KR100566549B1 - UV-curable urethane acrylate oligomer and UV-curable paints composition containing it - Google Patents

Abstract

The present invention relates to an ultraviolet curable urethane acrylate oligomer mixture and an ultraviolet curable coating composition comprising the same, wherein a chlorine group-containing polyester polyol and a polyether polyol are reacted with an isocyanate compound, and then the remaining unreacted isocyanate is a hydroxyl group-containing acrylic. In the case of a paint using a urethane acrylate oligomer mixture obtained by addition reaction with a latex, a hydroxy group-containing fluorine monomer, and a hydroxy group polyalkylene glycol macromer, compared to those using a general urethane acrylate oligomer, the resistance to cigarette, non-pollution and aging The ultraviolet cured coating film which is excellent in adhesiveness, curability, chemical-resistance, etc. can be obtained.

Description

UV-curable urethane acrylate oligomer mixture with excellent resistance to cracking and time-lapse adhesion and UV-curable paint composition using the same {UV-curable urethane acrylate oligomer and UV-curable paints composition containing it}

The present invention relates to a UV-curable urethane acrylate oligomer mixture having excellent Cigarette resistance and adhesion over time, and to a composition of UV-curable paints using the same, and more particularly, to UV-curable paints, giving cigarette resistance to cigarettes and the like. The surface of the upper floor has no surface damage, and it has low surface tension, so that water repellency and surface non-pollution are maximized, and it prevents hardening caused by oxygen even in the air condition, avoiding the conventional method which had to maintain the nitrogen atmosphere in production and application. Urethane acrylate oligomer mixtures and pigments used to overcome very high levels of non-pollution and fouling resistance against contaminants such as magic pens, ballpoint pens, crayon marks, and spatters. It relates to a UV-curable coating composition.

Conventionally, as a coating composition containing a general UV curing 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 , 3,912,516, 3,932,356 and 4,301,209, but the coating composition containing these UV-curable oligomers are not excellent in resistance to cigarette and yellowing, and are not directly applied to heat sources such as cigarettes. It caused damage.

The surface layer of such a conventional flooring material has a good non-pollution property but poor heat resistance even after applying UV curable coating composition made using a general urethane acrylate oligomer and curing under UV light under curing conditions.

The composition of the ultraviolet curable coating film composition at this time is 40 parts by weight of a general urethane acrylate oligomer, 2-hydroxy propyl acrylate, 20 parts by weight of monofunctional monomer, 15 parts by weight of 1,6 hexanediol diacrylate, trimethylol propane 10 parts by weight of triacrylate, 5 parts by weight of acetophenone photoinitiator, 8 parts by weight of a matting agent (silica), and 2 parts by weight of a silicone additive (Silicone).

Such UV curable coating composition not only lacks resistance to cigarette, but also lacks surface hardening (highly influenced by oxygen), so that it is not contaminated in a nitrogen atmosphere. Direct damage to the surface has been caused, and there is a problem that the adhesion of the coating film is remarkably degraded when exposed to a heat source due to insufficient adhesion to the material.                         

These 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 (8) or a polyether polyol represented by the following 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 (7).

Here, R ₃ is an aliphatic, cyclic aliphatic, aromatic compound or oligomer of these compounds, X is a compound represented by the formula (4), Y is a polyester polyol represented by the formula (8) or a polyether polyol of the formula (3).

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.

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

Here, the polyester polyol represented by the formula (8) 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, and glycol having two hydroxyl groups, that is, ethylene It is obtained by esterification condensation reaction of glycol, propylene glycol, butylene glycol, neopentyl glycol, hexamethylene glycol, etc., wherein a polyester polyol having a hydroxyl value of 30 to 600 and a molecular weight of 200 to 4,000 is used in consideration of curability and curable properties. It is desirable to.

The polyether polyol represented by the formula (3) is obtained by etherification condensation reaction of glycol having two hydroxyl groups, that is, ethylene glycol, tetrahydrofuran, and the like. Preference is given to using polyether polyols having a molecular weight of 200 to 4,000.

