KR100903209B1 - Michael addition intermediate and inter- photocurable polyurethane (meth)acrylate resin composition including the same - Google Patents

Abstract

A michael addition intermediate is provided to prepare a coating agent with excellent performance by not using separate photoinitiator which is harmful to the human body without environmental contamination. A michael addition intermediate includes hydroxyl groups at both ends and has a structure represented by chemical formula 1. In chemical formula 1, R1 and R5 which are the same and different, represent hydrogen, methyl group or C2~12 alkyl group; R2 and R4 which are the same and different, represent hydrogen or methyl; R3 is C1~12 alkyl group, benzyl group, benzoyl group, (meth)acryl group or amide group.

Description

MICHAEL ADDITION INTERMEDIATE AND INTER- PHOTOCURABLE POLYURETHANE (METH) ACRYLATE RESIN COMPOSITION INCLUDING THE SAME}

The present invention relates to a Michael addition intermediate and a built-in photocurable urethane (meth) acrylate resin composition comprising the same, and more particularly, the present invention relates to a Michael addition intermediate, which can be used as an ultraviolet and electron beam curable built-in photoinitiator, The built-in photocurable urethane (meth) acrylate resin composition, its manufacturing method, the built-in photocurable urethane (meth) acrylate resin manufactured from this, and a built-in photocurable coating composition.

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 disadvantage of using an initiator or photoinitiator is that airborne pollution in the working process is reduced due to the generation of highly volatile, unreacted, toxic, low molecular weight organics produced by the decomposition of these initiators by themselves into smaller molecules and at the atomic level. Not only can it occur, but it can also harm the human body. 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.

Recently, several new approaches have been published to overcome these problems and limitations of use, which have been addressed by the use of intrinsic photoinitiators to apply (meth) acrylate monomers and / or oligomers and / or other photoinitiator resins. I tried to solve.

However, this starts with compounds known to function as photoinitiators (or suitable derivatives), or to produce compounds that function as (meth) acrylate monomers and / or oligomers, photoinitiators for efficient self-initiation. The approach produces a low functional resin which is very slow in its curing reactivity and is also a low volatility low molecular weight monomer acrylate series and / or methacrylate that is added for properties and processability in the middle or final stage of the reaction. Fugitive emissions such as family tend to be easily absorbed through the skin, which can cause worker health stability issues and deleterious effects on the environment.

Therefore, there is a need for research on the development of a technology that can produce a photo-curable (meth) acrylate resin more environmentally and safely without using a separate photoinitiator. In particular, there is a need for research on the development of technology that does not use any compound known to function as a photoinitiator in forming a (meth) acrylate oligomer having a built-in photoinitiator.

The present invention seeks to provide a Michael addition intermediate capable of producing a coating of good performance without separately using photoinitiators that cause air pollution or are harmful to humans.

The present invention also provides a built-in photocurable urethane (meth) acrylate resin composition comprising the Michael addition intermediate and a method for producing the same.

The present invention also provides a built-in photocurable urethane (meth) acrylate resin prepared using the composition and a built-in photocurable coating composition comprising the same.

The present invention provides Michael addition intermediates comprising hydroxyl groups at both ends.

The present invention also provides a built-in photocurable urethane (meth) acrylate resin composition comprising the Michael addition intermediate, and a method for producing the same.

The present invention also provides a photocurable urethane (meth) acrylate resin prepared using the photocurable urethane (meth) acrylate resin composition and a photocurable paint composition containing the same.

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

The present invention can generally be used as a single chemical monomer that is stable and responsive when forming a molecular structure such as a prepolymer by introducing hydroxy at both ends of the Michael addition intermediate having a (meth) acrylate end. It is characterized by excellent performance.

In particular, the Michael addition intermediate of the present invention can be used by being limited to (meth) acrylate monomers and resins capable of radical reaction because the existing Michael addition intermediate terminal is a (meth) acrylate group. Since the Michael addition intermediate is a reactive hydroxyl group at both ends, it can be used as a short chain diol when applied to a reaction such as polyurethane synthesis. Control is possible.

In general, acrylic resins and urethane (meth) acrylate resins require a minimum of capping groups capable of at least some degree of crosslinking in their prepolymer structure in order for the polymer to have good physical properties, and the prepolymer molecular weight must be at least 10,000. There is a limit condition such as, and its use range is very limited.

However, the Michael addition intermediate of the present invention can be used any number irrespective of the molecular weight of the prepolymer by introducing a hydroxyl group at both ends to provide excellent coating performance when applied as a coating through a very wide range of use and excellent curing reactivity Can be.

In addition, the Michael addition intermediate of the present invention can be used as a built-in photoinitiator, and in the preparation of urethane (meth) acrylate oligomers by using no compound known to function as a photoinitiator, according to the conventional photoinitiator Side effects can be solved.

The present invention provides Michael addition intermediates comprising hydroxyl groups at both ends.

Michael addition intermediates according to the invention may be referred to as Michael addition resins, Michael oligomers, Michael adducts, or Michael addition products.

Preferably, the Michael addition intermediate of the present invention may be represented by the following formula (1):

[Formula 1]

In the formula,

R ₁ and R ₅ are the same as or different from each other, and each is hydrogen, a methyl group, or an alkyl group having 2 to 12 carbon atoms,

R ₂ and R ₄ are the same as or different from each other, and each is hydrogen or a methyl group,

R <_3> is a C1-C12 alkyl group, benzyl group, benzoyl group, a (meth) acryl group, or an amide group.

Also, preferably, the Michael addition intermediate of the present invention may be represented by the following Chemical Formula 2 or 3.

[Formula 2]

[Formula 3]

Michael addition intermediates of the invention may be those comprising a (meth) acrylate "michael acceptor" comprising a β-dicarbonyl "michael donor" and a hydroxy group.

