems such as odor, toxicity, air pollution, energy saving energy saving by productivity and simplification of equipment, and energy saving by reducing labor cost. It is used in a wide range of fields. However, in order to improve the fast curing property and coating property, which are the characteristics of the photocurable composition, a relatively low molecular weight reactive monomer or an organic solvent is often used in combination, and the toxicity, odor, flammability, irritability, etc. of these organic solvents and reactive monomers are often used. It is a problem.

Therefore, for the purpose of solving such a problem, (1) a method of introducing a hydrophilic site into the active energy ray-curable compound by copolymerization or the like to have self-water dispersibility or self-emulsification, and (2) a low molecular weight of a conventional active energy ray-curable compound A method of dispersing or emulsifying using a type or polymer type emulsifier, and (3) using a combination of an active energy ray-curable compound dispersed or emulsified in the above method with an acrylic emulsion or a water-soluble polymer, or the like. Precurable compounds and active energy radiation curable emulsions are being developed. However, the emulsions obtained by these methods, etc., have insufficient dispersibility, problems with water resistance, solvent resistance, acid resistance, photosensitivity, adhesiveness, etc. of the cured film, and the reality is still not commercialized.

In order to solve the said problem, Unexamined-Japanese-Patent No. 2-300204 has disclosed the manufacturing method of the emulsion which introduce | transduced the polymerizable double bond into the particle surface. In this case, although a crosslinking density can be made to some extent by introduce | transducing a polymeric double bond into a particle surface, it does not satisfy | fill characteristics, such as water resistance, solvent resistance, acid resistance, photosensitive characteristic, adhesiveness, etc. of hardened | cured material. Moreover, the manufacturing process is complicated and the cost becomes difficult. In addition, Japanese Patent Application Laid-Open No. 9-157495 discloses a polymer emulsion in which emulsion particles are three-dimensionally crosslinked and a method for producing the same. In this manufacturing method, it is simple and easy to manufacture, and the crosslinking density is also improved and effective. However, it does not sufficiently satisfy the properties of the cured product such as water resistance, solvent resistance, acid resistance, photosensitive properties, and adhesiveness of the cured film. Japanese Unexamined Patent Application Publication No. 8-302240 discloses a photocurable composition of a crosslinking emulsion method in which a composition chemically bonds polymerizable compounds in micelles of an emulsion by a polymerization reaction. However, since the chemical bond of hardened | cured material is too strong, it is inferior to adhesiveness with a base material, and does not satisfy | fill the characteristic of hardened | cured material, such as water resistance elsewhere. Patent 3030351 discloses a photocurable emulsion resin composition using a water-soluble polymer. However, there is a problem that the water resistance is insufficient because a water-soluble high polymer is used.

Accordingly, the present invention reduces the VOC problem as much as possible, improves the productivity, and furthermore, the cured product is a photocurable composition having excellent water resistance (non-water resistance), acid resistance, solvent resistance, photosensitive properties, adhesiveness, and the like, and a curing method thereof. The task is to obtain.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching and examining in order to solve the said subject about the photocurable composition and its hardening method, the present inventors finally completed this invention. That is, the present invention provides a photocurable composition comprising a variable surfactant as an emulsifier in a photocurable composition containing (1) a reactive monomer and / or a reactive prepolymer, a photoinitiator, an emulsion particle, and an emulsifier, and (2) an emulsion particle. The photocurable composition according to the above ①, which is a polymer emulsion obtained by reacting a vinyl monomer and an emulsifier, ③ the photocurable composition according to the above ① or ②, wherein the variable surfactant is a thermally variable and / or photovariable surfactant, and ④ the above ① After coating using the photocurable composition in any one of-③, it is related with the hardening method of the photocurable composition characterized by heat-treating and / or irradiating an active energy ray.

The emulsion particles used in the present invention are polymer emulsions obtained by emulsion polymerization of vinyl monomers in the presence of a variable surfactant, and a method of forcibly emulsifying crosslinkable emulsion particles, non-crosslinkable polymer compounds and polymer resins in the presence of a variable surfactant. Non-crosslinkable emulsion particles and the like obtained by, for example.

