KR20110037117A - Self- photocurable epoxy resin composition including the same - Google Patents

Abstract

PURPOSE: A self-photocurable epoxy resin composition and a coating composition including the same are provided to control a coating agent with excellent properties without use of a photoinitiator causing atmospheric environment pollution. CONSTITUTION: A self-photocurable epoxy (meth)acrylate resin composition comprises: an epoxy (meth)acrylate prepolymer which is a copolymer of at least one epoxy compound, at least one Michael's donor, at least one (meth)acrylic acid having a carboxyl group; and a (meth)acrylate monomer. A β-dicarbonyl Michael's donor is at least one kind selected from the group consisting of β-ketoester, β-diketone, β-ketoamide, and β-ketoanilide.

Description

Magnetic photocurable epoxy resin composition and coating composition comprising same {SELF- PHOTOCURABLE EPOXY RESIN COMPOSITION INCLUDING THE SAME}

The present invention relates to ultraviolet and electron beam photocurable epoxy resin compositions and coating compositions.

In general, initiators or photoinitiators are mainly used in resins synthesized by applying all or part of (meth) acrylate monomers and / or oligomers. (Meth) acrylate monomers and oligomers may be crosslinked by free radical chaining mechanisms, which may require any free radical generating species such as peroxides, hydroperoxides, or azo compounds, They can decompose at room temperature upon heating or in the presence of an accelerator to form radicals.

Another means of initiation reaction is to decompose the photoinitiator into free radicals using ultraviolet (UV) or electron beam (EB) wavelengths. For many applications, this method offers the possibility of very fast reaction rates, because of their high energy upon exposure of UV or EB radiation, which results in instantaneous transformation of liquid reactive compositions into solids by crosslinking. to be.

The disadvantages of using an initiator or photoinitiator are air pollution in working processes due to the generation of highly volatile unreacted toxic low molecular weight organics that are produced by the decomposition of these initiators to their own molecular and atomic levels by the active reactions of these initiators. Not only can cause damage to the human body of the operator. That is, a disadvantage of the use of initiators to achieve efficient free radical reactions is that fugitive emissions, such as the generation of low molecular weight fragments, in which decomposition of initiators and photoinitiators can volatilize during and / or after the manufacturing process, is easily achieved through the human skin. It tends to be absorbed, leading to harmful effects on health, consumers and the environment and safety issues.

 Therefore, there is a need for research on the development of a technology that can produce a self-photocurable epoxy (meth) acrylate resin more environmentally and safely without using a separate photoinitiator.

The present invention is to provide a magnetic photocurable epoxy (meth) acrylate resin composition and a magnetic photocurable coating composition comprising the same, which can produce a coating of excellent performance without using a photoinitiator that causes air pollution or harmful to the human body. do.

The self-photocurable epoxy (meth) acrylate resin composition of the present invention is a self-photocurable epoxy (meth) which is a copolymer of (meth) acrylic acid having at least one epoxy compound, at least one Michael donor, and at least one carboxyl group. It is characterized by containing an acrylate prepolymer and a (meth) acrylate monomer.

Here, the epoxy compound is bisphenol-A liquid epoxy resin, bisphenol-A solid epoxy resin, hydrogenated bisphenol-A epoxy resin, bromineated epoxy resin, cresol novolac epoxy resin, phenol novolac type It is characterized in that at least any one or more from the group selected from epoxy resin, BPA- novolak-type epoxy resin or a mixture thereof.

And the β-dicarbonyl Michael donor is at least one or more from the group consisting of β-keto ester, β-diketone, β-ketoamide and β-ketoanilide, or the β-dicarbonyl Michael donor is ethyl It is characterized in that at least one or more selected from the group consisting of acetoacetate, 2,4-pentanedione, and acetoacetanilide.

In addition, the (meth) acrylic acid having a carboxyl group is characterized in that at least one or more of the group selected from methacrylic acid or acrylic acid and mixtures thereof.

The (meth) acrylate monomer is characterized in that at least any one or more of the group selected from monofunctional monomers or polyfunctional monomers and mixtures thereof.