In the present invention, "Michael Doner" is a compound corresponding to the electron donor in the Michael Addition is added to the α, β unsaturated carbonyl compound and a compound having active methylene to α, β unsaturated nitrile Corresponding examples include compounds containing β-carbonyl and the like. The term "Michael Acceptor" refers to a compound corresponding to an electron acceptor in the Michael addition reaction, and particularly includes a (meth) acrylate compound having an unsaturated double bond.

In the present invention, there is a (meth) acrylate "Michael Receptor" containing the hydroxy group, such as hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxybutyl acrylate, and the like Β-dicarbonyl monomers that can participate in the addition reaction as a "donor" include β-keto esters, β-diketones, β-ketoamides, β-ketoanilides, and / or other β-dicarbonyl compounds. It may contain one or more of these.

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-acetoacetoxy silethyl methacrylate, allyl acetoacetate, benzyl acetoacetate, 2,4-pentanedione, isobutyl acetoacetate, and 2-meth Methoxyethyl acetoacetates include, but are 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.

 In addition, in the Michael addition intermediate of the present invention, the acrylate including a hydroxy group may be a monofunctional hydroxy acrylate including one or more hydroxy groups or a two or more hydroxy groups to be a multifunctional hydroxy acrylate.

Preferably, the monofunctional hydroxy acrylate is hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl acrylate, 2-hydroxyethyl acrylate (HEA), 2- At least one selected from the group consisting of hydroxypropyl acrylate (HPA), 4-hydroxybutyl acrylate, 2-hydroxy-3-acryloyloxy propyl methacrylate, and 2-hydroxybutyl acrylate; or Two or more kinds can be mixed and used, More preferably, 2-hydroxypropyl acrylate (HPA) can be used.

Examples of the polyfunctional hydroxy acrylate include glycerin dimethacrylate, 2-hydroxy-3-acryloyloxy propyl methacrylate, pentaerythritol triacrylate, trimethylolpropane diallyl ether, pentaerythritol triallyl One or more selected from the group consisting of ether and dipentaerythritol pentaacrylate can be used and mixed.

Michael addition intermediates of the invention can be prepared in the presence of a catalyst. In particular, the Michael addition reaction in the present invention can be catalyzed by strong bases. 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 intermediates of the present invention can also be modified by adding amine synergists to enhance performance. Examples of such modifications may include incorporating primary or secondary amines in the uncured Michael addition resin. 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.

The present invention also provides a built-in photocurable urethane (meth) acrylate resin composition and a coating composition comprising a Michael addition intermediate containing a hydroxyl group at both ends.

The composition of the present invention may further comprise isocyanate reactive polyols and polyfunctional isocyanates.

In this case, as the isocyanate-reactive polyol, one containing a hydroxy group may be used, and the polyol may include two or more isocyanate-reactive residues.

The polyol may have a weight average molecular weight of 400 to 2000, preferably 600 to 1000.

The polyol may be at least one selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene glycols, acrylic polyols, and flame retardant polyols containing phosphorus (P). Preferably, the polyether polyol may be at least one selected from the group consisting of polypropylene glycol, polytetramethylene glycol, polypropylene glycol modified substance, and polyethylene glycol, wherein the polyester polyol includes an adipic acid system. It may be at least one selected from the group consisting of a ring-opening addition polymerization polyester polyol including a polycondensation polyester polyol and a lactone system.

In particular, examples of the polyol include monomolecular polyols such as ethylene glycol, propylene glycol, butanediol, 1,6 hexanediol, glycerol, trimethylolpropane, neopentyl glycol, pentaerythritol and the like, and polyethylene glycol, polypropylene glycol, and polyethylene propyllin glycol. , Polytetramethylene glycol, polycarbonate polyol, polycaprolactone polyol, polyester polyol, polyether polyol, fatty acid modified polyester polyol, fatty acid modified polyether polyol and the like and mixtures thereof can be preferably used.

As a polyfunctional isocyanate used for the built-in photocurable urethane (meth) acrylate resin composition which concerns on this invention, aromatic, alicyclic and aliphatic diisocyanate, polyisocyanate, etc. can be used 1 or more types.

Examples of aliphatic diisocyanates include hexamethylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate 1,4-tetramethylene diisocyanate, 1,10-decamethylene diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate Isocyanates and mixtures thereof, and aromatic diisocyanates include toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, 1,5-naphthalene diisocyanate, 4-methoxy-1,3- Phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 2,4-dimethyl-1,3-phenylene diisocyanate, 4,4-diisocyanate diphenyl ether, benzidine diisocyanate, 4, Single or two or more may be selected from 4'-diisocyanate dibenzyl, methylene-bis (4-phenylisocyanate) -1,3-phenylene diisocyanate.

The compositions of the present invention may also further comprise one or more additives selected from the group consisting of coatings, paints, adhesives, tackifiers, pigments, gloss modifiers, flow agents, leveling agents, quenchers, and dispersants. In particular, the resin composition of the present invention can be used in admixture with one or more additives such as pigments suitable for the flooring paint used.

In addition, the built-in photocurable urethane (meth) acrylate resin composition of the present invention may include 5 to 35 parts by weight, preferably 8 to 23 parts by weight of the Michael addition intermediate based on 100 parts by weight of the total composition. In addition, the isocyanate-reactive polyol is included in 20 to 70 parts by weight, preferably 30 to 50 parts by weight, based on 100 parts by weight of the total composition, and the multifunctional isocyanate is 10 to 40 parts by weight, preferably 100 parts by weight of the total composition. Preferably from 15 to 30 parts by weight, mono- and multifunctional (meth) acrylate monomer may be included in 10 to 40 parts by weight, preferably 13 to 32 parts by weight based on 100 parts by weight of the total composition.

The present invention also provides a step of reacting a β-dicarbonyl Michael donor with an acrylate Michael acceptor containing a hydroxyl group to produce a Michael addition intermediate comprising a hydroxyl group end, and the Michael addition Provided is a process for preparing a visceral photocurable urethane (meth) acrylate resin composition comprising mixing an intermediate with an isocyanate-reactive polyol and a polyfunctional isocyanate.

