KR100482028B1 - Mixture of urethanacrylate oligomer and UV-curable type paint composition - Google Patents

Abstract

The present invention does not use tertiary amines by constructing a resin structure so that the Norrish Type 1 initiator can abstract the hydrogen atom at the α position in the resin structure when preparing a urethane acrylate oligomer used in a conventional UV curable coating composition. It provides a mixture of urethane oligomers useful as a flooring material which provides non-slipness by adding functional fillers in the composition of paints by overcoming the surface of oxygen without overcoming the interference of oxygen, and providing a coating composition using the same. do.

Description

Mixture of urethane acrylate oligomers excellent in non-slip and non-pollution properties and UV curable paint composition comprising same {Mixture of urethanacrylate oligomer and UV-curable type paint composition}

The present invention relates to an ultraviolet curable coating composition having excellent non-slip and non-polluting properties, and more particularly, has an excellent non-slip and smooth texture on the surface of a floor decorative material by applying to an ultraviolet-curable paint. Ultraviolet curable type to be able to overcome Oxygen inhibition by oxygen even in air condition and to show very good non-pollution and pollution resistance against pollutants such as magic pen, ballpoint pen, crayon marks, spatter food, etc. It relates to a coating composition.

Conventionally, as a coating (coating) composition containing a general photocurable oligomer, for example, Korean Patent No. 74985, US Patent Nos. 3,782,961, 3,829,531, 3,874,905, 3,891,523, 3,895,171, 3,899,611 The coating compositions disclosed in US Pat. Nos. 3,912,516, 3,932,356, and 4,301,209 were used, but such coating compositions were not good in heat resistance and non-pollution, and did not have good non-slip properties. In addition, in order to improve the pollution resistance, it was necessary to reinforce the equipment such as nitrogen blowing.

The surface layer of such a conventional flooring material had a disadvantage of showing good fouling resistance after applying an ultraviolet curable coating composition made using a general urethane acrylate oligomer and curing with ultraviolet rays under nitrogen curing conditions, and to improve the fouling resistance The use of these additives has often resulted in slippery flooring injuries resulting in accidents such as falling down elderly people.

Here, looking at the manufacturing method of the urethane acrylate oligomer used for the ultraviolet curable coating film composition used for the generally known floor decoration material is as follows.

Urethane acrylate is mainly used in the UV curable coating composition for vinyl chloride flooring because of its advantages of providing its elasticity, excellent adhesion and a strong coating film.

Such urethane acrylate oligomers are reacted with an isocyanate functional group (NCO) of an aliphatic, cyclic aliphatic, aromatic, or oligomer of these isocyanate compounds with a polyester polyol represented by the following formula (2) or a polyether polyol represented by the formula (3) The remaining unreacted isocyanate is prepared by addition reaction with a hydroxyl group-containing acrylate represented by the following formula (4), and the obtained urethane acrylate oligomer is represented by the following formula (6).

Here, R ₃ is an aliphatic, cyclic aliphatic, aromatic compound or an oligomer of these compounds, X is a compound represented by the formula (4), Y is a polyester polyol represented by the formula (2) or a polyether polyol of the formula (3).

Here, R <_4> , R <_5> is a C2-C10 aliphatic or aromatic compound, n is 1-20.

Here, R <_6> , R <_7> is a C2-C10 aliphatic or aromatic compound, and o is 1-20.

R ₁ is hydrogen or a methyl group, and R ₈ is an alkylene group having 2 to 6 carbon atoms.

However, using a general urethane acrylate oligomer synthesized in the same manner as described above, it is impossible to obtain an ultraviolet-curable coating film composition having excellent heat resistance.However, in order to obtain an ultraviolet-curable coating composition having excellent stain resistance, an ultraviolet curing reaction process may be used. Nitrogen Blowing (maintains oxygen concentration below 100ppm) or serves to supply tertiary amine (Hydrogen) to UV curable coating composition to enable Norrish Type 1 initiator to be activated and to eliminate Radical extinction by oxygen It is a method to promote surface hardening by preventing it from being mixed with the Norrish Type 1 initiator, so that it is able to overcome the UV curing reaction disturbance caused by oxygen. May indicate contamination .