As said vinyl monomer, For example, aromatic monovinyl compounds, such as styrene, (alpha) -methylstyrene, fluorostyrene, and vinylpyridine, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl (Meth) acrylic acid ester monomers, such as hexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and N, N-dimethylaminoethyl (meth) acrylate, (meth Amide-based monomers such as vinyl cyanide compounds such as acrylonitrile, acid anhydrides of mono or dicarboxylic acids or dicarboxylic acids such as (meth) acrylic acid, maleic acid and itaconic acid, and styrene sulfides. Ionic monomers, such as sodium fonate and a sulfonated isoprene, etc. can be used. In addition, within the allowable ranges in terms of polymerization rate and stability during polymerization, conjugated double bond compounds such as butadiene and isoprene, vinyl esters such as vinyl acetate and α-olefins such as 4-methyl-1-pentene Can be used. These vinyl monomers may be used independently or may be used in combination of 2 or more type.

In addition, when it is desired to increase the crosslinking density by three-dimensionally crosslinking the emulsion particles, a crosslinkable vinyl monomer can be used. Examples of the crosslinkable vinyl monomers include divinylbenzene, ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane (meth) acrylate, and trimethylol ethane tri (meth). An acrylate, neopentyl glycol (meth) acrylate, methylenebisacrylamide, etc. can be illustrated. In the present invention, in addition to these crosslinkable vinyl monomers, in particular, vinylbenzene and ethylene glycol dimethacrylate can be preferably used. These crosslinkable vinyl monomers may be used independently, or may be used in combination of 2 or more type. These crosslinkable vinyl monomers may be used in combination with the above-mentioned single functional vinyl monomers, and the amount of the crosslinkable vinyl monomers is 20 mol% or less, preferably 0.1-20 mol%, and more preferably 0.5-20%, based on the total amount of vinyl monomers. 10 mol%.

The variable surfactant used in the present invention initially has a hydrophilic part and a hydrophobic part in one molecule, and any change is made by heat and / or active energy ray irradiation or the like to become hydrophobic. In addition, it has a function as an emulsifier which is usually used in the process of forming emulsion particles (particle formation, particle aggregation, stabilization of particles, etc.), and by heat and / or active energy ray irradiation, (i) the hydrophilic part of the molecular structure of the surfactant (hydrophilic part and hydrophobic part) is chemically changed to become a hydrophobic part, (ii) the hydrophilic part and a part of the hydrophobic part are physically decomposed to increase the proportion of the hydrophobic part, and (iii) decomposed It refers to surfactants having properties such as hydrophobization by crosslinking reaction between chemical substances.

Specifically, as the variable surfactant changed by heat treatment, for example, a variable surfactant composed of ion-forming groups such as ammonium salt, pyridinium salt, sulfonium salt, alsonium salt, and phosphonium salt may be exemplified. The former is thermally decomposed by heat treatment, and becomes hydrophobic by changing to any one of the above (i) to (iii).

On the other hand, in the photovariable surfactant by active energy ray irradiation, the chemical substance itself is photolyzed by active energy ray irradiation, or the chemical substance is decomposed through an acid generator or a basic generator by active energy ray irradiation. It can be mentioned. For example, as the chemical substance itself is photolyzed, variability having α-ketocarboxylate, β-ketocarboxylate, phenyl acetate, nitrophenyl acetate, azosulfonate salt, and the like in part of the structural skeleton of the surfactant Surfactant can be illustrated. Moreover, as a chemical substance which decomposes | dissolves through an acid generator by active energy ray irradiation, it has dioxirane, a 1, 3- dioxane ring, a siloxane, polyethyleneglycol monomethylester acetal, etc. in a part of structural framework of surfactant, for example. Variable surfactants can be exemplified and acetal bis (ammonium bromide) can be exemplified as a chemical substance decomposed through the basic generator.

These variable surfactants can also be used for the non-crosslinkable emulsion particles obtained by forcibly emulsifying the non-crosslinkable polymer compound and the polymer resin. Specific examples of the non-crosslinkable polymer compound and polymer resin include epoxy compounds, epoxy resins, polyester resins, urethane resins, polyurea resins, vinyl acetate, and the like. These can be made hydrophobic by forcibly stirring the mixture which consists of the reactive monomer mentioned later, a photoinitiator, a water-soluble organic solvent, and water in presence of a variable surfactant, and irradiating heat treatment and / or an active energy ray. . .