In a preferred example, the step of preparing the Michael addition intermediate may be carried out under the conditions of the reaction temperature 20 ~ 60 ℃ and 1 atm. In addition, mixing the Michael addition intermediate with an isocyanate-reactive polyol and a polyfunctional isocyanate to prepare a built-in photocurable urethane (meth) acrylate resin may be carried out under the conditions of the reaction temperature 40 ~ 90 ℃ and 1 atmosphere. have.

This invention also provides the urethane (meth) acrylate resin manufactured using the said built-in photocurable urethane (meth) acrylate resin composition.

The weight average molecular weight of the built-in photocurable urethane (meth) acrylate resin according to the present invention may be 600 to 30000, preferably 1000 to 10000.

Preferably, the built-in photocurable urethane (meth) acrylate resin according to the present invention may be represented by the following formula (4) and (5):

[Formula 4]

[Formula 5]

In the formula,

R ₆ and R ₁₁ are the same as or different from each other, each is a Michael addition intermediate,

R ₇ , R ₉ , and R ₁₂ are the same as or different from each other, and are each an aliphatic or aromatic isocyanate group,

R ₈ is a polyol or diol,

R ₁₀ and R ₁₃ are the same as or different from each other, and each is a (meth) acrylate group.

Also, preferably, the built-in photocurable urethane (meth) acrylate resin according to the present invention may be represented by the following Chemical Formula 6 or Chemical Formula 7:

[Formula 6]

[Formula 7]

In a preferred embodiment, the present invention is a built-in photoinitiator having a hydroxyl group functional group at both ends to make a built-in photo-initiated (meth) acrylate-end resin, that is, the Michael addition intermediate represented by the formula (1) reaction temperature 20 About 60 ° C., reaction time 4 hours to 12 hours, and prepared under 1 atmosphere, and then reacted with a monomer having both isocyanate and (meth) acrylate (between 40 ° C. and 90 ° C., under 1 atmosphere). A urethane reaction is carried out with diisocyanate at the terminal to form a prepolymer of isocyanate terminal, and then reacted with a monofunctional or polyfunctional (meth) acrylate having a hydroxyl group (between 40 ° C. and 90 ° C. under 1 atm). ) Polyfunctional urethane acrylate end-capped with an acrylate, that is, a built-in view represented by Formula 5 Urethane (meth) acrylate resin can be produced.

Alternatively, a urethane reaction is carried out with a diisocyanate at the end to form a prepolymer of the isocyanate end, followed by reaction with a polyol and a monofunctional or polyfunctional (meth) acrylate having a hydroxyl group (between 40 ° C. and 90 ° C. under 1 atm). The polyfunctional urethane acrylate end-capped with (meth) acrylate, that is, a built-in photocurable urethane (meth) acrylate resin represented by the formula (4) can be prepared.

A further aspect of the invention is the application of synthetic polyfunctional (meth) acrylates and urethane acrylate resins with Michael addition intermediates having hydroxyl groups at both ends in the backbone structure to the coating compositions to be used for floor coatings. .

The present invention also provides a built-in photocurable coating composition comprising the above-mentioned built-in photocurable urethane (meth) acrylate resin.

Additional aspects of the invention include providing a polyol to the reactor, providing a monomer having at least one isocyanate-reactive moiety to the reactor, providing a urethanization catalyst to the reactor, adding a polyfunctional isocyanate And maintaining the reaction mixture at the reaction-effective temperature provides a method for synthesizing a backbone acrylate end-capped polyurethane resin and a multifunctional acrylate resin.

Curing can be achieved by simply exposing to actinic or electron beam radiation in the absence of an exogenous photo-initiator to add. Curing can also be accomplished by using typical free radical generators. In particular, the urethane acrylate resin of the present invention is an energy source used at the time of curing as an ultraviolet light source capable of emitting UV light of 180 to 460 nm, such as low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon mercury lamp, and ultraviolet light. Fluorescent lamps, carbon arc lamps, ultraviolet lamps of the electrodeless microwave system and the like are preferable.

One aspect of the present invention provides that the enhancer can function by introducing or adding primary and / or secondary amines in the resin structure to promote curing of the resin of the present invention.

A further aspect of the present invention provides that the resin composition of the present invention is cured under standard UV-curing conditions to yield a coating that is not tacky and adhesive without the addition of typical photoinitiators.

In a further aspect of the present invention, there is provided a method of using the resin of the invention comprising applying the resin of the invention to a flooring, drying the resin and curing the resin. Application can be by any method known in the industry including, but not limited to, roll-coating, spray-coating, brush-coating, dip-coating, and electronic coating.

In the present invention, matters other than those described above can be added or subtracted as necessary, and therefore the present invention is not particularly limited.

The built-in photocurable urethane (meth) acrylate resin prepared using the Michael addition intermediate and the Michael addition intermediate containing a hydroxyl group at both ends of the present invention and the paint composition for flooring prepared using the resin are resin and paint preparation It can control the cross-link density at the time, secures excellent reactivity and stability, and hardens under standard UV curing conditions for floors and floors without using a separate photoinitiator. It is a resin and a coating composition which can express excellent performance even without a harmful environment to a human body, and have excellent physical properties without viscosity and adhesiveness.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

In Examples 1 to 11 and Comparative Examples 1 to 8 below, the physical properties of the resin and the paint 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 500 mJ / cm ² UV, evaluation values 1 (wet, uncured), 2 (sticky), 3 ( Smooth surfaces, flaws easily), 4 (tack free, can be scratched with a cotton swab), and 5 (tack free and flawless).

In addition, the minimum capacity for tack-free and defect-free curing indicates the 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 is 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 and Pollution Assessment

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, HSC, HSV, SIV, 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

Example 1: Synthesis of Boehmite Addition Intermediate (I)

Michael addition intermediates containing hydroxyl groups at both ends were prepared through a reaction as in Scheme 1 below.

