KR20020056028A - Photocure-type urethane acrylate oligomer - Google Patents

Abstract

PURPOSE: Provided is an ultraviolet curable urethane acrylate oligomer excellent in setting property, which enables a contaminant and its trace to be removed from decorative flooring to be removed by wiping with tissue or dry cloth when the flooring is contaminated by markers, ball point pen, shoe polish, and so on. CONSTITUTION: The oligomer is prepared by the steps of (i) reacting a mixture of polyester polyol of formula 2 and polyester polyol of formula 3 with a part of isocyanate functional group of isocyanate compound selected from aliphatic, cycloaliphatic, aromatic isocyanate compounds, or oligomers of these compounds; and (ii) addition reacting unreacted isocyanate with a mixture of hydroxyl group containing acrylate of formula 4 and hydroxyl group containing polyalkylene glycol macromer of formula 5 to form an urethane acrylate oligomer of formula 1. In the formulae, R3 represents an aliphatic, cycloaliphatic, aromatic compounds, or oligomer of these compounds, x1 is a compound of formula 4 or 5, Y represents a polyester polyol of formula 2 or a polyether polyol of formula 3, R3 and R4, which are same or different, represent an aliphatic or aromatic compound having C2-C10, n is 1-20, R5 and R6, which are same or different, represent an aliphatic or aromatic compound having C2-C10, o is 1-20, R1 represents hydrogen or methyl group, R8 and R9 represent an alkylene group of C2-C6.

Description

UV-curable urethane acrylate oligomer {Photocure-type urethane acrylate oligomer}

The present invention relates to an ultraviolet curable urethane acrylate oligomer, and more particularly, to be applied to an ultraviolet curable paint to have excellent stain resistance and non-pollution on the surface of the floor decoration material, and through a nitrogen purging device in production in the field. Very good non-pollution against pollutants such as magic pens, ballpoint pens, crayon marks, spattered foods by overcoming Oxygen inhibition even in air condition without curing process or adding amine compound to resin composition And urethane acrylate oligomers which are intended to exhibit fouling resistance.

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 they were not excellent in fouling resistance and non-pollution, and had to be reinforced with facilities such as nitrogen blowing to improve fouling resistance.

On the other hand, the surface layer of the conventional floor decoration material has a disadvantage that shows good fouling resistance after applying the ultraviolet curable coating film composition made using a general urethane acrylate oligomer and curing with ultraviolet light (under nitrogen blowing conditions).

The composition of the ultraviolet curable coating film composition at this time contains a general urethane acrylate oligomer, a monofunctional monomer, a photoinitiator, a quencher, etc.

However, in order to obtain an ultraviolet curable coating composition having excellent fouling resistance by using a general urethane acrylate oligomer, nitrogen blowing is performed during the ultraviolet curing reaction (maintained at an oxygen concentration of 100 ppm or less), or to the ultraviolet curable coating composition. A mixture of a tertiary amine (which acts to supply Hydrogen to activate the Norrish Type II initiator and promotes surface hardening by preventing Radical extinction by oxygen) is combined with the Norrish Type II initiator. Therefore, it is possible to exhibit good non-pollution and fouling resistance against pollutants such as magic only by overcoming the UV curing reaction obstacle caused by oxygen.

However, in the case of nitrogen blowing, the installation cost and maintenance cost of nitrogen are very large, which makes it difficult to apply in general air condition.When using a tertiary amine, yellowing occurs after a long time, and when the humidity in summer is high, so-called blooming ( It is difficult to use because it may cause a blooming phenomenon.

The present invention is to solve the problems of the prior art, its purpose is to overcome the curing obstacles caused by oxygen interference during surface curing under oxygen conditions, there is no yellowing phenomenon, excellent pollution resistance and non-pollution resistance on the surface of the flooring material By providing a UV-curable coating composition having a light, it is excellent UV curability that can easily remove contaminants and traces simply by wiping with a tissue or dry cloth during contamination by magic, ballpoint pen, shoe polish, and other household goods It is to provide a curable urethane acrylate oligomer.

The ultraviolet curable urethane acrylate oligomer of the present invention for achieving the above object is aliphatic, cyclic aliphatic, aromatic or these isocyanates with a mixture of polyester polyols represented by the following formula (2) and polyether polyols represented by the following formula (3) After reacting some isocyanate functional group of selected isocyanate compound in the oligomer of the compound, the remaining unreacted isocyanate is hydroxy group containing acrylate represented by the following formula (4) and the hydroxyl group containing polyalkylene glycol macromer represented by the following formula (5) It is characterized by that it is prepared by addition reaction with a mixture of the following formula (1).

Formula 1

Wherein R ₃ is an aliphatic, cyclic aliphatic, aromatic compound or oligomer of these compounds,

X ₁ is a compound of Formula 4 or 5,

Y is a polyester polyol of the formula (2) or a polyether polyol of the formula (3).