In addition, although the usage-amount when manufacturing emulsion particle | grains using a variable surfactant can be arbitrarily contained according to the particle size, stability, crosslinking density, and the characteristic of hardened | cured material of an emulsion particle, the compounding quantity is 0.01-0.01 with respect to the vinyl monomer whole quantity. About 80% by weight, preferably 0.1 to 50% by weight. More preferably, it is 0.1-10 weight%. Moreover, in order to improve the standing stability of the emulsion particle whose average particle diameter is 100 nm or more, it is preferable to use 5 weight% or more of a variable surfactant.

The temperature at the time of emulsion polymerization using a variable surfactant is about 50-95 degreeC, Preferably it is 65-85 degreeC. In addition, the density | concentration at the time of emulsion polymerization is performed in the range of about 10-50 weight%, Preferably it is 15-40 weight% of the ratio of solid content which combined the vinyl monomer and a variable surfactant.

Moreover, as a polymerization initiator used for obtaining crosslinkable emulsion particle | grains by emulsion polymerization using the variable surfactant of this invention, if it is used by normal emulsion polymerization, there will be no restriction | limiting in particular. For example, water-soluble radical polymerization initiators such as persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate, hydrogen peroxide, organic peroxides and aqueous azo initiators, or the like, or the persulfate and sodium hydrogen sulfite, hydrogen thiosulfate Redox-based polymerization initiators combined with various reducing agents such as sodium and ascorbic acid can be used. It is preferable to make the usage-amount of a polymerization initiator into the range of 0.005-5 mol% with respect to vinyl monomer whole quantity.

The photocurable composition of this invention demonstrated above can manufacture crosslinkable emulsion particle by the manufacturing method etc. which are described in Unexamined-Japanese-Patent No. 9-157495, etc. The average particle diameter of the crosslinkable emulsion particle obtained by this method can obtain the particle about 0.05-500 micrometers.

In the present invention, in order to improve the water resistance, acid resistance, solvent resistance, and photosensitivity of the cured product, the following reactive prepolymer or reactive monomer can be contained inside and outside the emulsion particles. Specifically, epoxy (meth) acrylate, polyurethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, silicone (meth) acrylate, polybutadiene (meth) as a reactive prepolymer Acrylate, polyamide (meth) acrylate, etc. can be illustrated. Moreover, as a reactive monomer, vinyl monomers, such as styrene, vinyl acetate, and N-vinyl pyrrolion, butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-dodecyl acrylate Monofunctional monomers such as isophoronyl acrylate, dicyclopentenyloxyethyl acrylate and phenoxyethyl acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol Diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, bisphenol A diethoxy diacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate And polyfunctional monomers such as dipentaerythritol hexaacrylate. The usage-amount of these reactive monomers or reactive prepolymers is about 0.1-200 weight% normally in a photocurable composition, Preferably it is the range of 1-100 weight%.

Moreover, in order to harden | cure the photocurable composition of this invention with an ultraviolet-ray, a photopolymerizable initiator is contained. On the other hand, when hardening with an electron beam, a photoinitiator becomes unnecessary. As a photoinitiator, what is normally used for an ultraviolet curable compound can be used. For example, acetophenone, benzophenone, benzoin ether, chloroacetophenone, diethoxyacetophenone, α-aminoacetophenone, benzylmethyl ketal, thioxanthone, α-acyl oxime ester, acylphosphine oxide, glycoxy ester, 3-ketocoumarin, 2-ethylanthraquinone, campaquinone, Michler ketone, etc. can be illustrated. These photoinitiators are usually used in the emulsion composition in an amount of 0.1 to 20% by weight, preferably 1 to 10% by weight.

You may mix a water-soluble organic solvent with the photocurable composition of this invention. As the water-soluble organic solvent, for example, an organic solvent having good affinity with water such as methanol, ethanol, propanol, isopropanol, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane or the like can be used. In particular, it is preferable that an emulsion composition can be removed by azeotropy. The compounding quantity of a water-soluble organic solvent can be mix | blended in the range of 0.1-50 weight%, Preferably it is 1-10 weight%.