Scheme 1

260 g (2 mol) of hydroxypropyl acrylate, 130 g (1 mol) of ethyl acetoacetate, and 2.41 g of tetra-n-butylammonium bromide were placed in a 1000 ml glass reactor. The reactor was covered with a cover equipped with a mechanical stirrer, reflux cooler, and a temperature monitoring thermocouple. The mixture was allowed to react under stirring. Heat was applied over 50 minutes to raise the temperature to 60 ° C. Thereafter, the reaction mixture was maintained at 60 ° C. for 8 hours, and the mixture was cooled to room temperature to obtain a Michael addition intermediate represented by the following Chemical Formula 2 having a hydroxyl group functional group at the sock end.

[Formula 2]

Example 2: Synthesis of Boehmite Addition Intermediate (II)

260 g (2 mol) of hydroxypropyl acrylate, 158 g (1 mol) of isobutyl acetoacetate and 2.41 g of tetra-n-butylammonium bromide were placed in a 1000 ml glass reactor. The reactor was covered with a cover equipped with a mechanical stirrer, reflux cooler, and a temperature monitoring thermocouple. The mixture was allowed to react under stirring. Heat was applied over 50 minutes to raise the temperature to 60 ° C. Thereafter, the reaction mixture was maintained at 60 ° C. for 8 hours, and the mixture was cooled to room temperature to obtain a Michael addition intermediate represented by the following Chemical Formula 2 having a hydroxyl group functional group at the sock end.

[Formula 3]

Example 3: Preparation of built-in photocurable urethane (meth) acrylate resin

390 g (1 mol) of Michael addition intermediates, 50.0 g of acetone and 0.1 g of dibutyltin dilaurate were placed in a 5000 ml glass reactor containing hydroxyl group functionalities at both ends of Example 1. The reactor was covered with a cover fitted with a mechanical stirrer, reflux cooler, temperature monitoring thermocouple, and additional funnel. The funnel was fixed to a pressure-equilibrated sidearm filled with 444 g (2 moles) of isophorone diisocyanate (IPDI). The system was kept under a dry nitrogen blanket flushed with dry nitrogen. The reactor contents were stirred and heated over 20 minutes to raise the temperature to 50 ° C. IPDI was dripped over 1 hour, maintaining temperature at 50 degreeC. After the addition of IPDI, the temperature was raised to 70 ° C. over 3 hours.

The reaction was monitored by FT-IR. The reaction mixture was kept at 60 ° C. until the intensity at 3400 cm ⁻¹ (−OH band) reached a constant minimum. Then 260 g (2 moles) of hydroxypropyl acrylate were each added and the mixture was further stirred and heated.

Phenothiazine (0.01 g) was added during this step to prevent gelation.

The reaction was monitored by FT-IR. When the strength at 2300 cm ^-1 (-NCO band) reached a constant minimum value (after 18 hours), the acetone was removed by vacuum distillation at a pressure of 40 mmHg at 60 ° C to remove the built-in photocurable urethane (meth) acrylate resin. Got it.

Example 4: Preparation of built-in photocurable urethane (meth) acrylate resin

390 g (1 mol) of Michael addition intermediates, 50.0 g of acetone, 500 g (0.5 mol) of polyethylene glycol, 500 g (0.5 mol) of polytetramethylene glycol and di containing both hydroxyl groups at both ends of Example 1 0.1 g of butyltin dilaurate was placed in a 5000 ml glass reactor. The reactor was covered with a cover fitted with a mechanical stirrer, reflux cooler, temperature monitoring thermocouple, and additional funnel. The funnel was fixed to a pressure-equilibrated sidearm filled with 504 g (3 moles) of hexamethylene diisocyanate (HDI). The system was kept under a dry nitrogen blanket completely flushed with dry nitrogen. The reactor contents were stirred and heated over 20 minutes to raise the temperature to 50 ° C. HDI was dripped over 1 hour, maintaining temperature at 50 degreeC. After addition of HDI, the temperature was raised to 70 ° C. over 3 hours.

The reaction was monitored by FT-IR. The reaction mixture was kept at 60 ° C. until the intensity at 3400 cm ⁻¹ (−OH band) reached a constant minimum. Then 596 g (2 mol) of pentaerythritol triacrylate were added and the mixture was further stirred and heated.

Phenothiazine (0.01 g) was added during this step to prevent gelation.

The reaction was monitored by FT-IR. When the strength at 2300 cm ^-1 (-NCO band) reached a constant minimum value (after 18 hours), the acetone was removed by vacuum distillation at a pressure of 40 mmHg at 60 ° C to remove the built-in photocurable urethane (meth) acrylate resin. Got it.

Example 5: Preparation of built-in photocurable urethane (meth) acrylate resin

5000 ml glass reactor containing 390 g (1 mol) of Michael addition intermediates, 50.0 g of acetone, 1000 g (1 mol) of polyethylene glycol and 0.1 g of dibutyltin dilaurate containing both hydroxyl groups at both ends of Example 1 Put on. The reactor was covered with a cover fitted with a mechanical stirrer, reflux cooler, temperature monitoring thermocouple, and additional funnel. The funnel was fixed to a pressure-equilibrated sidearm filled with 666 g (3 moles) of isophorone diisocyanate (IPDI). The reactor contents were stirred and heated over 20 minutes to raise the temperature to 50 ° C. IPDI was dripped over 1 hour, maintaining temperature at 50 degreeC. After the addition of IPDI, the temperature was raised to 70 ° C. over 3 hours.

The reaction was monitored by FT-IR. The reaction mixture was kept at 60 ° C. until the intensity at 3400 cm ⁻¹ (−OH band) reached a constant minimum. Then 298 g (1 mol) of pentaerythritol triacrylate and 130 g (1 mol) of hydroxypropyl acrylate were added and the mixture was further stirred and heated.

Phenothiazine (0.01 g) was added during this step to prevent gelation.