Formula 2

In formula, R <_4> , R <_5> is the same or different, and is C2-C10 aliphatic or aromatic compound, n is 1-20.

Formula 3

In the above formula, R ₆ and R ₇ are the same as or different from each other, and are an aliphatic or aromatic compound having 2 to 10 carbon atoms, and o is 1 to 20.

Formula 4

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

Formula 5

In the above formula, R ₁ is hydrogen or a methyl group, and R ₉ is an alkylene group having 2 to 6 carbon atoms.

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

In the present invention, in order to solve the problem of having to separate nitrogen treatment or tertiary amine treatment when applying the conventional UV-curable urethane oligomer to the flooring material, the initiator of the Norrish Type II in the hydrogen structure in the resin structure can be abstracted It is manufactured to allow excellent surface hardening by overcoming oxygen interference without using a separate nitrogen purging device or using a tertiary amine.

Looking at the manufacturing method of the urethane acrylate oligomer of the present invention in detail.

First, the polyester polyol of Formula 2 and the polyether polyol of Formula 3 are used to react with some isocyanate functional groups (NCO) in aliphatic, cyclic aliphatic, aromatic or oligomers of these isocyanate compounds, and then the remaining unreacted isocyanate is The hydroxy group-containing acrylate of Formula 4 and the hydroxy group-containing polyalkylene glycol macromer of Formula 5 are prepared by addition reaction together, and the final prepared form is represented as in Formula 1.

The polyester polyol of the 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, and the like; It is obtained by esterification condensation reaction of glycol having two hydroxyl groups, that is, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexamethylene glycol, etc. Preference is given to using 200 to 4,000 polyester polyols.

The polyether polyol of Chemical Formula 3 is used for the purpose of allowing Norrish Type II initiator to abstract the hydrogen atom at the α position in the resin structure, which is used for preparing the oligomer, which has two hydroxyl groups. That is, it is obtained by etherification condensation reaction of ethylene glycol, tetrahydrofuran, or the like produced by polymerizing ethylene oxide, and considering the curability and cured product properties, it is preferable to use a hydroxyl value of 80 to 1000 and a molecular weight of 100 to 4,000. Do.

More preferably, o in the above formula (3), that is, a polymerization degree of 2 to 10, a hydroxyl group of 30 to 600, and a molecular weight of 200 to 4,000 is used.

Examples of the hydroxy group-containing acrylate of Formula 4 include hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl acrylate, hydroxy propyl methacrylate, hydroxy butyl acrylate and hydroxy butyl methacrylate. , Hydroxy pentyl acrylate, hydroxy pentyl methacrylate, hydroxy hexyl acrylate, hydroxy hexyl methacrylate and the like.

The hydroxyl group-containing polyalkylene glycol glycol macromer of the formula (5) is polyethylene glycol glycol monoacrylate, polyethylene glycol glycol monopropylene methacrylate polypropylene propylene glycol monopropylene polyethylene glycol polybutylene glycol monoacrylate Polybutylene glycol monomethacrylate, polypentylene glycol, monoacrylate, polypentylene glycol monomethacrylate, and the like are preferably those having a hydroxyl group of 150 to 550 and a molecular weight of 100 to 4,000.

Diisocyanates used for the synthesis of such general urethane acrylate oligomers 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 oligomers of these compounds Etc.

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. In particular, in order to achieve efficient surface curing during ultraviolet curing, it is preferable to use trifunctional isocyanates or composite structures thereof.

The equivalent ratio of the isocyanate compound, the polyester polyol and the polyether polyol is suitably 0.5 to 1.2 equivalents of the polyether polyol to 2 equivalents of the isocyanate compound, respectively, and 0.6 to 1.3 equivalents of the polyester polyol are applied in consideration of the curing properties.

If the polyether polyol is less than 0.6 equivalent to 2 equivalents of isocyanate compound, the surface hardenability may be remarkably lowered and the mechanical properties of the coating may be poor. If the amount is more than 1.3 equivalent, the cured coating is more flexible than necessary due to the increase in molecular weight. Persistence may be degraded.

More preferably, 2 equivalents of isocyanate are mixed with 0.9 to 1.2 equivalents of polyether polyol and 0.6 to 1.3 equivalents of polyester polyol to react.

In addition, in order to further improve surface curing during UV curing, Norrish Type II initiators may abstract hydrogen atoms at the α position in the cured portion of the resin structure to unreacted isocyanates of intermediates obtained by addition reaction of polyester polyols or polyether polyols. In order to prepare so as to be prepared, by addition reaction of the hydroxyl group-containing polyalkylene macromer of the formula (5), in consideration of the toughness of the final coating film (toughness) of the hydroxyl group-containing acrylate monomer by partial addition reaction, ultraviolet Urethane acrylate oligomers having excellent surface hardenability upon curing are prepared.