However, in case of nitrogen blowing, the equipment cost and maintenance cost of nitrogen are very high, which makes it difficult to apply in general air condition. When using tertiary amine, it causes yellowing problem and summer humidity after long time. If it is high, it is difficult to use because it may cause so-called blooming phenomenon. In addition, it maintains a slippery property, and the elderly have a safety problem by causing accidents that fall when water, oils, etc. get on the surface of the flooring material.

Accordingly, the present inventors are trying to overcome the limitation in applying the urethane oligomer obtained according to the above method as an ultraviolet curable paint, the hydrogen atom of the α-position in the resin structure of the Norrish Type 1 initiator As a result of constructing the resin structure to be abstractable, it was possible to overcome the oxygen interference without using tertiary amines, so that excellent surface hardening was possible. It has been found that the injury can be minimized to complete the present invention.

Accordingly, an object of the present invention is to provide a mixture of ultraviolet curable urethane acrylate oligomers capable of improving non-slip and non-pollution properties.

Another object of the present invention is to provide a UV curable coating composition comprising a mixture of the urethane acrylate oligomers as described above.

The mixture of the ultraviolet curable urethane acrylate oligomer of the present invention for achieving the above object is aliphatic, cyclic using a polyether polyol represented by the following formula (3) alone or a mixture with a polyester polyol represented by the following formula (2) After reacting some isocyanate functional groups of an isocyanate compound selected from aliphatic, aromatic or oligomers of these isocyanate compounds, the remaining unreacted isocyanate is represented by the following hydroxyl group-containing polyalkylene glycol macromer represented by the following formula (5) Obtained by addition reaction as a mixture with a hydroxy group-containing acrylate, the reaction equivalent ratio of the isocyanate compound and the hydroxy group-containing polyalkylene glycol macromer represented by the formula (5) is isocyanane It is a hydroxyl group containing polyalkylene glycol macromer 0.5-1.5 equivalent with respect to 2 equivalents of a hydrate compound, The hydroxyl group containing polyalkylene glycol macromer represented by the said Formula (5), and the hydroxyl group containing acrylic represented by the said Formula (4) The rate equivalent ratio is 1: 9-5: 5, and the urethane acrylate oligomer which X is a compound represented by general formula (4) among the urethane acrylate oligomer represented by following general formula (1), and the urethane acryl which is a compound represented by general formula (5) It is characterized in that the rate oligomer and X consists of a mixture of at least two or more compounds selected from urethane acrylate oligomers, which are compounds represented by formulas (4) and (5), respectively.

Here, R ₃ is an aliphatic, cyclic aliphatic, aromatic compound or oligomer of these compounds, X ₁ and X ₂ is a compound selected from a compound represented by the formula (4) and a compound represented by the formula (5), Y is represented by the formula (2) Polyesterpolyols or polyetherpolyols of formula (3).

R ₁ is hydrogen or a methyl group, and R ₁₀ is an alkylene group having 2 to 6 carbon atoms.

The present invention will be described in more detail as follows.

The mixture of the ultraviolet curable urethane acrylate oligomer according to the present invention is obtained by further using a polyalkylene glycol macromer represented by the formula (5) when preparing a urethane acrylate oligomer, which is usually used in an ultraviolet curable coating composition.

Method for producing a urethane acrylate oligomer mixture of the present invention to satisfy such properties, first, using a polyether polyol represented by the formula (3) alone, or mixed with the polyester polyol represented by the formula (2) To an isocyanate functional group (NCO) of an isocyanate compound selected from conventional aliphatic, cyclic aliphatic, aromatic or oligomers of these isocyanate compounds.

Here, the polyester polyol represented by Formula 2 is an acid having two carboxyl groups, that is, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, etc. It was obtained by esterification condensation reaction with ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexamethylene glycol and the like, and at this time, a polyester polyol having a hydroxyl value of 30 to 600 and a molecular weight of 200 to 4,000 in consideration of curability and cured product properties, etc. It is preferable to use.