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.

Diisocyanates used for the synthesis of such general urethane acrylate oligomers, isophorone diisocyanate, 4,4-dihexyl 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, the oligomer of the isocyanate compound is trifunctional of 1,6-hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate, biuret of toluene diisocyanate, and isocyanurate (ISOCYANURATE) structure. Triisocyanates or composite structures thereof and the like can be used.

The equivalent ratio of the isocyanate compound to the polyester polyol or polyether polyol is suitably 0.5 to 1.5 equivalents of the polyester polyol or polyether polyol to 2 equivalents of the isocyanate compound, and if the polyol is less than 0.5 equivalent, the adhesion and mechanical properties of the coating film are poor. If it exceeds 1.5 equivalent, the curability is poor. A more preferable equivalent ratio is 0.8-1.2 equivalent of polyester polyol or polyether polyol to 2 equivalent of isocyanate. In addition, a urethane acrylate oligomer is prepared by a known method by addition reaction of the hydroxy group-containing acrylate represented by Formula 4 to the unreacted isocyanate of the intermediate obtained by addition reaction of polyester polyol or polyether polyol. At this time, the isocyanate compound and the hydroxy group-containing acrylate equivalent ratio are 0.5-1.5 equivalents of the hydroxy group-containing acrylate to 2 equivalents of the isocyanate compound, and if the hydroxy group-containing acrylate is less than 0.5 equivalent, the curability is poor, and the amount is greater than 1.5 equivalents. Its surface adhesion and mechanical properties are poor.

Using the general urethane acrylate oligomers synthesized above, it is impossible to obtain a composition having excellent heat resistance and UV-curable coating film composition. However, in order to obtain a UV-curable coating composition having excellent stain resistance, nitrogen blowing is performed during the UV curing reaction process ( Maintain oxygen concentration below 100ppm) and act as a tertiary amine (hydrogen atom supply to UV curable coating composition) to activate Norrish Type 2 initiator and prevent surface extinction by oxygen. It is possible to show good non-contamination and fouling resistance to pollutants such as magic only when the curing conditions are maintained to overcome the UV curing reaction by oxygen by mixing with Norrish Type 2 initiator. have.

However, in these methods, nitrogen blowing is very difficult to apply in a general field (Air Condition) due to the high cost of equipment and maintenance of nitrogen, and when tertiary amine is used, it causes yellowing problems and summer humidity after a long time. Is high, it is difficult to use because it may cause a so-called blooming phenomenon.

In order to overcome these disadvantages, the present invention allows the fluorinated monomer having excellent heat resistance to be bonded to the resin backbone, and by applying a polyester polyol containing chlorine- to provide excellent adhesion even when exposed to a heat source for a long time. By adjusting the flexibility and strength of the cured coating film, the surface of the cured coating film is not damaged against heat sources such as cigarettes, and the non-polluting function is maximized by imparting water repellency due to low surface tension. By constructing the resin structure so that the hydrogen atom can be abstractable by the Norrish Type 2 initiator, it is possible to overcome the oxygen interference without the use of tertiary amines so that excellent surface hardening can be performed to maintain the non-polluting function.

Accordingly, it is an object of the present invention to impart Cigarette resistance to minimize surface damage caused by a heat source so that the durability of the flooring material is improved, and in case of ultraviolet curing, it overcomes the curing obstacles caused by oxygen interference in the air condition. It is possible to provide a UV-curable coating composition exhibiting contaminants to prevent surface damage caused by cigarettes, etc., and at the same time, simply wipe off with contaminants or dry cloth when contaminated by magic, ball pen, shoe polish, or other household goods. The present invention provides an ultraviolet curable urethane acrylate oligomer mixture having excellent resistance to cigarette and a UV-curable coating composition using the same, which makes the adhesion of the UV-curable coating film to a material stable even when exposed to heat for a long time.