The self-photocurable epoxy (meth) acrylate resin composition of the present invention has 20 to 65% by weight of the epoxy compound, 5 to 15% by weight of the Michael donor and the carboxyl group with respect to 100 parts by weight of the total composition. Another characteristic is that it contains 10 to 25% by weight of the acrylic acid and 20 to 40% by weight of the (meth) acrylate monomer.

Next, the magnetic photocurable coating composition of the present invention is selected from the group consisting of surfactants, antioxidants, light stabilizers, phosphate adhesion promoters, silane coupling agents, thermal polymerization inhibitors, levelers, quencher, dispersant, antifoaming agent It is characterized by further comprising at least an additive.

The magneto-photocurable coating composition of the present invention is further characterized by including the magneto-photocurable epoxy (meth) acrylate resin composition.

The self-photocurable resin composition and the coating composition according to the present invention can produce an excellent coating composition without causing a pollution of the air environment or using a photoinitiator that is harmful to a human body, thereby providing an environmentally friendly paint composition. Has

The self-photocurable epoxy (meth) acrylate resin composition of the present invention is a self-photocurable epoxy (meth) acrylate prepolymer which is a copolymer of (meth) acrylic acid having a carboxyl group with at least one epoxy compound, at least one Michael donor, ( It is characterized by containing a meth) acrylate monomer. And the (meth) acrylic acid having the carboxyl group is characterized in that the methacrylic acid or acrylic acid and mixtures thereof in more detail.

The self-photocurable epoxy (meth) acrylate resin composition of the present invention may contain 10 to 75 parts by weight, preferably 20 to 65 parts by weight of the epoxy compound with respect to 100 parts by weight of the total composition. In addition, the Michael donor may be included in 3 to 22 parts by weight, preferably 5 to 15 parts by weight based on 100 parts by weight of the total composition. The (meth) acrylic acid is included 7 to 40 parts by weight, preferably 10 to 25 parts by weight based on 100 parts by weight of the total composition, the (meth) acrylate monomer is 10 to 60 parts by weight based on 100 parts by weight of the total composition Part, preferably 20 to 40 parts by weight.

Hereinafter, the present invention will be described in more detail.

The present invention generally exhibits excellent performance that can be used as a single chemical monomer that is stable and reactive in itself when creating a molecular structure such as a prepolymer by introducing a Michael donor into an epoxy (meth) acrylate resin composition. There is a characteristic.

In addition, by introducing the Michael donor of the present invention to prepare a Michael addition-polymerized self-curing epoxy (meth) acrylate resin composition and a coating composition using the same, by using no compound known to function as a photoinitiator, The side effects of the conventional photoinitiator can be solved.

The present invention also provides a self-photocurable epoxy (meth) acrylate resin composition and a coating composition comprising a Michael addition polymer containing a double bond at both ends.

      In general, there are various known methods for introducing a double bond at both ends of an epoxy prepolymer substituted with an epoxy compound, but a preferred method is 2 moles of photocuring with respect to 1 mole of epoxy prepolymer. There exists a method (prepolymer method) which makes the (meth) acrylic acid containing a carboxyl group react. As the photocurable carboxyl group-containing (meth) acrylic acid used at this time, it is preferable to use an acrylic acid or methacrylic acid and mixtures thereof.

Examples of the epoxy compounds include bisphenol-A liquid epoxy resins, bisphenol-A solid epoxy resins, bisphenol-F epoxy resins, hydrogenated bisphenol-A epoxy resins, bromineated epoxy resins, and cresol novolac epoxy resins. A resin, a phenol novolak type epoxy resin, a BPA-novolak type epoxy resin, a DCPD type epoxy resin compound may be used alone or in combination. Among them, bisphenol-A type liquid epoxy resin, bisphenol-A type solid epoxy resin and these It is preferable to use a mixture thereof.

    In addition, the (meth) acrylic acid which has the said low molecular weight carboxyl group can use methacrylic acid or an acrylic acid individually or in mixture.

In addition, in the present invention, the "Michael Doner" refers to an electron donor in the Michael Addition in which an α, β unsaturated carbonyl compound and a compound having active methylene are added to α, β unsaturated nitrile. As a corresponding compound, the compound etc. which contain (beta) -carbonyl are mentioned especially. The term "Michael Acceptor" refers to a compound corresponding to an electron acceptor in the Michael addition reaction, and particularly includes a (meth) acrylic acid or a (meth) acrylate compound having an unsaturated double bond. have.