At this time, the equivalent ratio of the isocyanate compound and the hydroxyl group-containing polyalkylene macromer is 0.5 to 1.0 equivalents of the hydroxyl group-containing polyalkylene macromer to 2 equivalents of the isocyanate compound, and the hydroxyl group-containing polyalkylene macromer is less than 0.5 equivalent. If the surface curability of the back surface is poor, the surface curing is faster than necessary if more than 1.5 equivalents, when manufacturing the final UV curable coating composition, the matte type is very high gloss can be difficult to control the gloss.

Here, the ratio of hydroxy group-containing polyalkylene macromer and hydroxy group-containing acrylate equivalent is about 2: 8 to 5: 5, and when it is out of this range, other physical properties such as strength and flexibility of the curable and cured coating film are different. Poor That is, when there are few hydroxyl group containing polyalkylene 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, flexibility, etc. Mechanical properties are poor.

Therefore, in consideration of surface hardenability and mechanical properties, the equivalent ratio is preferably 3: 7 to 4: 6.

Such UV curable urethane acrylate oligomers having excellent surface hardenability of the present invention are manufactured so that Norrish Type II initiators can abstract hydrogen atoms at the α position in the resin structure, thereby overcoming ultraviolet curing obstacles caused by oxygen interference even under air conditions. And excellent surface hardenability.

An example of a specific synthesis method for producing such a UV-curable urethane acrylate oligomer excellent surface curability is as follows.

That is, attaching isocyanate to a synthesis apparatus by weighing isocyanate in a four-necked round flask equipped with a thermometer, and then weighing a polyester polyol or polyether polyol and an appropriate amount of catalyst into a dropping tube and mounting the flask to the flask; Reacting by constantly adding the contents of the dropping tube in a dropping tube for 30 to 60 minutes while maintaining the reaction temperature at 50 to 60 ° C; after confirming the isocyanate content, the hydroxyl group-containing polyalkylene macromer and the hydroxy-containing acrylic Mounting the rate mixture on a flask by weighing an appropriate amount of polymerization inhibitor in a dropping tube as needed; The reaction is carried out by constantly adding the mixture in a dropwise tube for 60 to 120 minutes while maintaining the reaction temperature at 50 to 70 ℃: and the urethane acrylate oligomer is prepared by terminating the reaction when the final isocyanate% is 0 .

Hereinafter, described in detail through the preferred embodiment of the present invention as follows, the present invention is not limited by the embodiment.

Example 1

0.6 equivalent of polyester polyol produced by condensation reaction of adipic acid with hexamethylene glycol to 2 equivalents of hexamethylene methylene diisocyanate trimer (NIPPON POLYURETHAN, Japan name: Ｃｏｒｏｎａｔｅ ＨＸ) Urethane acrylate oligomers having excellent surface and curing properties were prepared using UV equivalents, 0.6 equivalents of hydroxyethyl acrylate, and 0.6 equivalents of polyethylene glycol glycol monoacrylate (polymerization degree of ethylene oxide oxide).

Example 2

0.6 equivalents of polyester polyols produced by condensation reaction of adipic acid and ethylene glycol to 2 equivalents of hexamethylene benzene diisocyanate trimer (Japan Nichire Co., Ltd., product name: Ｃｏｒｏｎａｔｅ ＨＸ), polyether polyol (Korean polyol, product name: 0.6P / E60.6) , Urethane acrylate oligomers having excellent surface and curing properties during UV curing were prepared using 0.8 equivalents of hydroxy ethyl acrylate and 0.8 equivalents of polyethylene glycol glycol monoacrylate (polymerization degree of ethylene oxide oxide).

Example 3

0.6 equivalent of polyester polyol produced by condensation reaction of isophthalic acid with ethylene glycol in 2 equivalents of hexamethylene benzene diisocyanate trimer (Japanese Nichire, diisocyanate trimer, product name: Ｃｏｒｏｎａｔｅ ＨＸ), polyether polyol (Korean polyol, product name: ＰＥＧ １０. 2 equivalents, polyether polyol (Korea Polyol Co., Ltd. product name: PEP300) 0.3 equivalent, 0.6 equivalents of hydroxyethyl acrylate, 0.6 equivalents of polyethylene glycol glycol monomethacrylate (polymerization degree of ethylene oxide oxide) Urethane acrylate oligomers having excellent surface cure properties were prepared.

Comparative Example 1

Hexamethylene methylene diisocyanate trimer (Japan Nichio-n) isocyanate trimer The conventional urethane acrylate oligomer was prepared in the same manner as in Example 1, except that 0.5 equivalent of hydroxypropyl acrylate was applied to 0.6 equivalent.