The polyether polyol represented by Chemical Formula 3 is used for the purpose of enabling the Norrish Type 1 initiator to abstract the hydrogen atom at the α position in the resin structure, which is a glycol having two hydroxyl groups, that is, ethylene glycol and tetrahydro. It is obtained by etherification condensation reaction of furan or the like or prepared by polymerizing ethylene oxide, and considering the curability and cured product properties, the degree of polymerization is 2 to 10, and it is preferable to use a hydroxyl value of 30 to 1000 and a molecular weight of 100 to 4,000. Do.

Examples of the diisocyanate used in the synthesis of urethane acrylate oligomers having excellent heat resistance include isophorone diisocyanate, 4,4-dicyclohexyl methane diisocyanate, 1,6-hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, 2, 4,4-trimethyl 1,6-hexamethylene diisocyanate, octadecylene diisocyanate, 1,4-cyclohexylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and these compounds Oligomers and the like.

In particular, oligomers of isocyanate compounds include 1,6-hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate, biuret of toluene diisocyanate, and isocyanurate (ISOCYANURATE) structure. Trifunctional triisocyanates or composite structures thereof and the like can be used, and trifunctional isocyanates or composite structures thereof are preferably used in order to achieve efficient surface hardening during ultraviolet curing.

The equivalent ratio of the isocyanate compound and the polyether polyol alone or a mixture of the polyester polyol is suitably 0.6 to 1.3 equivalents of the polyether polyol to 2 equivalents of the isocyanate compound, and 0.6 to 1 equivalent of the polyester polyol is applied in consideration of curing properties. It is desirable to.

When the polyether polyol is less than 0.6 equivalents to 2 equivalents of isocyanate compound, the surface hardenability may be remarkably lowered and the mechanical properties of the coating film may be degraded. If the polyether polyol is more than 1.3 equivalent, the cured coating film is more flexible than necessary by increasing the molecular weight. The non-pollution persistence can be lowered. More preferred equivalent ratios are 2 equivalents of isocyanate, 0.8-1.0 equivalents of polyether polyol, and 0.6-0.9 equivalents of polyester polyol.

Conventionally, after reacting some isocyanate groups of the isocyanate groups with polyether polyols or polyester polyols as described above, the remaining unreacted isocyanates that do not participate in the reaction are mainly used polyalkylene glycol macromers represented by the formula (5) In the present invention, the polyether polyol represented by Chemical Formula 3 is mainly reacted with an isocyanate compound, and in some cases, in order to improve hardenability. Some polyester polyols represented by the formula (2) are used.

In the present invention, the polyalkylene glycol macromer represented by Chemical Formula 5 is mainly reacted with unreacted isocyanate that does not participate in the reaction, but is partially reacted by using a hydroxyl group-containing acrylate represented by Chemical Formula 4. .

The hydroxy group-containing acrylate represented by the formula (4) is hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl acrylate, hydroxy propyl methacrylate, hydroxy butyl acrylate, hydroxy butyl methacryl Hydroxy pentyl acrylate, hydroxy pentyl methacrylate, hydroxy hexyl acrylate, hydroxy hexyl methacrylate and the like.

As the hydroxyl group-containing polyalkylene glycol glycol macromer represented by the above formula (5), polyethyleneethylene glycol glycol monoacrylate, polyethylene glycol glycol monoacrylate, polypropylene glycol glycol monoacrylate, polybutyl Len glycol glycol monoacrylate, polybutylene glycol monomethacrylate, polypentylene glycol glycol monoacrylate, polypentylene glycol monomethacrylate, and the like. Such hydroxyl group-containing polyalkylene glycol macromers preferably have a hydroxyl value of 15 to 500 and a molecular weight of 100 to 4,000.