In the present invention, the β-dicarbonyl monomer which may participate in the addition reaction as the “Michael donor” is β-keto ester, β-diketone, β-ketoamide, β-ketoanilide, and / or other β-dica And a carbonyl compound, and may include one or more of them.

In particular, the present invention provides β-ketoesters (e.g. ethyl acetoacetate), β-ketoanilides (e.g. acetoacetanilide), β-ketoamides (e.g. acetoacetamide) or Michael depending on the properties and reactivity of the desired resin. It can be carried out as a mixture of donors.

Preferably, the β-dicarbonyl michael donor may be at least one selected from the group consisting of ethyl acetoacetate, 2,4-pentanedione, and acetoacetanilide.

Suitable β-dicarbonyl donor compounds having a functionality of 2 include ethyl acetoacetate, methyl acetoacetate, 2-ethylhexyl acetoacetate, lauryl acetoacetate, t-butyl acetoacetate, acetoacetanilide, N-alkyl acetoacetide Anilide, acetoacetamide, 2-acetoacetosylethyl acrylate, 2-acetoacetosylethyl methacrylate, allyl acetoacetate, benzyl acetoacetate, 2,4-pentanedione, isobutyl acetoacetate, and 2-methoxy Ethyl acetoacetate, including but not limited to.

Suitable β-dicarbonyl donor compounds having a functionality of 4 include 1,4-butanediol diacetoacetate, 1,6-hexanediol diacetoacetate, neopentyl glycol diacetoacetate, cyclohexane dimethanol diacetoacetate, and Ethoxylated bisphenol A diacetoacetates, including but not limited to.

    Suitable β-dicarbonyl donor compounds having a functionality of 6 include, but are not limited to, trimethylol propane triacetoacetate, glycerin triacetoacetate, and polycaprolactone triacetoacetate.

Michael addition polymerizations of the present invention can be prepared in the presence of a catalyst. In particular, the Michael addition reaction in the present invention can be promoted by a strong base. One example of such a base that can be used is diazabicycloundecene (DBU) that is sufficiently strong and readily solubilized in the monomer mixture. Other cyclic amidines such as diazabicyclo-nonene (DBN) and guanidine, or potassium hydroxide, are also suitable for use as catalysts in this reaction. Group I alkoxide bases such as potassium tetbutoxide with sufficient solubility in the reaction medium are also typically suitable to promote the desired reaction. Quaternary hydroxides and alkoxides such as tetrabutyl ammonium hydroxy groups or benzyltrimethyl ammonium methoxide may constitute other classes of base catalysts that promote Michael addition reactions.

The Michael addition polymerization reaction of the present invention can also be modified by adding an amine synergist to enhance performance. Examples of such modifications may include incorporation of primary or secondary amines into the uncured Michael adduct. Typical primary amines may include ethanolamine, methyl-1,6-hexanediamine, 3-aminopropyltrimethoxysilane, diaminopropane, benzyl amine, triethylenetetraamine, isophorone diamine and mixtures thereof.

Typical secondary amines may include dimethylamine, dibutyl amine, diethanolamine (DEA), piperidine, morpholine and mixtures thereof. If the liquid michael addition resin is modified with primary or secondary amines, the modified amine may simply react with the liquid uncured Michael addition resin.

Moreover, as a monofunctional monomer among the (meth) acrylate monomers of this invention, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, t-octyl (meth) acrylate, N, N-dimethyl (Meth) acrylate, N-vinyl caprolactam, N-vinylpyrrolidone, isobutoxy (meth) acrylamide, diacetone (meth) acrylamide, hydroxypropyl (meth) acrylate, hydroxyethyl (meth) Acrylate, hydroxybutyl acrylate, isobonyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentadiene (meth) acrylate, methoxypoly Propylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, poly Pylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, epoxy diethylene glycol (meth ) Acrylate, butoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, styryl (meth) acrylate, octadecyl (meth) acrylate, lauryl (meth) acrylate, dodecyl ( Meta) acrylate, isodecyl (meth) acrylate, nonyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isoamyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl ( Meth) acrylate, butyl (meth) acrylate, isopropyl (meth) acrylate, propyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, or a mixture thereof. As the polyfunctional monomer, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tri Propylene glycol diacrylate, trimethylolpropane trioxyethyl (meth) acrylate, tricyclodecane dimethanol diacrylate, or a mixture thereof is preferable.