Experimental Example

30 parts by weight of each urethane acrylate oligomer prepared according to Examples 1 to 3 and Comparative Example 1, 10 parts by weight of pentaerythritol tetra acrylate (manufactured by UCB, Belgium), 1,6-hexanediol diacrylate 20% by weight Part, tripropylene glycol glycol diacrylate 20 parts by weight, polyethylene glycol glycol diacrylate 15 parts by weight, 4.5 parts by weight of photoinitiator (product made by CIBA-GEIGY, Switzerland, product name: IRGACURE 184), silicone acrylate (manufactured by UCB Belgium, product name: EBECRYL 350) Prepared UV-curable coating film composition with viscosity of 700-1,500 cps at 25 ° C using 0.5 parts by weight, coated with bar coater No.12 on PCC flooring material, and cured energy at 400mJ / ㎠ UV curing (UV irradiation apparatus: manufactured by the American American Ultrabiore Inc.), the results are shown in Table 1 below.

Pollution resistance Curable Adhesion % Elongation Example 1 ◎ ◎ ◎ 90 Example 2 ◎ ◎ ◎ 92 Example 3 ◎ ◎ ◎ 95 Comparative Example 1 △ X △ 90 (Note) ◎ ： Very good O: Good, △: Somewhat bad, X: Poor

In this test, the coating thickness of the specimen used was 15 micrometer (μm).

Adhesiveness was measured by the JIS D 0202 test method.In case of fouling resistance, pollutants were wiped off with a dry cloth after 24 hours after contamination, and the presence of traces was observed. Is an oil-based magic pen, ballpoint pen, pen-type ink (black / blue), calligraphic ink, colored pencil, crayons, highlighter pen, soy sauce, miso, red pepper, kimchi broth, bean paste, wine, wine, coffee, mustard, cola, yellow (yellow) ), Oral medicine, athlete's foot medicine, dye, manicure, oil / water paint, and dog urine.

Elongation was measured using Instron by elogation, and the film of the cured coating film was measured by floating on a glass plate.

Curability is measured using IL390B and observed the surface hardening state at the time of curing at 400mPa / cm2.

As described in detail above, when using the UV-curable urethane acryl excellent in curing properties according to the present invention, it is possible to obtain an ultraviolet-cured coating film having excellent contamination resistance, adhesion, curing property, and mechanical properties.

Claims (4)

The mixture of the polyester polyol represented by the following formula (2) and the polyether polyol represented by the following formula (3) is reacted with some isocyanate functional groups of an isocyanate compound selected from aliphatic, cyclic aliphatic, aromatic or oligomers of these isocyanate compounds, and then The reaction isocyanate is prepared by addition reaction with a mixture of a hydroxyl group-containing acrylate represented by the following formula (4) and a hydroxyl group-containing polyalkylene glycol macromer represented by the following formula (5), wherein the polyisocyanate compound 0.5 to 1.2 equivalents of the ester polyol, 0.6 to 1.3 equivalents of the polyether polyol, and a 2: 8 to 5: 5 equivalent ratio of the hydroxy group-containing polyalkylene macromer and the hydroxy group-containing acrylate Next episode featuring Urethane acrylate oligomer represented by the formula (1). Formula 1 Wherein R ₃ is an aliphatic, cyclic aliphatic, aromatic compound or oligomer of these compounds, X ₁ is a compound of Formula 4 or 5, Y is a polyester polyol of the formula (2) or a polyether polyol of the formula (3). Formula 2 In formula, R <_4> , R <_5> is the same or different, and is C2-C10 aliphatic or aromatic compound, n is 1-20. Formula 3 In the above formula, R ₆ and R ₇ are the same as or different from each other, and are an aliphatic or aromatic compound having 2 to 10 carbon atoms, and o is 1 to 20. Formula 4 In the above formula, R ₁ is hydrogen or a methyl group, and R ₈ is an alkylene group having 2 to 6 carbon atoms. Formula 5 In the above formula, R ₁ is hydrogen or a methyl group, and R ₉ is an alkylene group having 2 to 6 carbon atoms. The method of claim 1, wherein the polyester polyol represented by the formula (2) is at least one acid selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, phthalic acid, terephthalic acid; It is prepared by esterification condensation with at least one glycol selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and hexamethylene glycol, having a hydroxyl group of 30 to 600 and a molecular weight of 200 to 4,000. Urethane acrylate oligomer made into. The polyether polyol of claim 1 is obtained by etherification condensation of ethylene glycol tetrahydrofuran, and has a degree of polymerization (o) of 2 to 10, a hydroxyl group of 30 to 600, and a molecular weight of 200 to Urethane acrylate oligomer, characterized in that 4,000. The urethane acrylate oligomer according to claim 1, wherein a hydroxyl group-containing polyalkylene macromer is used in an amount of 0.5 to 1.0 equivalents based on 2 equivalents of isocyanate compounds.