The reaction was monitored by FT-IR. When the strength at 2300 cm ^-1 (-NCO band) reached a constant minimum value (after 18 hours), the acetone was removed by vacuum distillation at a pressure of 40 mmHg at 60 ° C to remove the built-in photocurable urethane (meth) acrylate resin. Got it.

Example 6: Preparation of built-in photocurable urethane (meth) acrylate resin

390 g (1 mol) of Michael addition intermediates, 50.0 g of acetone, 1300 g (2 mol) of polytetramethylene glycol and 0.1 g of dibutyltin dilaurate were added to the terminal containing the hydroxyl group functional groups at both ends of Example 1. Placed in ml glass reactor. The reactor was covered with a cover fitted with a mechanical stirrer, reflux cooler, temperature monitoring thermocouple, and additional funnel. The funnel was fixed to a pressure-equilibrated sidearm filled with 888 g (4 moles) of isophorone diisocyanate (IPDI). The reactor contents were stirred and heated over 20 minutes to raise the temperature to 50 ° C. IPDI was dripped over 1 hour, maintaining temperature at 50 degreeC. After the addition of IPDI, the temperature was raised to 70 ° C. over 3 hours.

The reaction was monitored by FT-IR. The reaction mixture was kept at 60 ° C. until the intensity at 3400 cm ⁻¹ (−OH band) reached a constant minimum. Then 596 g (2 mol) of pentaerythritol triacrylate were added and the mixture was further stirred and heated.

Phenothiazine (0.01 g) was added during this step to prevent gelation.

The reaction was monitored by FT-IR. When the strength at 2300 cm ^-1 (-NCO band) reached a constant minimum value (after 18 hours), the acetone was removed by vacuum distillation at a pressure of 40 mmHg at 60 ° C to remove the built-in photocurable urethane (meth) acrylate resin. Got it.

Example 7: Preparation of built-in photocurable urethane (meth) acrylate resin

418 g (1 mol) of Michael addition intermediate, 50.0 g of acetone, and 0.1 g of dibutyltin dilaurate were placed in a 5000 ml glass reactor containing hydroxyl group functional groups at both ends of Example 2. The reactor was covered with a cover fitted with a mechanical stirrer, reflux cooler, temperature monitoring thermocouple, and additional funnel. The funnel was fixed to a pressure-equilibrated sidearm filled with 444 g (2 moles) of isophorone diisocyanate (IPDI). The system was kept under a dry nitrogen blanket flushed with dry nitrogen. The reactor contents were stirred and heated over 20 minutes to raise the temperature to 50 ° C. IPDI was dripped over 1 hour, maintaining temperature at 50 degreeC. After the addition of IPDI, the temperature was raised to 70 ° C. over 3 hours.

The reaction was monitored by FT-IR. The reaction mixture was kept at 60 ° C. until the intensity at 3400 cm ⁻¹ (−OH band) reached a constant minimum. Then 260 g (2 moles) of hydroxypropyl acrylate were each added and the mixture was further stirred and heated.

Phenothiazine (0.01 g) was added during this step to prevent gelation.

The reaction was monitored by FT-IR. When the strength at 2300 cm ^-1 (-NCO band) reached a constant minimum value (after 18 hours), acetone was removed by vacuum distillation at a pressure of 40 mmHg at 60 ° C to remove the built-in photocurable urethane (meth) acrylate resin. Got it.

Example 8 Interior Photocurable Paint Composition for Flooring

70% by weight of the built-in photocurable urethane (meth) acrylate resin prepared in Example 6, 15% by weight of hydroxyethyl acrylate, 8% by weight of acryloyl morpholine and beta-carboxyethylacrylic acid in a reactor equipped with a stirrer 6 wt% of the rate, 1 wt% of the slip and antifoaming agent were mixed and stirred for 30 minutes to prepare a built-in photocurable paint for flooring.

Example 9 Interior Photocurable Paint Composition for Flooring

70 wt% of the built-in photocurable urethane (meth) acrylate resin prepared in Example 3 in a reactor with a stirrer, 15 wt% of hydroxyethyl acrylate, 8 wt% of acryloyl morpholine, beta-carboxyethylacrylic 6 wt% of the rate, 1 wt% of the slip and antifoaming agent were mixed and stirred for 30 minutes to prepare a built-in photocurable paint for flooring.

Example 10 Interior Photocurable Paint Composition for Flooring

70 wt% of the built-in photocurable urethane (meth) acrylate resin prepared in Example 7 in a reactor with a stirrer, 15 wt% of hydroxyethyl acrylate, 8 wt% of acryloyl morpholine, beta-carboxyethylacrylic 6 wt% of the rate, 1 wt% of the slip and antifoaming agent were mixed and stirred for 30 minutes to prepare a built-in photocurable paint for flooring.

Example 11 Interior Photocurable Paint Composition for Flooring

70 wt% of the built-in photocurable urethane (meth) acrylate resin prepared in Example 4 in a reactor with a stirrer, 15 wt% of hydroxyethyl acrylate, 8 wt% of acryloyl morpholine, beta-carboxyethylacrylic 6 wt% of the rate, 1 wt% of the slip and antifoaming agent were mixed and stirred for 30 minutes to prepare a built-in photocurable paint for flooring.

Comparative Example 1: Preparation of photocurable urethane (meth) acrylate resin

260 g (2 mol) of hydroxypropyl acrylate and 0.1 g of dibutyltin dilaurate were placed in a 1000 ml glass reactor. The reactor was covered with a cover fitted with a mechanical stirrer, reflux cooler, temperature monitoring thermocouple, and additional funnel. The funnel was fixed to a pressure-equilibrated sidearm filled with 222 g (1 mole) of isophorone diisocyanate. The system was kept under a dry nitrogen blanket completely flushed with dry nitrogen. The reactor contents were stirred and heated over 20 minutes to raise the temperature to 50 ° C. IPDI was dripped over 1 hour, maintaining temperature at 50 degreeC. After the addition of IPDI, the temperature was raised to 70 ° C. over 3 hours.