In order to manufacture the coating composition of the present invention comprising the magnetic photocurable epoxy (meth) acrylate resin composition of the present invention, in addition to the composition, surfactant, antioxidant, light stabilizer, phosphate adhesion promoter, silane coupling agent, heat It is preferable to further add an alloying agent, a smoothing agent, a quencher, a dispersant, an antifoaming agent and the like. In particular, the resin composition of the present invention may be used in admixture with one or more additives such as pigments suitable for flooring materials (PVC, floor) and interior paints used.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention. However, the following examples and comparative examples are provided only to more easily understand the present invention, and the present invention is not limited to the following examples.

In Examples 1 to 8 and Comparative Examples 1 to 7 below, the physical properties of the resin and the coating composition were measured by various test methods as described below, and the purpose of defining the properties by means obvious to those skilled in the art. The following test methods were used.

Test environmental conditions

The test environment, i.e., the place where the test is to be performed, should be a place where direct sunlight does not exist and where there is very little gas, vapor, dust and ventilation at a temperature of 20 ± 2 ℃ and a humidity of 65 ± 5% (hereinafter referred to as room temperature). After the coating was left for 72 hours or more was used for the test.

Curing reaction and Coating  evaluation

The resins and coating compositions thus prepared were applied to glass coatings, and the curing reactions were then evaluated based on the evaluation of the coatings after irradiation of 400 mJ / cm ² UV, evaluation values 1 (wet, uncured), 2 (sticky), 3 ( Slippery surfaces, flaws are easily wound), 4 (sticky, can be scratched with a cotton swab), and 5 (sticky and flawless).

In addition, the minimum capacity for tack free and blemish free showed a total capacity (mJ / cm ² ) to achieve “5” according to the scale, wherein the color difference (yellow change) of the film surface at this time was ΔE Represented by.

Adhesion  evaluation

After coating the prepared resin and paint composition on the flooring material (PVC, Floor) and irradiated with 1000 mJ / cm ² and cured to evaluate the adhesion by the method of ASTM D 3359-87.

Steam resistance  And Pollutant  evaluation

In the steam resistance test, the resin and paint composition were coated on the flooring material (PVC, Floor) and cured by irradiation at 1000 mJ / cm ² , followed by curing by Han Kyung-hee steam cleaner (model HS series, HSC series, HSV series, SI series, SV). The surface cracks should be observed with the naked eye after about 25 minutes on the specimen.The contamination test should be good after removing it with dry cloth after 30 seconds of the same oily magic contamination. Can be.

Thus, the evaluation result visually discriminated is shown by the following classification.

[Steam Resistance and Pollution Evaluation Criteria]

X: severe coating damage, Δ: moderate coating damage, ○: good coating (with minor traces), ◎: coating defect

In addition, in the Example and the comparative example, all shown by% are weight% unless there is a notice.

Example 1 Preparation of Magnetic Photocurable Epoxy Acrylate Resin

Into a 5 liter round bottom flask equipped with a stirrer was added 2244 g (6 mol) of a liquid bisphenol-A epoxy having an epoxy equivalent of 187, 864 g (12 mol) of an acrylic acid having an acid equivalent of 72, and a 1 g quaternary ammonium salt. 0.5 g of hydroquinone was added as a polymerization inhibitor. The reaction was maintained at 125 ° C. to proceed with the reaction. During the reaction, the concentration of the acid was measured to confirm that the concentration of the acid reached 2 mgKOH / g or less, and then the reaction temperature was lowered to 60 ° C or lower, 260 g (2 mol) of ethyl acetoacetate, tetra-n-butylammonium 4.2 g of bromide was added thereto. Thereafter, the reaction mixture was maintained at 60 ° C. for 8 hours, and then 842 g of 1,6-hexanediol diacrylate as a reactive diluent was added thereto to obtain a self-photocurable epoxy acrylate resin.