As mentioned above, said photocurable composition can be used as an aqueous dispersion. The addition method to the emulsion particles of the aqueous dispersion may be batch addition, continuous addition or intermittent addition, or a combination thereof. Moreover, the density | concentration of the emulsion particle at the time of adding an aqueous dispersion is about 10-50 weight%, Preferably it is 15-40 weight%. The temperature at the time of addition is about 20-70 degreeC, Preferably it is 30-50 degreeC.

In addition, when preparing a non-crosslinkable emulsion particle using a noncrosslinkable high molecular compound and a polymer resin in presence of a variable surfactant, a noncrosslinkable high molecular compound and a polymer resin, the said variable surfactant, a reactive monomer, a photoinitiator, and a water-soluble organic solvent And emulsion particles can be produced by mixing water and forcibly stirring.

Next, as a hardening method of obtaining hardened | cured material using the photocurable composition of this invention, the hardening method by heat processing and / or active energy ray irradiation is mentioned. Specifically, as the heat treatment temperature in the case of using the thermally variable surfactant, the ion former is decomposed by treatment in the range of 120 to 200 ° C, preferably 130 to 150 ° C. Thermal decomposition becomes inadequate at the temperature below 120 degreeC, and it is difficult to obtain a target hardened | cured material. Moreover, it is effective that the ultraviolet-ray as an active energy ray in the case of using the said light-variable surfactant is a wavelength of 150-500 mmicro, especially the wavelength range of 300-400 mmicro. As a light source to be used, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a carbon arc lamp, an ultraviolet fluorescent lamp, a chemical lamp, a xenon lamp, a zirconium lamp, etc. are preferable. Moreover, as a method of obtaining hardened | cured material using the photocurable composition which consists of this invention, after preliminary drying at the temperature of 60-110 degreeC, it irradiates with an ultraviolet-ray and further dries to the temperature of 120-200 degreeC. The method can also be adopted.

The photocurable composition which consists of this invention is a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a polystyrene film, a polyimide film, a polyamideimide film, a polyimide copper clad laminated board, a rigid board, a glass plate, for example. It can apply to the base materials, such as paper and harden | cure by the said method, and can obtain a hardened | cured material, It is not limited to the said base material.

Examples of coating methods include methods such as a gravure coat method, a kiss coat method, a dip method, a spray coat method, a curtain coat method, an air knife coat method, a blade coat method, a reverse roll coat method, a screen printing method, and an electrostatic spray coat method. Although it can employ | adopt, it is not limited to these.

Moreover, although arbitrary pigment | dye, a pigment, a leveling agent, an antifoamer, a filler, etc. can be added to the photocurable composition of this invention, it is not specifically limited.

According to one Embodiment of the photocurable composition of this invention and its hardening method, (I) the photocurable emulsion mainly consisting of a reactive monomer, a photoinitiator, and a variable surfactant is obtained. (II) The emulsion is coated on the copper foil surface of the polyimide film copper clad laminate so that the thickness after the drying treatment is about 10 g / m ² , and dried at 80 ° C. for 20 minutes. (III) The obtained coating film surface is photocured with the illuminance of 500 mj / cm <^2> using a 3KW ultrahigh pressure mercury lamp. (IV) Furthermore, it dries at 150 degreeC for 30 minutes. (V) The cured film obtained by these hardening methods is evaluated according to an evaluation item.

Example

Hereinafter, although this invention is demonstrated concretely using an Example, this invention is not limited to these Examples. In addition, in an Example, a part means a weight part. In addition, the evaluation item and method in an Example depend on the following method.

1) Water resistance (non-water resistance): After immersing the sample which has a cured film on the copper foil of the polyimide film copper clad laminated board in non-aqueous water of 80 degreeC-90 degreeC for 1 hour, the water droplet of the surface of a cured film is wiped off, and JISK5400 cross cut test ( Adhesion with copper foil was evaluated by cross cut test).

100/100: O 80/100: (triangle | delta) 80 or less / 100: It was set as x.

2) Acid resistance: The sample was immersed at room temperature for 30 minutes using 10% hydrochloric acid and 10% sulfuric acid solution, and evaluated in the same manner as in 1).