The ultraviolet curable urethane acrylate oligomer mixture of the present invention for achieving the above object is aliphatic, cyclic aliphatic, using a chlorine group-containing polyester polyol represented by the following formula (2) and a polyether polyol represented by the following formula (3) After reacting some isocyanate functional groups of an isocyanate compound selected from an aromatic or oligomer of these isocyanate compounds, the remaining unreacted isocyanate is a hydroxy group-containing acrylate represented by the following formula (4), and a hydroxy group-containing fluorine monomer represented by the following formula (5) , and then 0.6 to 1 equivalent of polyester polyol jidoe obtained by addition reaction of a hydroxyl group-containing polyalkylene glycol macromer represented by the formula (6), about 2 times the amount of the isocyanate compound represented by the above formula (2), 0.6-1.3 equivalents of polyether polyol represented by Formula 3, 0.5-1 equivalent of hydroxy group-containing fluorine monomer represented by Formula 5, 0.3-0.7 equivalents of polyalkylene macromer represented by Formula 6, and Formula 4 Urethane which is a hydroxy group-containing acrylate represented by 0.1 to 0.4 equivalent ratio, and among the urethane acrylate oligomer represented by the following formula (1), Y is a polyester polyol represented by the formula (2) and X is a compound represented by the formula (4) Acrylate oligomers, urethane acrylate oligomers, all of which X is a compound represented by formula (5), urethane acrylate oligomers, all of which X is a compound represented by formula (6), urethane acrylates, wherein X is a compound represented by formulas (4) and (5), respectively Oligomers, urethanes, wherein X is a compound represented by formulas (5) and (6), respectively Relate oligomer, urethane acrylate oligomer, each X is a compound represented by Formula 4 and 6; Urethane acrylate oligomers, wherein Y is a polyether polyol represented by formula (3) and X is a compound represented by formula (4), urethane acrylate oligomers, where X is a compound represented by formula (5), all X are represented by formula (6) Phosphorus urethane acrylate oligomer, urethane acrylate oligomer, wherein X is a compound represented by formula (4) and formula (5), urethane acrylate oligomer, where X is a compound represented by formulas (5) and 6, respectively, and represented by formulas (4) and (6) A mixture of compounds selected from urethane acrylate oligomers, wherein the compound comprises at least one urethane acrylate oligomer, wherein Y is a chlorine group-containing polyester polyol represented by formula (2), and X is a hydroxyl represented by formula (5). Urethane acrylate which is a time-containing fluoromonomer It is characterized by including at least one or more oligomers.

Formula 1

Wherein R ³ is an aliphatic, cyclic aliphatic, aromatic compound or oligomer of these compounds, X is selected from compounds represented by Formulas 4, 5 and 6, and Y is a polyester polyol represented by Formula 2 and a poly Selected from ether polyols.

Formula 2

Here, R <_3> is a C2-C6 aliphatic or aromatic compound with 2-4 chloro groups, R <_5> is a C2-C10 aliphatic or aromatic compound and m is 1-4.

Formula 5

Wherein, R ₂ is hydrogen, R ₉ is alkylene having 2 to 4 carbon atoms.

Formula 6

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.

Urethane acrylate oligomer mixture with excellent non-pollution resistance and excellent UV curability due to its excellent resistance to cigarettes, no surface damage to cigarettes, overcoming oxygen interference during UV curing under air conditions, and UV-curable coatings. .

The urethane acrylate oligomer mixture was reacted with an isocyanate functional group (NCO) of aliphatic, cyclic aliphatic, aromatic or oligomers of these isocyanate compounds using a polyester polyol and a polyether polyol containing a chlorine group represented by Formula 2 above. Next, the remaining unreacted isocyanate is used mainly for the hydroxy group-containing fluorine monomer represented by the formula (5), but in consideration of the surface curing property, and the hydroxy-containing polyalkylene glycol macromer represented by the formula (6) and represented by the formula (4). The hydroxyl group-containing acrylate is used by some addition reaction, and the final prepared form is represented by the above formula (1).