At this time, the equivalent ratio of the isocyanate compound and the polyalkylene glycol macromer represented by Formula 5 is 0.5-1.5 equivalents of the hydroxyl group-containing polyalkylene glycol macromer to 2 equivalents of the isocyanate compound, and the hydroxyl group-containing polyalkylene If the glycol macromer is less than 0.5 equivalent, the surface hardenability is poor, if more than 1.5 equivalent surface curing is faster than necessary, when manufacturing the final UV curable coating composition, the matte type is very high gloss can be difficult to control the gloss.

In addition, the equivalent ratio of the hydroxy group-containing polyalkylene glycol macromer of Formula 5 and the hydroxy group-containing acrylate of Formula 4 is about 1: 9 to 5: 5, and if it is out of this range, it is curable and cured. Other physical properties such as strength and flexibility of the coating film are poor. That is, when there are few hydroxyl group containing polyalkylene glycol macromers, surface hardenability becomes poor, and the non-contamination and stain resistance of a final cured coating film fall remarkably, and when there are few hydroxyl group containing acrylates, adhesiveness, strength, and flexibility Mechanical properties are poor. Therefore, in consideration of surface hardenability and mechanical properties, the hydroxyl group-containing polyalkylene glycol macromer and the hydroxyl group-containing acrylate equivalent ratio are preferably 2: 8 to 4: 6.

Through such a series of processes it is possible to obtain a urethane acrylate oligomer as a mixture, specifically, the urethane acrylate oligomer, X of the urethane acrylate oligomer represented by the general formula (1) is a compound represented by the general formula (4), X Are all in the form of a mixture of at least two compounds selected from the group consisting of a urethane acrylate oligomer and a compound represented by the formula (5) and a urethane acrylate oligomer represented by the formula (5). Such a mixture of urethane acrylate oligomers is prepared so that Norrish Type 1 initiators can be abstractable at the α position in the resin structure to overcome UV interference caused by oxygen interference in air condition and to exhibit excellent surface hardenability. Has characteristics.

The specific method for producing a UV-curable urethane acrylate oligomer mixture having excellent heat resistance is to weigh the isocyanate in a four-necked round flask equipped with a thermometer and attach it to a synthesis apparatus, followed by a mixture of polyether polyol alone or polyester polyol, and Loading an appropriate amount of catalyst into the flask by weighing it in a dropping tube; Maintaining the reaction temperature at 50 to 60 ° C. for 30 to 60 minutes to continuously add the contents of the dropping tube to react the reaction; Checking the prescribed isocyanate content, and then adding the hydroxy group-containing polyalkylene glycol macromers and the hydroxy-containing acrylate mixture to the dropping tube, if necessary, by weighing an appropriate amount of polymerization inhibitor into the dropping tube and mounting it in the flask; Reacting by constantly adding the mixture into the dropwise tube for 60 to 120 minutes while maintaining the reaction temperature at 50 to 70 ° C; The reaction is terminated when the final isocyanate content reaches zero.

The urethane acrylate oligomer mixture obtained as described above is applied to an ultraviolet curable paint, which may include a reactive monomer, a photoinitiator, a leveling agent, a quencher, and other additives.