3) Solvent resistance: The sample was immersed for 30 minutes at room temperature using toluene and acetone and evaluated in the same manner as in 1).

4) Pencil hardness: The copper foil-shaped cured film was evaluated by the JISK5400 pencil scratch test method. The measured value of the photosensitive property of the cured film was judged by this measured value.

≥H: O ≥B: △ F <: ×

5) Emulsion particle size: Emulsion particle size was measured using Culter Model N4SD (product of COULTER ELECTRONICS, INC).

6) Electrical insulation resistance: A cured film is formed on the IPC pattern made by etching copper foil by the above method, and it is processed by 50 degreeC and 85% RH for 160 hours by JIS C0022 high temperature and high humidity test method, and high resistance measuring instrument (HIGH The insulation resistance after applying for 1 minute at 500 V using RESISTANCE METER (manufactured by Yokogawa Hewlett Packard Co., Ltd.) was measured.

Example 1

Into a 1 liter reactor equipped with a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser, 440 g of ion-exchanged water, 0.24 mg of copper sulfate, and 22 g of an α-ketocarboxylate-type surfactant were stirred, followed by a 28% aqueous ammonia solution. PH was adjusted to 3.5. Subsequently, 28.8 g of methyl methacrylate, 12.3 g of butyl acrylate, and 0.4 g of sodium thiosulfate were added, and the mixture was stirred and mixed at 30 ° C. through nitrogen gas. The polymerization was then initiated by adding 14 g of 5% aqueous ammonium persulfate solution. In the step where exothermic by polymerization was initiated, a mixed solution of 131 g of methyl methacrylate and 56.1 g of butyl acrylate was added dropwise for 2 hours. At this time, the dropping rate was adjusted so that the temperature would not exceed 60 ° C. After completion of the dropwise addition, the mixture was kept at 60 ° C for 3 hours to obtain emulsion particles having an average particle diameter of 90 nm.

Next, 963.8 g of ion-exchanged water was added to the obtained emulsion to adjust the concentration to 15%, and then cooled to 40 ° C. 50 g of pentaerythritol tetraacrylate PE-4A (manufactured by Kyoeisha Kagaku Co., Ltd.), 1.5 g of photoinitiator Dalcure 1173 (Merck Co., Ltd.), α-ketocarboxyl in this 15% concentration emulsion 0.1 g of an acidic surfactant and 91.2 g of ion-exchanged water were added to a dispersion obtained by emulsifying (10000 rpm, 5 minutes) with a homogenizer (manufactured by Homogenizer; manufactured by JANKE & KUNKEL Co., Ltd.), and stirred at room temperature for 5 hours to obtain an average particle diameter of 95 The photocurable composition containing nm photovariable surfactant was obtained.

Example 2

A photocurable composition containing a photovariable surfactant having an average particle diameter of 95 nm was obtained in the same manner except that a diazo sulfonate type surfactant was used as the photovariable surfactant instead of the photovariable surfactant used in Example 1.

Example 3

A photocurable composition containing an optically variable surfactant having an average particle diameter of 97 nm was obtained in the same manner except that the phenylacetic acid type surfactant was used instead of the optically variable surfactant used in Example 1.

Example 4

Instead of the photovariable surfactant used in Example 1, an acid-decomposable surfactant that decomposes through an acid generator by irradiation with an active energy ray, and a surfactant TRITON SP (union carbide composed of a special hydrophobic group and a hydrophilic group of ethylene oxide chain) A photocurable composition containing an acid-decomposable surfactant having an average particle diameter of 97 nm was obtained in the same manner except that the product was manufactured by Japan Co., Ltd.).

Example 5

Instead of the acid-decomposable surfactant used in Example 4, as a basic decomposable surfactant that decomposes through a basic generator by irradiation with an active energy ray, except that an acetal bis (ammonium bromide) -based surfactant is used. In the same manner as in Example 1, a photocurable composition containing a basic decomposition surfactant having an average particle diameter of 100 nm was obtained.

Example 6

Next, a photocurable composition containing a thermally variable surfactant having an average particle diameter of 95 nm was obtained in the same manner as in Example 1 except that an ammonium salt type surfactant was used as the thermally variable surfactant.