Phenothiazine (0.01 g) was added during this step to prevent gelation.

The reaction was monitored by FT-IR. When the intensity | strength in 2300 cm <^-1> (-NCO band) became a fixed minimum (after 18 hours), reaction was completed and the photocurable urethane (meth) acrylate resin was obtained.

Comparative Example 2: Preparation of photocurable urethane (meth) acrylate resin

500 g (0.5 mol) polyethylene glycol, 500 g (0.5 mol) polytetramethylene glycol and 0.1 g dibutyltin dilaurate were placed in a 5000 ml glass reactor.

The reactor was covered with a cover fitted with a mechanical stirrer, reflux cooler, temperature monitoring thermocouple, and additional funnel. The funnel was fixed to a pressure-equilibrated sidearm filled with 336.0 g (2 moles) of hexamethylene diisocyanate (HDI). The system was kept under a dry nitrogen blanket completely flushed with dry nitrogen. The reactor contents were stirred and heated over 20 minutes to raise the temperature to 50 ° C. HDI was dripped over 1 hour, maintaining temperature at 50 degreeC. After addition of HDI, the temperature was raised to 70 ° C. over 3 hours.

The reaction was monitored by FT-IR. When the strength at 3400 cm ⁻¹ (−OH band) reached a constant minimum (after 10 hours) 596.0 g (2 mol) of pentaerythritoltriacrylate was added and the mixture was further stirred and heated.

Phenothiazine (0.01 g) was added during this step to prevent gelation.

The reaction was monitored by FT-IR. When the intensity | strength in 2300 cm <^-1> (-NCO band) became a fixed minimum (after 18 hours), reaction was completed and the photocurable urethane (meth) acrylate resin was obtained.

Comparative Example 3: Preparation of Photocurable Urethane (Meta) Acrylate Resin

1300 g (2 mol) of polytetramethylene glycol and 0.1 g of dibutyltin dilaurate were placed in a 5000 ml glass reactor.

The reactor was covered with a cover fitted with a mechanical stirrer, reflux cooler, temperature monitoring thermocouple, and additional funnel. The funnel was fixed to a pressure-equilibrated sidearm filled with 666.0 g (3 moles) of isophorone diisocyanate (IPDI). The system was kept under a dry nitrogen blanket flushed with dry nitrogen. The reactor contents were stirred and heated over 20 minutes to raise the temperature to 50 ° C. IPDI was dripped over 1 hour, maintaining temperature at 50 degreeC. After the addition of IPDI, the temperature was raised to 70 ° C. over 3 hours.

The reaction was monitored by FT-IR. When the intensity at 3400 cm ⁻¹ (−OH band) reached a constant minimum (after 10 hours), 596.0 g (2 moles) of pentaerythritoltriacrylate was added and the mixture was further stirred and heated.

Phenothiazine (0.01 g) was added during this step to prevent gelation.

The reaction was monitored by FT-IR. When the intensity | strength in 2300 cm <^-1> (-NCO band) became fixed minimum value (after 18 hours), reaction was completed and the photocurable urethane (meth) acrylate resin was obtained.

Comparative Example 4: Preparation of photocurable urethane (meth) acrylate resin

1300 g (2 mol) of polytetramethylene glycol and 0.1 g of dibutyltin dilaurate were placed in a 5000 ml glass reactor.

The reactor was covered with a cover fitted with a mechanical stirrer, reflux cooler, temperature monitoring thermocouple, and additional funnel. The funnel was fixed to a pressure-equilibrated sidearm filled with 666.0 g (3 moles) of isophorone diisocyanate (IPDI). The system was kept under a dry nitrogen blanket flushed with dry nitrogen. The reactor contents were stirred and heated over 20 minutes to raise the temperature to 50 ° C. IPDI was dripped over 1 hour, maintaining temperature at 50 degreeC. After the addition of IPDI, the temperature was raised to 70 ° C. over 3 hours.

The reaction was monitored by FT-IR. When the intensity at 3400 cm ⁻¹ (−OH band) reached a constant minimum (after 10 hours), 260.0 g (2 moles) of hydroxypropylacrylate were added and the mixture was further stirred and heated.

Phenothiazine (0.01 g) was added during this step to prevent gelation.

The reaction was monitored by FT-IR. When the intensity | strength in 2300 cm <^-1> (-NCO band) became fixed minimum value (after 18 hours), reaction was completed and the photocurable urethane (meth) acrylate resin was obtained.

Comparative Example 5 Preparation of Photocurable Urethane (Meta) acrylate Resin

576.0 g of trimers of hexamethylene diisocyanate (Desmodur N3300, Bayer), 390.0 g of hydroxypropyl acrylate and 0.1 g of dibutyltin dilaurate were placed in a 1000 ml glass reactor. The reactor was covered with a cover fitted with a mechanical stirrer, reflux cooler, temperature monitoring thermocouple, and additional funnel. The system was kept under a dry nitrogen blanket completely flushed with dry nitrogen. The reactor contents were stirred and heated over 20 minutes to raise the temperature to 45 ° C. The temperature was raised to 60 ° C. over 3 hours. Phenothiazine (0.01 g) was added during this step to prevent gelation. The reaction was monitored by FT-IR. When the intensity at 2300 cm ^-1 (-NCO band) reached a constant minimum value (after 18 hours), the reaction was completed to obtain a hard type photocurable urethane (meth) acrylate resin.

Comparative Example 6: Photocurable Paint Composition for Flooring

67 wt% of the photocurable urethane (meth) acrylate resin prepared in Comparative Example 1, 15 wt% of hydroxyethyl acrylate, 8 wt% of acryloyl morpholine, and beta-carboxyethyl acrylate in a reactor equipped with a stirrer 6% by weight, 1% by weight of slip and antifoaming agent, 3% by weight of photoinitiator (Irgacure 184, Shivagai Co., Ltd.) were mixed and stirred for 60 minutes to prepare a built-in photocurable paint for flooring.