In this case, the reactive monomer is polymerized together with the mixture of the urethane acrylate oligomer to affect the physical properties of the coating film, one or more monomers can be used, mainly used is an acrylic ester monomer and a monomer having a monofunctional vinyl group. to be. Here, the acrylic acid ester is produced by esterifying an alcohol and an unsaturated carboxylic acid, 1,4 butanediol diacrylate, 1,6 hexane diol diacrylate, neopentyl glycol diacrylate, pentaerythritol tetra methacrylate, Trimethylol propane triacrylate, ethylhexyl methacrylate, pentyl acrylate, hexyl acrylate, cyclohexyl methacrylate, 1,4 butanediol diacrylate, tripropylene glycol diacrylate, 1,6 divinyl perfluoro -n-hexane and the like, and can be used in a 1 / 9-9 / 1 weight ratio with the urethane acrylate oligomer mixture, of which 1,6 divinyl perfluoro-n-hexane 1/3 / 3 / When used in a 1 weight ratio, it is more preferable for improving heat resistance. On the other hand, monomers having a monofunctional vinyl group include N-vinyl-2 pyrrolidone, vinyl acetate, vinyl butyrate, vinyl isobutylate, vinyl caprate, vinyl caproate, vinyl captylate, vinyl cetyl ether, and vinyl cyclohexa. Nol, hydroxy ethyl acrylate, hydroxy propyl acrylate, vinyl-n-decanoate, vinyldecyl ether, vinyl isodecyl ether, vinyl lauryl ether, vinyl octadecyl ether, 2,2,2-trifluoro Ethyl acrylate, 2,2,2-trifluoro ethylmethacrylate 2-bromo 3,3,3-trifluoropropene, 4-bromo-3,3,4,4-tetrafluoro- 1-butene, etc., N-vinyl-2 pyrrolidone, hydroxy propyl acrylate, hydroxyethyl acrylate and the like are useful for easily adjusting the viscosity of the varnish coating and increasing the curing rate. , Oligomer It can be used in a 1 / 9-9 / 1 weight ratio with the mixture, especially in the present invention, 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoro ethylmethacrylate 2-bro Heat sources such as cigarettes when parent 3,3,3-trifluoropropene and 4-bromo-3,3,4,4-tetrafluoro-1-butene are used in a 1 / 3-3 / 1 weight ratio It is excellent in heat resistance. In addition, the other reactive monomers are related to the viscosity of the varnish, the flexibility of the coating film, the hardness, the adhesion, and the like.

The photoinitiator uses a conventional polymerization initiator which is activated by ultraviolet rays, and in particular, benzophenone series, benzyl dimethyl ketal series, acetophenone series, anthraquinone series, thioxanthone series, etc. are 0.5-10 wt% in the total coating composition. Use as much as possible.

As the photoinitiator, hydroxy-cyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenyl, acetophenone, benzophenone, phenyl-2-hydroxy 2-propyl ketone and the like can be mainly used.

The rebaling agent uses a silicone diacrylate-based or silicone polyacrylate-based compound so as to be 0.1 to 5% by weight in the total coating composition.

When semi-gloss or matte is required for the coating film composition, a matting agent may be used, but the silica-based matting agent may be used in an amount of 1 to 10% by weight based on the required glossiness.

In addition, the present invention uses a spherical functional particulate polymer (hereinafter referred to as a functional filler) obtained through acrylic resin suspension polymerization technology and polyurethane resin polymerization technology in order to impart non-slipness. The physical properties of the final cured coating film is improved, in particular, scratch resistance is improved, the feel is flexible, there is a high-quality texture, it is possible to further provide a matte effect. Moreover, depending on the surface conditions, there may be a significant difference in non-pollution. In particular, considering the cured product properties, the maximum effect can be obtained when using about 2 to 5% by weight.

Of course, other additives can be used in a known UV-curable coating composition by varying the amount added according to the requirements.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples. In the following examples, the oligomer of the present invention is prepared by varying the components, and then prepared by using a known method to compare with the conventional one.

Preparation Example 1 Preparation of Inventive Urethane Acrylate Oligomer Mixture

In a four-necked round-necked flask equipped with a thermometer, 2 equivalents of hexamethylenemethane diisocyanate trimer (Nippon polyurethane, product name: Coronate HX) was weighed and attached to the synthesis apparatus, and then, adipic acid and hexamethylene glycol were separately condensed. 0.1 equivalent of the prepared polyester polyol (hydroxyl value 132, molecular weight 850) and 0.4 equivalent of poly (ether ether) polyol (Korean polyol, product name: PEG 400, hydroxyl value 280.5, molecular weight 400) were loaded into the flask, and then the reaction temperature was 50 to 60 ° C. The polyester polyol and polyether polyol were introduced into a reactor containing an isocyanate compound through a dropwise tube over 30 to 60 minutes while maintaining the reaction mixture.