The chlorine group-containing polyester polyol represented by the formula (2) is an acid having two carboxyl groups, that is, chloroacetic anhydride, hetic acid, tetrachlorophthalic anhydride, etc. glycol having two hydroxyl groups, that is, ethylene glycol and propylene. It is obtained from esterification condensation reaction of glycol, butylene glycol, neopentyl glycol, hexamethylene glycol and the like, in which a polyester polyol having a hydroxyl value of 50 to 500 and a molecular weight of 300 to 3,000 is used in consideration of adhesion, flexibility, and curability. It is preferable. In particular, in order to improve the Cigarette resistance, it is preferable to use a high content of chlorine.

The polyether polyol represented by the formula (3) is used for the purpose of enabling the Norrish Type 2 initiator to abstract the hydrogen atom at the α position in the resin structure, which is used for the preparation of the oligomer having two hydroxyl groups. Glycols, that is, those obtained by etherification condensation reactions such as ethylene glycol, tetrahydrofuran, or polymerized ethylene oxide, and those having a hydroxyl value of 30 to 600 and a molecular weight of 200 to 4,000 are preferable in consideration of curability and curable properties. Do.                     

 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 fluorine monomer represented by Formula 5, ethanol is mainly used as 2,2,2-trifluoro.

The hydroxy group-containing polyalkylene glycol glycol macromer represented by Chemical Formula 6 is present in an intermediate obtained by addition reaction of an isocyanate compound with a chlorine group-containing polyester polyol and a polyether polyol in order to further improve surface curing during ultraviolet curing. The hydrogen atom at the α position is used to enable the Norrish Type 2 initiator to be abstractable. Specific examples include polyethyleneethylene glycol glycol monoacrylate, polyethylene glycol glycol monomethacrylate, polypropylenepropylene glycol glycol monoacrylate, polypropylenepropylene glycol monomethacrylate, polybutylene glycol monoacrylate, polybutylene glycol monoacrylate, Pentylene glycol glycol monoacrylate, polypentylene glycol glycol monomethacrylate, and the like.

Meanwhile, as the diisocyanate compound, isophorone diisocyanate, 4,4-dihexyl 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 oligomers of these compounds.

In particular, the oligomer of the isocyanate compound is trifunctional of 1,6-hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, isophorone diisocyanate, biuret of toluene diisocyanate, and isocyanurate (ISOCYANURATE) structure. Triisocyanates or composite structures thereof may be used, and trifunctional isocyanates or composite structures thereof may be preferably used in order to achieve efficient surface hardening during UV curing.

 The equivalent ratio of the isocyanate compound and the polyester polyol or polyether 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.

When the polyester polyol is less than 0.6 equivalent, the adhesion with time is poor, and if the equivalent is more than 1 equivalent, the resin compatibility becomes poor and the wettability of the coating may be degraded when the coating is applied.

When the polyether polyol is less than 0.6 equivalent, the surface hardenability may be remarkably degraded and the mechanical properties of the coating film may be deteriorated. If the equivalent weight is greater than 1.3 equivalent, the cured coating film is more flexible than necessary, and thus the non-pollution persistence is reduced. Can be.                     

 More preferred equivalent ratios are 2 equivalents of isocyanate to 0.8 to 1.0 equivalents of polyether polyol and 0.6 to 0.9 equivalents of polyester polyol.

 In addition, in order to improve Cigarette resistance and non-pollution resistance of UV-curable coating film composition, the unreacted isocyanate of the intermediate obtained by addition reaction of the isocyanate compound with the chlorine group-containing polyester polyol of Formula 2 and the polyether polyol of Formula 3 above The hydroxyl group-containing fluorine-monomer represented by the formula (5) is reacted by addition.