Example 2 Preparation of Magnetic Photocurable Epoxy Methacrylate Resin

Into a 5 liter round bottom flask equipped with a stirrer was added 2244 g (6 mol) of a liquid bisphenol-A epoxy having an epoxy equivalent of 187, 1032 g (12 mol) of an acrylic acid having an acid equivalent of 72, and a 1 g quaternary ammonium salt. 0.5 g of hydroquinone was added as a polymerization inhibitor. The reaction was maintained at 125 ° C. to proceed with the reaction. During the reaction, the concentration of the acid was measured to confirm that the concentration of the acid reached 2 mgKOH / g or less, and then the reaction temperature was lowered to 60 ° C or lower, 260 g (2 mol) of ethyl acetoacetate, tetra-n-butylammonium 4.2 g of bromide was added thereto. Thereafter, the reaction mixture was maintained at 60 ° C. for 8 hours, and then 842 g of 1,6-hexanediol diacrylate as a reactive diluent was added thereto to obtain a self-photocurable epoxy methacrylate resin.

Example 3 Preparation of Magnetic Photocurable Epoxy Acrylate Resin

Into a 5 liter round bottom flask equipped with a stirrer was charged 2850 g (3 mol) of solid bisphenol-A epoxy having an epoxy equivalent of 475, 432 g (6 mol) of an acrylic acid having an acid equivalent of 72, and 1 g of a quaternary ammonium salt. 0.5 g of hydroquinone was added as a polymerization inhibitor. The reaction was maintained at 125 ° C. to proceed with the reaction. During the reaction, the concentration of the acid was measured to confirm that the concentration of the acid reached 2 mgKOH / g or less, and then the reaction temperature was lowered to 60 ° C or lower, 260 g (2 mol) of ethyl acetoacetate, tetra-n-butylammonium 4.2 g of bromide was added thereto. Thereafter, the reaction mixture was maintained at 60 ° C. for 8 hours, and then 842 g of 1,6-hexanediol diacrylate as a reactive diluent was added thereto to obtain a self-photocurable epoxy acrylate resin.

Example 4 Preparation of Magnetic Photocurable Epoxy Acrylate Resin

Into a 5 liter round bottom flask equipped with a stirrer was added 2244 g (6 mol) of a liquid bisphenol-A epoxy having an epoxy equivalent of 187, 864 g (12 mol) of an acrylic acid having an acid equivalent of 72, and a 1 g quaternary ammonium salt. 0.5 g of hydroquinone was added as a polymerization inhibitor. The reaction was maintained at 125 ° C. to proceed with the reaction. During the reaction, the concentration of the acid was measured until the concentration of the acid reached 2 mgKOH / g or less. 4.2 g of butylammonium bromide was added thereto. Thereafter, the reaction mixture was maintained at 60 ° C. for 8 hours, and then 842 g of 1,6-hexanediol diacrylate as a reactive diluent was added thereto to obtain a self-photocurable epoxy acrylate resin.

Example 5 Magnetic Photocurable Coating Composition

75% by weight of the magneto-photocurable epoxy acrylate resin prepared in Example 1, 12% by weight of hydroxyethyl acrylate, 11.8% by weight of trimethylolpropane triacrylate, 1% by weight of slip and defoamer, 0.2 wt% of the antioxidant was mixed and stirred for 60 minutes to prepare a magnetic photocurable coating composition.

Example 6 Magnetic Photocurable Coating Composition

75% by weight of the magneto-photocurable epoxy acrylate resin prepared in Example 2, 12% by weight of hydroxyethyl acrylate, 11.8% by weight of trimethylolpropanetriacrylate, 1% by weight of slip and antifoaming agent in a reactor equipped with a stirrer, 0.2 wt% of the antioxidant was mixed and stirred for 60 minutes to prepare a magnetic photocurable coating composition.