When the residual amount of isocyanate is 1.5 equivalents (measured in NCO%), 1.2 equivalents of hydroxypropyl acrylate, polyethylene glycol, monoacrylate, and 0.4 equivalent of polyethylene glycol oxide linkage (n = 6, molecular weight 436) are weighed into a dropping tube. Was added dropwise for 60 to 120 minutes while maintaining the temperature at 50 to 70 ℃ to confirm that the final isocyanate became 0%, the polymerization inhibitor was added to terminate the reaction.

In order to confirm the mixture of the obtained urethane acrylate oligomer, the structure was confirmed by instrumental analysis (FT-IR).

Preparation Example 2 Preparation of Inventive Urethane Acrylate Oligomer Mixture

The reaction method was the same as in Preparation Example 2, to 2 equivalents of hexa-methylene-diisocyanate trimer, 0.5 equivalent of poly (ether ether) polyol (Korean polyol, product name: PEG 600, hydroxyl value 187, molecular weight 600), 1.1 equivalent of hydroxy ethyl acrylate, The urethane acrylate oligomer mixture was prepared using 0.5 equivalent of polyethylene glycol mono acrylate (polymerization degree of ethylene oxide linkage n = 9, molecular weight 480).

In order to confirm the obtained urethane acrylate oligomer mixture, the structure was confirmed by instrumental analysis (FT-IR).

Example 1

400 parts of the ultraviolet curable urethane acrylate oligomer mixture prepared in Preparation Example 1, polyethylene glycol diacrylate (Miwon Corporation, trade name M-280), 150 parts of 1,6 hexanediol diacrylate (Miwon Corporation trade name: HDDA), 80 parts of hydroxy propyl acrylate, 25 parts of photoinitiator (trade name: IR184), 25 parts of photobenzoin benzophenone (Ciba-Geigy), 10 parts of leveling agent (SK-UCB company EBECRYL350), quencher (DEGUSSA : 100 parts of TS100) and 30 parts of non-slip fillers (ARTPEARL trade name C-200T, Japan) were stirred to prepare an ultraviolet curable coating composition having a viscosity of 800 cps at 25 ° C. Physical property test results are shown in Table 1 below.

Example 2

400 parts of the ultraviolet curable urethane acrylate oligomer mixture prepared in Preparation Example 1, 200 parts of polyethylene glycol diacrylate (Miwon Corporation, trade name M-280), 1,6 hexanediol diacrylate (Miwon Corporation brand name: HDDA) 150 Parts, hydroxypropyl acrylate 80 parts, photoinitiator (Ciba-Geigy trade name: IR184) 25 parts, photoinitiator benzophenone (Ciba-Geigy company) 25 parts, leveling agent (SK-UCB company EBECRYL350) 10 parts, quencher ( 70 parts of DEGUSSA brand name: TS100 and 30 parts of non-slip filler (ART PEARL Japan, brand name C-400T) were stirred to prepare an ultraviolet curable coating composition having a viscosity of 708 cps at 25 ° C. Physical property test results are shown in Table 1 below.

Example 3

400 parts of ultraviolet-curable urethane acrylate oligomer mixtures prepared in Preparation Example 2, 200 parts of polyethylene glycol diacrylate (Miwon Corporation, trade name M-280), 1,6hexanediol diacrylate (Miwon Corporation brand name: HDDA) 150 Parts, hydroxypropyl acrylate 80 parts, photoinitiator (Ciba-Geigy trade name: IR184) 25 parts, photoinitiator benzophenone (Ciba-Geigy company) 25 parts, leveling agent (SK-UCB company EBECRYL350) 10 parts, quencher ( 70 parts of DEGUSSA brand name: TS100) and 30 parts of non-slip filler (ART PEARL Japan, brand name C-200T) were stirred to prepare an ultraviolet curable coating composition having a viscosity of 708 cps at 25 ° C. Physical property test results are shown in Table 1 below.