In addition, in order to further improve surface curing during UV curing, the Norrish Type 2 initiator can abstract the hydrogen atom at the α position in the intermediate obtained by addition reaction of an isocyanate compound with a chlorine group-containing polyester polyol and a polyether polyol. In order to add and react the hydroxyl group-containing polyalkylene macromer represented by the formula (6), and in addition to the hydroxyl group-containing acrylate monomer in consideration of the hardenability (toughness) of the final coating film surface during ultraviolet curing Urethane acrylate oligomers having excellent curability are prepared.

At this time, the equivalent ratio of the isocyanate compound and the hydroxy group-containing fluorine-monomer / hydroxy group-containing polyalkylene macromer / hydroxy group-containing acrylate is 2 equivalents of the isocyanate compound and the hydroxy group-containing fluorine-monomer / hydroxy group-containing polyalkylene mark 0.5-1.0 / 0.3-0.7 / 0.1-0.4 equivalents of acrylate / hydroxy group-containing acrylate are suitable.If the hydroxy group-containing fluorine-monomer is less than 0.5 equivalents, the heat resistance is poor. If the hydroxy group-containing polyalkylene macromer is less than 0.3 equivalent, the surface hardenability is poor. If it is more than 0.7 equivalent, the cured coating film may be weakened more than necessary. In addition, if the hydroxyl group-containing acrylate is less than 0.1 equivalent, the curability is inferior, and if it is more than 0.4 equivalent, the coating film may become hard.

Here, the hydroxy group-containing fluorine monomer / hydroxy group-containing polyalkylene macromer / hydroxy group-containing acrylate equivalent ratio is about 5: 3: 2 to 6: 3: 1, and when it is out of this range, the curable and cured coating film Poor strength and flexibility of other physical properties . In other words, when the content of the hydroxy group-containing fluorine monomer is small, the tar-tracing property becomes weak among the cigarette resistance, and when the amount of the hydroxy group-containing polyalkylene macromer is low, the surface hardenability is poor. When contamination and stain resistance are remarkably reduced, and when there are few hydroxy group containing acrylates, mechanical properties, such as curability, coating film strength, and flexibility, become poor.

Therefore, in consideration of surface hardenability and mechanical properties, the equivalent ratio is preferably 5.5: 3: 1.5.

The UV curable urethane acrylate oligomer having excellent surface hardenability according to the present invention has a halogen-based structure in the resin structure, so that it can have excellent resistance to cigarette resistance and low surface tension when applied to UV-curable paints. Even if exposed, it has the characteristic to have little influence on body adhesiveness.

The ultraviolet curing urethane acrylate oligomer which is excellent in such Cigarette resistance and time-lapse adhesion is manufactured by the following synthesis method.

That is, attaching isocyanate to a synthesis apparatus by weighing isocyanate in a four-necked round flask equipped with a thermometer, and then weighing polyester polyol and polyether polyol and an appropriate amount of catalyst in a dropping tube and mounting the flask on the flask; Reacting by constantly adding the contents of the dropping tube dropwise for 30 to 60 minutes while maintaining the reaction temperature at 50 to 60 ° C; After confirming the specified isocyanate content, add a hydroxy group, fluorine monomer, hydroxy group-containing polyalkylene macromer, and hydroxy group-containing acrylate mixture to the dropping tube, if necessary, add an appropriate amount of polymerization inhibitor to the dropping tube, and mount it in the flask. Making a step; 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 urethane acrylate oligomer mixture is prepared by terminating the reaction when the final% isocyanate reaches zero.