Example 7 Magnetic Photocurable Coating Composition

75% by weight of the magneto-photocurable epoxy acrylate resin prepared in Example 3, 12% by weight of hydroxyethyl acrylate, 11.8% by weight of trimethylolpropanetriacrylate, 1% by weight of slip and antifoaming agent in a reactor equipped with a stirrer, 0.2 wt% of the antioxidant was mixed and stirred for 60 minutes to prepare a magnetic photocurable coating composition.

Example 8 Magnetic Photocurable Coating Composition

75% by weight of the magneto-photocurable epoxy acrylate resin prepared in Example 4, 12% by weight of hydroxyethyl acrylate, 11.8% by weight of trimethylolpropane triacrylate, 1% by weight of slip and antifoaming agent, in a reactor equipped with a stirrer. 0.2 wt% of the antioxidant was mixed and stirred for 60 minutes to prepare a magnetic photocurable coating composition.

[Comparative Example 1] Preparation of photocurable epoxy acrylate resin

Into a 5 liter round bottom flask equipped with a stirrer was added 2244 g (6 mol) of a liquid bisphenol-A epoxy having an epoxy equivalent of 187, 864 g (12 mol) of an acrylic acid having an acid equivalent of 72, and a 1 g quaternary ammonium salt. 0.5 g of hydroquinone was added as a polymerization inhibitor. The reaction was maintained at 125 ° C. to proceed with the reaction. During the reaction, the concentration of the acid was measured and confirmed until the concentration of the acid reached 2 mgKOH / g or less.The reaction temperature was then lowered to 100 ° C or lower, and 842 g of 1,6-hexanediol diacrylate, a reactive diluent, was added thereto. The photocurable epoxy acrylate resin was obtained.

[Comparative Example 2] Preparation of photocurable epoxy methacrylate resin

Into a 5 liter round bottom flask equipped with a stirrer, 2244 g (6 mol) of a liquid bisphenol-A epoxy having an epoxy equivalent of 187, 1032 g (12 mol) of a methacrylic acid having an acid equivalent of 86, and 1 g of a quaternary ammonium salt were added. . 0.5 g of hydroquinone was added as a polymerization inhibitor. The reaction was maintained at 125 ° C. to proceed with the reaction. During the reaction, the concentration of the acid was measured and confirmed until the concentration of the acid reached 2 mgKOH / g or less.The reaction temperature was then lowered to 100 ° C or lower, and 842 g of 1,6-hexanediol diacrylate, a reactive diluent, was added thereto. The photocurable epoxy methacrylate resin was obtained.

Comparative Example 3 Preparation of Photocurable Epoxy Acrylate Resin

Into a 5 liter round bottom flask equipped with a stirrer was charged 2850 g (3 mol) of solid bisphenol-A epoxy having an epoxy equivalent of 475, 432 g (6 mol) of an acrylic acid having an acid equivalent of 72, and 1 g of a quaternary ammonium salt. 0.5 g of hydroquinone was added as a polymerization inhibitor. The reaction was maintained at 125 ° C. to proceed with the reaction. During the reaction, the concentration of the acid was measured and confirmed until the concentration of the acid reached 2 mgKOH / g or less.The reaction temperature was then lowered to 100 ° C or lower, and 842 g of 1,6-hexanediol diacrylate, a reactive diluent, was added thereto. The photocurable epoxy acrylate resin was obtained.

[Comparative Example 4] Photocurable coating composition

72 wt% of the photocurable epoxy acrylate resin prepared in Comparative Example 1, 12 wt% of hydroxyethyl acrylate, 11.8 wt% of trimethylolpropanetriacrylate, 1 wt% of slip and antifoaming agent, and oxidation 0.2 weight% of an inhibitor and 3 weight% of a photoinitiator (Irgacure 184, Shibagai Co., Ltd.) were mixed and stirred for 60 minutes to prepare a photocurable paint.

[Comparative Example 5] Photocurable coating composition

72 wt% of the photocurable epoxy methacrylate resin prepared in Comparative Example 2, 12 wt% of hydroxyethyl acrylate, 11.8 wt% of trimethylolpropanetriacrylate, 1 wt% of slip and antifoaming agent, in a reactor equipped with a stirrer, 0.2 weight% of antioxidant and 3 weight% of photoinitiator (Irgacure 184, Shibagai Co., Ltd.) were mixed and stirred for 60 minutes to prepare a photocurable paint.