Example 7

Moreover, the photocurable composition containing the thermally variable surfactant of 95 nm of average particle diameters was obtained by the method similar to Example 1 except having used sulfonium salt type surfactant as a thermally variable surfactant.

Comparative Example 1

A photocurable composition having an average particle diameter of 80 nm was obtained in the same manner as in Example 1 except that instead of the variable surfactant used in Example 1, sodium lauryl benzene sulfonate usually used as an emulsifier was used.

Comparative Example 2

A photocurable composition having an average particle diameter of 85 nm was obtained in the same manner as in Example 1, except that sodium lauryl sulfate commonly used as an emulsifier was used instead of the variable surfactant used in Example 1.

The emulsion compositions obtained in Examples 1 to 7 and Comparative Examples 1 and 2 were respectively coated on a 10Z polyimide film copper clad laminate so that the thickness after the drying treatment was 10 g / m ² . Then, the resultant was dried at 80 ° C. for 20 minutes, photocured at a roughness of 500 mj / cm ² using a 3 KW high pressure mercury lamp, and then the obtained photocured film was heat treated at 150 ° C. for 30 minutes to obtain a cured film. These cured films were evaluated according to the evaluation items. In addition, the measurement of the said insulation resistance was evaluated using what obtained by coating and hardening using the wiring pattern previously etched by the IPC evaluation pattern using the polyimide film copper clad laminated board. As a result of the evaluation, the results of Examples 1 to 7 and Comparative Examples 1 and 2 are shown in Table 1.

Degradable surfactants Emulsifier Water resistance Acid resistance Solvent resistance Photosensitive characteristics Insulation Resistance Photolysis Pyrolysis Molding (Non-water resistant) 10% hydrochloric acid 10% sulfuric acid toluene Acetone Pencil hardness Early 160 hours later Example 1 α-ketocarboxylate type ○ ○ ○ ○ ○ ○ 2.00E + 13 2.00E + 13 Example 2 Diazosulfonic Acid Type ○ ○ ○ ○ ○ ○ 3.00E + 13 2.00E + 13 Example 3 Phenyl acetate type ○ ○ ○ ○ ○ ○ 2.00E + 13 2.00E + 13 Example 4 TRITON SP ○ ○ ○ ○ ○ ○ 4.00E + 13 2.00E + 13 Example 5 Acetal type bis (ammonium bromide) type ○ ○ ○ ○ ○ ○ 2.00E + 13 2.00E + 13 Example 6 Ammonium Salt Type ○ ○ ○ ○ ○ ○ 2.00E + 14 8.00E + 13 Example 7 Sulfonium salt type ○ ○ ○ ○ ○ ○ 2.00E + 14 9.00E + 13 Comparative Example 1 Sodium laurylbenzenesulfonate × × × ○ ○ ○ 2.00E + 12 2.00E + 10 Comparative Example 2 Sodium Lauryl Sulfate × × × ○ ○ ○ 2.00E + 12 2.00E + 10 TRITON SP (trade name) in Table 1: Anionic activator consisting of hydrophilic properties of special hydrophobic groups and ethylene oxide chains

As is apparent from Table 1, the photocurable composition of the present invention and the cured product formed by the curing method are excellent in water resistance (non-water resistance), acid resistance, solvent resistance, photosensitive properties, adhesiveness, and electrical insulation, such as paint, printing, and the like. It can be used for applications such as inks, surface coatings, photoresists, adhesives, etc., which contributes to the industry.

Claims (4)

A photocurable composition containing a reactive monomer and / or a reactive prepolymer, a photoinitiator, emulsion particles, and an emulsifier, wherein the photocurable composition contains a variable surfactant as an emulsifier. The photocurable composition according to claim 1, wherein the emulsion particles are polymer emulsions obtained by reacting a vinyl monomer and an emulsifier, and contain a variable surfactant as an emulsifier. The photocurable composition according to claim 1 or 2, wherein the variable surfactant is a heat variable and / or light variable surfactant. After coating using the photocurable composition in any one of Claims 1-3, heat processing and / or active energy ray irradiation process, The hardening method of the photocurable composition characterized by the above-mentioned.