The urethane acrylate oligomer obtained as described above having excellent heat resistance 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 urethane acrylate oligomer mixture to affect the physical properties of the coating film, and one or more monomers may be used, and mainly used are monomers having an acrylic ester monomer and a monofunctional vinyl group. 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 perflow Rho-n-hexane and the like, can be used in a 1 / 9-9 / 1 weight ratio with the urethane acrylate oligomer, 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 cyclo Hexanol, hydroxy ethyl acrylate, hydroxy propyl acrylate, vinyl-n-decanoate, vinyldecyl ether, vinyl isodecyl ether, vinyl lauryl ether, vinyl octadecyl ether, 2,2,2-triflo Low ethyl acrylate, 2,2,2-trifluoro ethylmethacrylate 2-bromo-3,3,3-trifluoropropene, 4-bromo-3,3,4,4-tetraflo Ro-1-butene and the like, N-vinyl-2-pyrrolidone, hydroxy propyl acrylate, hydroxyethyl acrylate, etc. are useful for easily adjusting the viscosity of varnish coating and increasing the curing rate. It is used for the oligomer and 1 / 9-9 / 1 weight ratio can be used.

The photoinitiator uses a conventional polymerization initiator activated by ultraviolet rays, and in particular, 0.5 to 10% by weight of the benzophenone series, acetophenone series, benzyl dimethyl ketal anthraquinone series, thioxanthone series, etc. Use if possible.

As such photoinitiators, 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 leveling 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. The silica-based matting agent may be used in an amount of 1 to 10% by weight based on the required glossiness.

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

200 parts of polyester polyol (hydroxyl value 132, molecular weight 850) produced by condensation reaction of chloroacetic anhydride with hexamethylene glycol in 390 parts of hexamethylene methylene isocyanate trimer (Nippon Polyurethane, Nippon Polyurethane, product name: Coronate HX) 150 parts of ether polyols (Korean polyol, product name: PEG 400, hydroxyl value 280.5, molecular weight 400), 130 parts of 2,2,2-trifluoroethanol, 180 parts of hydroxyethyl acrylate, polyethylene glycol + monoacrylate acrylate 80 parts (ethylene The urethane acrylate oligomer mixture was prepared using the degree of polymerization n = 6) of the oxide bond, and the viscosity of the urethane acrylate oligomer mixture was 8500 cps.

Preparation Example 2 Preparation of Inventive Urethane Acrylate Oligomer

180 parts of polyester polyols (hydroxya value 60, molecular weight 1,870) synthesized by condensation reaction of tetrachlorophthalic anhydride with neopentylglycol in 390 parts of hexamethylene methane isocyanate trimer (Nippon Polyurethane, product name: Cooronate HX) , 130 parts of polyether polyol (Korean polyol, product name: PEG 600, 187, molecular weight 600), 150 parts of hydroxy ethyl acrylate, 100 parts of 2,2,2-trifluoroethanol, 50 parts of polyethylene glycol glycol monoacrylate The urethane acrylate oligomer mixture was prepared using (polymerization degree n = 9 of ethylenexoxide bond), and the viscosity of this urethane acrylate oligomer mixture was 11000 cps.

Example 1: Preparation of the Invention UV Curable Coating Composition

400 parts of ultraviolet curable resins prepared in Preparation Example 1, 200 parts of polyethylene glycol 400 diacrylate (Miwon Corporation, trade name M-280), 150 parts of 1,6 hexanediol diacrylate (Miwon Corporation brand name: HDDA), hydride Roxypropyl 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 (DEGUSSA TS 100) was stirred to prepare an ultraviolet curable coating film composition having a viscosity of 800 cps at 25 ° C.

Physical property test results are shown in Table 1.                     

Example 2 Preparation of the Invention UV Curable Paint Composition

400 parts of ultraviolet curable resins prepared in Preparation Example 2, 200 parts of polyethylene glycol 400 diacrylate (Miwon Corporation, trade name M-280), 160 parts of 1,6 hexanediol diacrylate (Miwon Corporation brand name: HDDA), hydrate Oxyethyl 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 (DEGUSSA TS 100) was stirred to prepare an ultraviolet curable coating film composition having a viscosity of 750 cps at 25 ° C.

Physical property test results are shown in Table 1.