[Comparative Example 6] Photocurable coating composition

72 wt% of the photocurable epoxy acrylate resin prepared in Comparative Example 3, 12 wt% of hydroxyethyl acrylate, 11.8 wt% of trimethylolpropanetriacrylate, 1 wt% of slip and antifoaming agent, oxidation 0.2 wt% of the inhibitor and 3 wt% of the photoinitiator (Irgacure 184, Shivagaigi Co., Ltd.) were mixed and stirred for 60 minutes to prepare a photocurable paint.

Comparative Example 7 Photocurable Coating Composition

72% by weight of photocurable epoxy acrylate resin (Kukdo Chemical, KDU-651), 12% by weight of hydroxyethyl acrylate, 11.8% by weight of trimethylolpropanetriacrylate, slip agent and antifoaming agent 1% by weight, 0.2% by weight of antioxidant, 3% by weight of photoinitiator (Irgacure 184, Shivagaigi Co., Ltd.) were mixed and stirred for 60 minutes to prepare a photocurable paint.

Curability was measured by the self-photocurable epoxy (meth) acrylate resin and the photocurable epoxy (meth) acrylate resin prepared in Examples 1 to 4 and Comparative Examples 1 to 3, and the minimum for tack free and defect free curing Energy (mJ / cm ² ) was confirmed, and the adhesion was evaluated by the method of ASTM D 3359-87 after coating on the flooring. The measurement results are shown in Table 1 below.

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Remarks UV curable 5 5 5 5 Not hardened Not hardened Not hardened 400mJ / ㎠ Minimum capacity for tack free and defect free curing (mJ / ㎠) 100 100 150 100 - - - Reverberation Evaluation No fuzz No fuzz No fuzz No fuzz Has a sting Has a sting Has a sting Olfactory discrimination Adhesion 100/100 100/100 100/100 100/100 - - -

As shown in the measurement results of Table 1, Comparative Examples 1 to 3, which are general photocurable epoxy (meth) acrylate resins, cannot be UV cured without the photoinitiator, and the magnetic photocurable epoxy of Examples 1 to 4 according to the present invention. The (meth) acrylate resin showed good UV curability without the photoinitiator. Adhesion with the flooring material obtained good results.

In addition, the curability was measured by the magnetic photocurable coating composition prepared in Examples 5 to 8, and the minimum energy (mJ / cm ² ) for adhesion-free and defect-free curing was confirmed, and after coating on the flooring ASTM D 3359- Adhesion was evaluated by the method of 87, reverberation by smell, and steam resistance and fouling resistance were measured when applied to the actual site. The measurement results are shown in Table 2 below.

division Example 5 Example 6 Example 7 Example 8 Remarks UV curable 5 5 5 5 400mJ / ㎠ Minimum capacity for tack free and defect free curing (mJ / ㎠) 250 245 310 248 Reverberation Evaluation No fuzz No fuzz No fuzz No fuzz Olfactory discrimination Adhesion 100/100 100/100 100/100 100/100 My MEK Last Name (Count) 200 times ↑ 200 times ↑ 200 times ↑ 200 times ↑ Steam resistance ◎ ◎ ◎ ◎ Visual discrimination Pollutant ◎ ◎ ◎ ◎ Visual discrimination

X: coating film severe, △: coating film middle, ○: coating film good (minor traces), ◎: coating film defect

As shown in the measurement results of Table 2, the magnetic photocurable coating compositions of Examples 5 to 8 according to the present invention have a slight difference in curability due to the molecular design of the magnetic photocurable epoxy (meth) acrylate resin without a photoinitiator. However, overall showed good UV curability and good results in adhesion with the flooring material, steam resistance, and contamination.