Comparative Example 7: Photocurable Paint Composition for Flooring

67 wt% of the photocurable urethane (meth) acrylate resin prepared in Comparative Example 4, 15 wt% of hydroxyethyl acrylate, 8 wt% of acryloyl morpholine, and beta-carboxyethyl acrylate in a reactor equipped with a stirrer 6% by weight, 1% by weight of slip and antifoaming agent, 3% by weight of photoinitiator (Irgacure 184, Shivagai Co., Ltd.) were mixed and stirred for 60 minutes to prepare a photocurable paint for flooring.

Comparative Example 8: Photocurable Paint Composition for Flooring

67 wt% of the photocurable urethane (meth) acrylate resin prepared in Comparative Example 5, 15 wt% of hydroxyethyl acrylate, 8 wt% of acryloyl morpholine, and beta-carboxyethyl acrylate in a reactor equipped with a stirrer 6% by weight, 1% by weight of slip and antifoaming agent, 3% by weight of photoinitiator (Irgacure 184, Shivagai Co., Ltd.) were mixed and stirred for 60 minutes to prepare a photocurable paint for flooring.

Curability was measured using the built-in photocurable urethane (meth) acrylate resin and photocurable urethane (meth) acrylate resin prepared in Examples 3 to 7 and Comparative Examples 2 to 3, and the minimum for tack free and defect free curing The 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 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 2 Comparative Example 3 Remarks UV Curability 5 5 5 5 5 Not hardened Not hardened 500 mJ / cm ² conditions Minimum capacity for tack free and defect free curing (mJ / cm ² ) 100 200 300 300 200 - - Reverberation Evaluation No fuzz No fuzz No fuzz No fuzz No fuzz Has a sting Has a sting Olfactory discrimination Color Difference / Yellow (△ E) 1 or less 1 or less 1 or less 1 or less 1 or less - - Evaluation after 20 irradiations under 500mJ / cm ² condition Adhesion 100/100 100/100 100/100 100/100 100/100 - -

As shown in the measurement results of Table 1, Comparative Examples 2 to 3, which are general photocurable urethane (meth) acrylate resins, cannot be UV cured without the photoinitiator, and the built-in photocurable urethanes of Examples 3 to 7 according to the present invention. The (meth) acrylate resin showed good UV curability even without a photoinitiator. Adhesion with the flooring material obtained good results.

In addition, the curability was measured by the built-in photocurable coating composition for the flooring material prepared in Examples 8 to 11, confirmed the minimum energy (mJ / cm ² ) for tack-free and defect-free curing, after coating the flooring ASTM D The adhesion was evaluated by the method of 3359-87, the reverberation by smell was evaluated, and the steam resistance and the contamination resistance were evaluated when applied to the actual site. The measurement results are shown in Table 2 below.

division Example 8 Example 9 Example 10 Example 11 Remarks Curable 5 5 5 5 500 mJ / cm ² conditions Minimum capacity for tack free and defect free curing (mJ / cm ² ) 355 132 245 254 MEK resistance (count) More than 200 More than 200 More than 200 More than 200 Reverberation Evaluation No fuzz No fuzz No fuzz No fuzz Olfactory discrimination Color Difference / Yellow (△ E) 1 or less 1 or less 1 or less 1 or less Evaluation after 20 irradiations under 500mJ / cm ² condition Adhesion 100/100 100/100 100/100 100/100 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 intrinsic photocurable coating compositions of Examples 8 to 11 according to the present invention have a slight difference in curability due to the molecular design of the intrinsic photocurable urethane (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 built-in photocurable coating composition for flooring prepared in Examples 9 to 10 and Comparative Examples 6 to 8, and confirmed the minimum energy (mJ / cm ² ) for tack-free and defect-free curing, After coating on the flooring, the adhesiveness was evaluated by the method of ASTM D 3359-87, the reverberation by smell was evaluated, and the steam resistance and fouling resistance were measured when applied to the actual site. The measurement results are shown in Table 3 below.

division Example 9 Example 10 Comparative Example 6 Comparative Example 7 Comparative Example 8 Remarks Curable 5 5 5 4 5 500 mJ / cm ² conditions Minimum capacity for tack free and defect free curing (mJ / cm ² ) 132 245 435 725 254 MEK resistance (count) More than 200 More than 200 More than 200 150 ~ 170times More than 200 Reverberation Evaluation No fuzz No fuzz There is an afterglow There is an afterglow There is an afterglow Olfactory discrimination Color Difference / Yellow (△ E) 1 or less 1 or less 4 3 2 Evaluation after 20 irradiations under 500mJ / cm ² condition Adhesion 100/100 100/100 100/100 100/100 100/100 Steam resistance ◎ ◎ ◎ ◎ ◎ Visual discrimination Pollutant ◎ ◎ ◎ ◎ ◎ Visual discrimination

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

As shown in the measurement results of Table 3, the curable photocurable coating compositions of Examples 9 to 10 according to the present invention have a slight difference in curability due to the molecular design of the photocurable urethane (meth) acrylate resin without a photoinitiator. However, overall showed good UV curability, Comparative Examples 6 to 8 prepared by mixing a conventional photoinitiator at the time of preparing the coating composition is a hard type Comparative Example 8 is similar to the UV curability of Comparative Example 6 Example 7 was found to be poor UV curing.

In particular, in Comparative Examples 6 to 8 there was a fine odor after curing, it was found that the color difference / yellowing (△ E) is much lower than the Example.

In addition, Examples 9 to 10 obtained good results in adhesion with the flooring material, steam resistance, and contamination.