Example 3 Preparation of the Invention UV Curable Coating Composition

200 parts of the ultraviolet curable resins prepared in Preparation Example 1, 200 parts of the ultraviolet curable resins prepared in Preparation Example 2, 200 parts of tripropylene glycol diacrylate, polyethylene glycol 400 diacrylate (Miwon Corporation name: M-280) 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 100 parts of (DEGUSSA brand name: TS100) were stirred to prepare an ultraviolet curable coating composition having a viscosity of 830 cps at 25 ° C.

Physical property test results are shown in Table 1.

Comparative Example 1

400 parts of urethane acrylate resin (SK-UCB company, EBECRYL284), 1.6 parts of 1.6 hexanediol diacrylate (Miwon Corporation name: HDDA) 160 parts, hydroxy propyl acrylate part 280 parts, photoinitiator (Ciba-Geigy company name: IR184) 25 In addition, by stirring a photoinitiator benzophenone (25 parts of Ciba-Geigy), 10 parts of a leveling agent (SK-UCB company EBECRYL350), 100 parts of a matting agent (DEGUSSA brand name: TS100), an ultraviolet curable coating composition having a viscosity of 800 cps at 25 ℃ Prepared. Physical property test results are shown in Table 1 below.

Comparative Example 2

Urethane acrylate resin (SK-UCB company, EBECRYL830) 400 parts of polyethylene glycol 400 diacrylate (M-280), 160 parts of hydroxypropyl acrylate, 280 parts of photoinitiator (Ciba-Geigy company name: IR184) 25 parts, photoinitiator benzophenone (Ciba-Geigy company) 25 parts), a leveling agent (10 parts of SK-UCB company EBECRYL350) 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.

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.

The specific measuring method is as follows.

(1) Resistance to cigarette: Visual observation of carbonization trace after cigarette light x 5min

(2) Non-pollution: Wipe the residue after wiping it with tissue after 10min of black magic contamination

(3) Ultraviolet curability: Observe the tack-freeness of the cured coating film after passing through the UV curing device using an illuminometer (IL390B)

(4) Adhesion over time: measured by JIS D0202 (Cross-Cut, Tape Test)

(5) Alkali resistance: Observation of coating state after immersion in 5% sodium hydroxide aqueous solution at room temperature x 24 hours

(6) Acid resistance: 5% hydrochloric acid aqueous solution room temperature × 24 hours immersion after observation

(7) Saline resistance: 5% sodium chloride aqueous solution at room temperature x 24 hours

(8) Abrasion resistance: CS-10, 1000g Load, 100 times using a dual abrasion tester (Model 505 from Teledyne Taber)

(9) Weather resistance: Discoloration (yellowing) observation after 7 days of QUV

Example Comparative Example One 2 3 One 2 Cigarette resistance ◎ ◎ ◎ △ × Non-polluting ◎ ◎ ◎ × × Curable ◎ ◎ ◎ △ △ Chip structure tile adhesion 100/100 100/100 100/100 100/100 20/100 Chemical resistance Alkali resistance ◎ ◎ ◎ △ × Acid resistance ◎ ◎ ◎ ◎ ◎ Saline resistance ◎ ◎ ◎ ○ △ Abrasion Resistance (mg) 3 3 4 9 10 Yellowing resistance ○ ○ ○ △ △ ◎: excellent, ○: good, △; Somewhat bad, x: bad

As described in detail above, according to the present invention, the chlorine group-containing polyester polyol and the polyether polyol are reacted with an isocyanate compound, and then the remaining unreacted isocyanate is a hydroxy group-containing fluorine monomer and a hydroxy group-containing polyalkylene glycol mark. In the case of a paint using a urethane acrylate oligomer mixture obtained by addition reaction with a romamer and a hydroxy group-containing acrylate, it has a very high resistance to cigarette, non-pollution, time-lapse adhesion, curability, and chemical resistance, as compared with a general urethane acrylate oligomer. It can be seen that an excellent ultraviolet cured coating film can be obtained.