In addition, the curability was measured by the magnetic photocurable coating composition and the photocurable coating composition prepared in Examples 5, 7 and Comparative Examples 4-7, and the minimum energy (mJ / cm ² ) for adhesion-free and defect-free curing was measured. After the coating on the flooring material, the adhesion was evaluated by the method of ASTM D 3359-87, and the reverberation by the smell was evaluated. When applied to the actual site, the steam resistance and the contamination were measured and evaluated. The measurement results are shown in Table 3 below.

division Example 5 Example 7 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Remarks UV curable 5 5 5 5 5 5 400mJ / ㎠ Minimum capacity for tack free and defect free curing (mJ / ㎠) 250 310 310 315 330 320 Reverberation Evaluation No fuzz No fuzz There is an afterglow There is an afterglow There is an afterglow There is an afterglow Olfactory discrimination Adhesion 100/100 100/100 100/100 100/100 100/100 100/100 My MEK last name (count) 200 times ↑ 200 times ↑ 200 times ↑ 200 times ↑ 200 times ↑ 200 times ↑ Color Difference / Yellow (△ E) 2.1 2 3.5 3.4 3.5 3.6 Evaluation after 20 irradiations under 400mJ / ㎠ Steam resistance ◎ ◎ ◎ ◎ ◎ ◎ Visual discrimination Pollutant ◎ ◎ ◎ ◎ ◎ ◎ Visual discrimination

X: severe coating damage, Δ: moderate coating damage, ○: good coating (minor traces), ◎: coating defect

As shown in the measurement results of Table 3, the magnetic photocurable coating compositions of Examples 5 and 7 according to the present invention had a slight difference in curability due to the molecular design of the magnetic photocurable epoxy (meth) acrylate resin without a photoinitiator. However, overall showed good UV curability, Comparative Examples 4-7 prepared by mixing a conventional photoinitiator when preparing the photocurable coating composition was similar to the UV-curable coating composition, but the curability of the photocurable coating composition, but cured There was a fine aftertaste smell, it was found that the color difference / yellowing (△ E) compared to the embodiment.

Further, Examples 5 and 7 obtained good results in adhesion with the flooring material, steam resistance, and contamination.

Claims (9)

Magnetophotocurable epoxy (meth) acrylate prepolymers that are copolymers of (meth) acrylic acid with at least one or more epoxy compounds, at least one or more Michael donors, and at least one or more carboxyl groups; And (Meth) acrylate monomers; Magnetic photocurable epoxy (meth) acrylate resin composition comprising a The method of claim 1, The epoxy compound is bisphenol-A liquid epoxy resin, bisphenol-A solid epoxy resin, hydrogenated bisphenol-A epoxy resin, bromineated epoxy resin, cresol novolac epoxy resin, phenol novolac epoxy resin , At least one or more of the group selected from the group selected from BPA- novolac-type epoxy resins or mixtures thereof. The method of claim 1, Magnetic photocurable epoxy (meth) acrylate resin, characterized in that the β-dicarbonyl Michael donor is at least one or more from the group consisting of β-keto ester, β-diketone, β-ketoamide and β-ketoanilide Composition The method of claim 1, The? -Dicarbonyl Michael donor is at least one or more selected from the group consisting of ethyl acetoacetate, 2,4-pentanedione, and acetoacetanilide, and a photocurable epoxy (meth) acrylate resin composition The method of claim 1, The (meth) acrylic acid having a carboxyl group is at least any one or more selected from the group selected from methacrylic acid or acrylic acid and mixtures thereof. The self-curing epoxy (meth) acrylate resin composition The method of claim 1, The (meth) acrylate monomer is at least any one or more selected from the group selected from monofunctional monomers or polyfunctional monomers and mixtures thereof. The magnetophotocurable epoxy (meth) acrylate resin composition The method of claim 1, 20 to 65% by weight of the epoxy compound, 100 to 5 parts by weight of the total composition, 5 to 15% by weight of the Michael donor, and 10 to 25 weight of the (meth) crylic acid having the carboxyl group. % And a (meth) acrylate monomer containing 20 to 40% by weight of a magnetophotocurable epoxy (meth) acrylate resin composition  The method of claim 1, Magnetic photocurable coating composition further comprising at least one additive selected from the group consisting of surfactants, antioxidants, light stabilizers, phosphate adhesion promoters, silane coupling agents, thermal polymerization inhibitors, leveling agents, quenchers, dispersants, and antifoaming agents. A magnetic photocurable coating composition comprising the magnetic photocurable epoxy (meth) acrylate resin composition according to claim 1.