Comparative Example 1

Urethane acrylate resin (SKUCB brand name EBECRYL 9269) 400 parts, 1,6 hexanediol diacrylate (trade name: HDDA) 160 parts, hydroxy propyl acrylate 280 parts, photoinitiator (Ciba-Geigy trade name: IR184) 25 parts, photoinitiator benzophenone (Ciba-Geigy) 25 parts), 10 parts of a leveling agent (EBECRYL350 manufactured by SK-UCB) and 100 parts of a matting agent (DEGUSSA trade name: TS100) were stirred to prepare an ultraviolet curable coating composition having a viscosity of 800 cps at 25 ° C. Physical property test results are shown in Table 1 below.

Comparative Example 2

Urethane acrylate resin (SKUCB brand name EBECRYL 9269) 400 parts, 1,6-hexanediol diacrylate (US-traded trade name :: HDDA) 160 parts, hydroxy propyl acrylate 280 parts, photoinitiator (Ciba-Geigy trade name: IR184) 25 parts, photoinitiator benzophenone (Ciba- 25 parts of Geigy), 10 parts of leveling agent (EBECRYL350 of SK-UCB company), 70 parts of matting agent (DEGUSSA brand name TS100), 30 parts of non-slip filler (ART PEARL Japan, brand name C-200T), An ultraviolet curable coating film composition of 850 cps was prepared. Physical property test results are shown in Table 1 below.

The UV curable coating composition of the present invention and the conventional photocurable coating composition obtained in accordance with the above Examples and Comparative Examples were applied to a PVC flooring and then subjected to a comparative test. In the following test, the coating film was coated with a thickness of 18 μm using a bar coater, and UV-cured at a curing energy of 700 mJ / cm 2 (UV irradiation apparatus: manufactured by American American Ultra Violet Co., Ltd.). The results are shown in Table 1 below.

Example Comparative example One 2 3 One 2 Non-slip ¹⁾ 2.5 3.2 2.98 1.2 2.5 Non-polluting ²⁾ ◎ ◎ ◎ × △ UV curable ³⁾ ◎ ◎ ◎ △ △ Adhesion ⁴⁾ 100/100 100/100 100/100 100/100 20/100 Chemical resistance Alkali resistance ⁵⁾ ◎ ◎ ◎ △ ○ Acid resistance ⁶⁾ ◎ ◎ ◎ ◎ ◎ Saline resistance ⁷⁾ ◎ ◎ ◎ ○ △ Abrasion Resistance (mg) ⁸⁾ 3 3 4 9 10 Weather resistance ⁹⁾ ○ ○ ○ ○ ○ (※ Legend) ◎: Good ○: Good, △: Slightly poor, X: Poor 1) Non-slipness: Measured by dynamic coefficient of friction based on DIN 53375 standard (The larger the value, the better the anti-slip function) 2 ) Non-pollution: Trace left after wiping with a tissue after 10 minutes of black magic contamination Visual observation 3): Curability measurement Observation of the tack-freeness of the cured coating film after passing through the UV curing device using an illuminometer (IL390B) 4): Measurement by JIS D0202 (Crros-Cut, Tape Test) 5): 5% sodium hydroxide aqueous solution room temperature X 24 hours immersed coating state 6): 5% hydrochloric acid aqueous solution room temperature X 24 hours immersion film state 7): 5% sodium chloride aqueous solution room temperature X Observation of coating state after 24 hours immersion 8): CS-10, 1000g Load, 1000 times 9) using a dual abrasion tester (Model 505 from Teledtne Taber): Discoloration (yellowing) after QUV X 7 days left

As described in detail above, in the case of the paint using the urethane acrylate oligomer mixture prepared according to the present invention, the stain resistance is significantly improved compared with the use of the general urethane acrylate oligomer, and the non-slip property when the functional filler is further added It is greatly improved and useful as a flooring material with excellent durability.