Claims (5)

(Correction) Some isocyanate functional groups of an isocyanate compound selected from aliphatic, cyclic aliphatic, aromatic or oligomers of these isocyanate compounds using a chlorine group-containing polyester polyol represented by the following formula (2) and a polyether polyol represented by the following formula (3) After the reaction, the remaining unreacted isocyanate is hydroxy group-containing acrylate represented by the following formula (4), hydroxy group-containing fluorine monomer represented by the following formula (5), and hydroxy group-containing polyalkylene glycol represented by the following formula (6) Obtained by addition reaction as a macromer , 0.6-1 equivalent of the polyester polyol represented by the formula (2), 0.6-1.3 equivalents of the polyether polyol represented by the formula (3), and 0.5-1 equivalent of the hydroxy group-containing fluorine monomer represented by the formula (5) relative to 2 equivalents of the isocyanate compound 0.3 to 0.7 equivalents of polyalkylene macromer represented by Formula 6 and 0.1 to 0.4 equivalent ratio of hydroxy group-containing acrylate represented by Formula 4 above; Of the urethane acrylate oligomer represented by Formula 1, wherein Y is a polyester polyol represented by Formula 2 and X is a compound represented by Formula 4, and urethane acrylate is a compound represented by Formula 5 Oligomers, urethane acrylate oligomers, wherein X is a compound represented by general formula (6), urethane acrylate oligomers, where X is a compound represented by formula (4) and formula (5), urethane acrylates where X is a compound represented by formulas (5) and (6), respectively Oligomers, urethane acrylate oligomers wherein X is a compound represented by formulas (4) and (6); Urethane acrylate oligomers, wherein Y is a polyether polyol represented by formula (3) and X is a compound represented by formula (4), urethane acrylate oligomers, where X is a compound represented by formula (5), all X are represented by formula (6) Phosphorus urethane acrylate oligomer, urethane acrylate oligomer, wherein X is a compound represented by formula (4) and formula (5), urethane acrylate oligomer, where X is a compound represented by formulas (5) and 6, respectively, and represented by formulas (4) and (6) A mixture of compounds selected from urethane acrylate oligomers, wherein the compound comprises at least one urethane acrylate oligomer, wherein Y is a chlorine group-containing polyester polyol represented by formula (2), and X is a hydroxyl represented by formula (5). Urethane acrylate which is a time-containing fluoromonomer UV-curable urethane acrylate oligomer mixture comprising at least one oligomer. Formula 1

Wherein R ³ is an aliphatic, cyclic aliphatic, aromatic compound or oligomer of these compounds, X is a compound selected from compounds represented by Formulas 4, 5 and 6, and Y is a polyester polyol represented by Formula 2 and Compound selected from polyether polyols . Formula 2

Here, R <_3> is a C2-C6 aliphatic or aromatic compound with 2-4 chloro groups, R <_5> is a C2-C10 aliphatic or aromatic compound and m is 1-4. 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

Wherein, R ₂ is hydrogen, R ₉ is alkylene having 2 to 4 carbon atoms. Formula 6

R ₁ is hydrogen or a methyl group, and R ₁₀ is an alkylene group having 2 to 6 carbon atoms. (Correction) The chlorine group-containing polyester polyol represented by the formula (2) is an ethylene group containing two chlorine group-containing carboxyl groups selected from chloroacetic anhydride, hete acid and tetrachlorophthalic anhydride. It is obtained from esterification condensation reaction with glycol having two hydroxyl groups selected from glycol, propylene glycol, butylene glycol, neopentyl glycol, and hexamethylene glycol, and is a polyester polyol having a hydroxyl value of 50 to 500 and a molecular weight of 300 to 3,000. UV curable urethane acrylate oligomer mixtures . (delete) (delete) (Correction) The ultraviolet curable coating composition containing the ultraviolet curable urethane acrylate oligomer mixture of Claim 1, a reactive monomer, a photoinitiator, etc.