Claims (26)

Including hydroxyl groups at both ends, Michael addition intermediate represented by the following formula (1): [Formula 1]

In the formula, R ₁ and R ₅ are the same as or different from each other, and each is hydrogen, a methyl group, or an alkyl group having 2 to 12 carbon atoms, R ₂ and R ₄ are the same as or different from each other, and each is hydrogen or a methyl group, R <_3> is a C1-C12 alkyl group, benzyl group, benzoyl group, (meth) acryl group, or an amide group. delete The method of claim 1, A Michael addition intermediate comprising a structure or functional group derived from an acrylate Michael acceptor comprising a β-dicarbonyl Michael donor and a hydroxy group. The method of claim 3, Michael-addition intermediate, characterized in that the β-dicarbonyl Michael donor comprises at least one selected from the group consisting of β-keto ester, β-diketone, β-keto amide, and β-ketoanilide. The method of claim 3, And said β-dicarbonyl michael donor comprises at least one member selected from the group consisting of ethyl acetoacetate, 2,4-pentanedione, and acetoacetanilide. The method of claim 3, The acrylate containing the hydroxy group is hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, 2-hydroxyethyl acrylate (HEA), 2-hydroxypropyl acrylate (HPA ), 4-hydroxybutyl acrylate, 2-hydroxy-3-acryloyloxy propyl methacrylate, and Michael, characterized in that it comprises one or more selected from the group consisting of 2-hydroxybutyl acrylate. Addition intermediates. The method of claim 3, The acrylate containing the hydroxy group is Michael addition intermediate, characterized in that 2-hydroxypropyl acrylate (HPA). The method of claim 3, The acrylate containing the hydroxy group is Michael addition intermediate, characterized in that the polyfunctional hydroxy acrylate. The method of claim 8, The multifunctional hydroxy acrylate is selected from the group consisting of glycerin dimethacrylate, 2-hydroxy-3-acryloyloxy propyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate Michael addition intermediate, characterized in that the species or more. Including hydroxyl groups at both ends, Built-in photocurable urethane (meth) acrylate resin composition comprising a Michael addition intermediate represented by the following formula (1) Michael addition intermediate. [Formula 1]

In the formula, R ₁ and R ₅ are the same as or different from each other, and each is hydrogen, a methyl group, or an alkyl group having 2 to 12 carbon atoms, R ₂ and R ₄ are the same as or different from each other, and each is hydrogen or a methyl group, R <_3> is a C1-C12 alkyl group, benzyl group, benzoyl group, (meth) acryl group, or an amide group. The method of claim 10, The resin is a built-in photocurable urethane (meth) acrylate resin composition comprising an acrylate end in the main chain. The method of claim 10, Built-in photocurable urethane (meth) acrylate resin composition further comprising an isocyanate-reactive polyol and a polyfunctional isocyanate. The method of claim 12, The isocyanate-reactive polyol is a built-in photocurable urethane (meth) acrylate resin composition comprising a hydroxyl group. The method of claim 12, The polyol is a visceral photocurable urethane (meth) acrylate resin composition comprising two or more isocyanate reactive moieties. The method of claim 12, The polyol has a weight average molecular weight of 400 to 2000 built-in photocurable urethane (meth) acrylate resin composition. The method of claim 12, Built-in photocurable urethane (meth) acryl, wherein the polyol is at least one selected from the group consisting of polyether polyols, polyester polyols, and polycarbonate polyols, polybutadiene glycols, acrylic polyols, and flame retardant polyols containing phosphorus (P). Rate resin composition. The method of claim 16, Built-in photocurable urethane (meth) acrylate resin composition wherein the polyether polyol is at least one selected from the group consisting of polypropylene glycol, polytetramethylene glycol, polypropylene glycol modified substance, and polyethylene glycol. The method of claim 16, Built-in photocurable urethane (meth) acrylate resin composition wherein the polyester polyol is at least one selected from the group consisting of polycondensation-based polyester polyols containing adipic acid system and ring-opening addition polymer-based polyester polyols including lactone system. The method of claim 12, The polyfunctional isocyanate is a visceral photocurable urethane (meth) acrylate resin composition selected from the group consisting of aliphatic, cycloaliphatic, and aromatic isocyanates. The method of claim 10, A built-in photocurable urethane (meth) acrylate resin composition further comprising at least one additive selected from the group consisting of coatings, paints, adhesives, pressure sensitive adhesives, pigments, gloss modifiers, flow agents, leveling agents, quenchers, and dispersants. The method of claim 10, Michael addition intermediate containing the hydroxyl group terminal is contained in 5 to 35 parts by weight based on 100 parts by weight of the total composition of the built-in photocurable urethane (meth) acrylate resin composition. The method of claim 12, The isocyanate-reactive polyol is included in 20 to 70 parts by weight based on 100 parts by weight of the total composition, The polyfunctional isocyanate is a built-in photocurable urethane (meth) acrylate resin composition containing 10 to 40 parts by weight based on 100 parts by weight of the total composition. Built-in photocurable urethane (meth) acrylate resin manufactured using the resin composition of any one of Claims 10-22. The method of claim 23, Built-in photocurable urethane (meth) acrylate resin of the weight average molecular weight of the resin is 600 to 30000. reacting the β-dicarbonyl michael donor with an acrylate michael acceptor including a hydroxyl group to prepare a Michael addition intermediate represented by the following Chemical Formula 1 including a hydroxyl group at both ends; And A method for producing a visceral photocurable urethane (meth) acrylate resin composition comprising mixing the Michael addition intermediate with an isocyanate reactive polyol, a polyfunctional isocyanate, and a monofunctional or polyfunctional (meth) acrylate monomer. [Formula 1]

In the formula, R ₁ and R ₅ are the same as or different from each other, and each is hydrogen, a methyl group, or an alkyl group having 2 to 12 carbon atoms, R ₂ and R ₄ are the same as or different from each other, and each is hydrogen or a methyl group, R <_3> is a C1-C12 alkyl group, benzyl group, benzoyl group, (meth) acryl group, or an amide group. The interior photocurable coating composition containing the interior photocurable urethane (meth) acrylate resin of Claim 23.