Claims (12)

(Correction) Some isocyanate functional groups of isocyanate compounds selected from aliphatic, cyclic aliphatic, aromatic or oligomers of these isocyanate compounds using a polyether polyol represented by the following formula (3) alone or a mixture with a polyester polyol represented by the following formula (2) and the reaction was jidoe then takes the remaining unreacted isocyanate, and then were subjected to addition reaction with a mixture of hydroxyl group-containing polyalkylene glycol macromer in the following hydroxyl group-containing acrylate of the formula (4) represented by the formula (5), The reaction equivalent ratio of the isocyanate compound and the hydroxyl group-containing polyalkylene glycol macromer represented by Chemical Formula 5 is 0.5 to 1.5 equivalents of the hydroxyl group-containing polyalkylene glycol macromer to 2 equivalents of the isocyanate compound. The hydroxy group-containing polyalkylene glycol macromer represented by the formula and the hydroxy group-containing acrylate equivalent ratio represented by the formula (4) is 1: 9 to 5: 5, In the urethane acrylate oligomer represented by the following formula (1), all X is represented by the formula (4) The compound consists of a mixture of at least two compounds selected from urethane acrylate oligomers, the urethane acrylate oligomers, wherein X is a compound represented by formula (5), and the urethane acrylate oligomers, wherein X is a compound represented by formulas (4) and (5), respectively. A mixture of UV-curable urethane acrylate oligomers. Formula 1 Here, R ₃ is an aliphatic, cyclic aliphatic, aromatic compound or oligomer of these compounds, X is a compound selected from a compound represented by the formula (4) and a compound represented by the formula (5) , Y is a polyester polyol represented by the formula (2) or Polyetherpolyol of formula (3). Formula 2 Here, R <_4> , R <_5> is a C2-C10 aliphatic or aromatic compound, n is 1-20. Formula 3 Here, R <_6> , R <_7> is a C2-C10 aliphatic or aromatic compound, and o is 1-20. Formula 4 R ₁ is hydrogen or a methyl group, and R ₈ is an alkylene group having 2 to 6 carbon atoms. Formula 5 R ₁ is hydrogen or a methyl group, and R ₁₀ is an alkylene group having 2 to 6 carbon atoms. (Correction) The polyester polyol of claim 1, wherein the polyester polyol represented by the formula (2) is an ethylene glycol having an acid having two carboxyl groups selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid and terephthalic acid , Obtained from esterification condensation reaction with a glycol having two hydroxyl groups selected from propylene glycol, butylene glycol, neopentyl glycol, and hexamethylene glycol, and having a hydroxyl polyhydric acid of 30 to 600 and a molecular weight of 200 to 4,000. A mixture of an ultraviolet curable urethane acrylate oligomer. (Correction) The polyether polyol represented by the formula (3) is obtained by etherification condensation of two hydroxyl groups selected from ethylene glycol and tetrahydrofuran, and has a degree of polymerization of 2 to 10. A mixture of ultraviolet curable urethane acrylate oligomers having a hydroxyl value of 30 to 1000 and a molecular weight of 100 to 4,000 . (delete) (Correction) The diisocyanate according to claim 1, wherein the diisocyanate is isophorone diisocyanate, 4,4- dicyclohexyl methane diisocyanate, 1,6-hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, 2,4,4- 1 selected from trimethyl 1,6-hexamethylene diisocyanate, octadecylene diisocyanate, 1,4- cyclohexylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and oligomers of these compounds A mixture of ultraviolet curable urethane acrylate oligomers, characterized in that they are at least one species. (delete) (delete) (Correction) The ultraviolet ray according to claim 1, which is used in an amount of 0.6 to 1.3 equivalents of the polyester polyol represented by the formula (2) and 0.6 to 1.3 equivalents of the polyether polyol represented by the formula (3) to 2 equivalents of the isocyanate compound. A mixture of curable urethane acrylate oligomers. (delete) (Correction) The ultraviolet curable coating composition containing the mixture of the ultraviolet curable urethane acrylate oligomer of Claim 1 , a reactive monomer, a photoinitiator, and a functional filler. (delete) The UV curable coating composition according to claim 10, wherein the functional filler is a spherical functional fine particle polymer obtained through an acrylic resin suspension polymerization technique and a polyurethane resin polymerization technique.