KR20080061134A - Urethane acrylate oligomer and method of manufacturing the same - Google Patents

Abstract

A urethane acrylate oligomer is provided to impart improved flexibility and adhesion to a coating layer, thereby preventing generation of cracks and separation of the coating layer on a film even after winding into the shape of a roll. A urethane acrylate oligomer is obtained by reacting 1 eq of isocyanate, 0.2-0.3 eq of polyether polyol represented by the following formula: HO-[-R1-O-R2-O-]n-H and 0.85-0.95 eq of a hydroxyl group-containing acrylate monomer, and has a molecular weight of 500-5000. In the formula, each of R1 and R2 represents a C2-C10 aliphatic alkylene; and n is a natural number of 1-20.

Description

Urethane acrylate oligomer and its manufacturing method {URETHANE ACRYLATE OLIGOMER AND METHOD OF MANUFACTURING THE SAME}

The present invention relates to a urethane acrylate oligomer and a method for producing the same, and more particularly, to a urethane acrylate oligomer and a method for producing the same which can increase the flexibility and adhesion of the coating film.

In general, a coating film is formed on the surface of a polyvinyl chloride (PVC) flooring or a polyethylene terephthalate (PET) film to improve durability, and the like, and the coating may be formed using an ultraviolet curable coating composition.

Generally, an ultraviolet curable coating composition contains a urethane acrylate oligomer, and the urethane acrylate oligomer is obtained by reacting an isocyanate, a polyester polyol, a hydroxy group-containing acrylate monomer, and the like.

In the case of the PET film, after coating the coating film on the characteristics of use, it is finally wound and stored in a roll, etc., in the case of forming a coating film with a conventional UV curable coating composition, in the process of winding the roll due to the lack of flexibility of the coating film Cracks may occur, and the coating may be peeled off due to insufficient photocuring.

Therefore, the technical problem of the present invention is to solve such a conventional problem, to provide a urethane acrylate oligomer that can increase the flexibility and adhesion of the coating film.

Another technical problem of the present invention is to provide a method for preparing the urethane acrylate oligomer.

The urethane acrylate oligomer according to one aspect of the present invention is obtained by reacting 1 equivalent of isocyanate, 0.2-0.3 equivalents of polyether polyol of formula (1) below, and 0.85-0.95 equivalents of hydroxyl group-containing acrylate monomer. The molecular weight of the urethane acrylate oligomer is 500 to 5000.

<Formula 1>

R 1 and R 2 in Formula 1 are each aliphatic alkylene having 2 to 10 carbon atoms, and n is a natural number of 1 to 20.

For example, the isocyanate is 1,6-hexamethylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, hexamethylene It may comprise at least one selected from the group consisting of isocyanate trimer, hexamethylene biuret type trimer and 2,6-toluene disocyanate.

In addition, the isocyanate may include trifunctional isocyanate and difunctional isocyanate, and the molar ratio of the trifunctional isocyanate and difunctional isocyanate may be 55:45 to 60:40.

The hydroxy group-containing acrylate monomer may include at least one selected from the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxybutyl acrylate.

According to the manufacturing method of the urethane acrylate oligomer which concerns on one characteristic of this invention, 40-60 degreeC by adding 1 equivalent of isocyanate and 0.2-0.3 equivalent of polyether polyol of Formula 1, a catalyst, and an acryl monomer for viscosity adjustment to a reaction container The isocyanate and polyether polyol are reacted.

<Formula 1>

(R 1 and R 2 in Formula 1 are each aliphatic alkylene having 2 to 10 carbon atoms, and n is a natural number of 1 to 20.)

0.85 to 0.95 equivalent of the hydroxyl group-containing acrylate monomer is added to the reaction vessel and reacted at 50 to 70 ° C. Next, additional catalyst is added to terminate the reaction.

The content of the acrylic monomer for viscosity control may be 10 to 30% by weight of the total weight of the polyether polyol and isocyanate combined, the acrylic monomer for viscosity adjustment is tripropylene glycol diacrylate, hexanediol diacrylate, trimethylolpropane It may include at least one selected from the group consisting of triacrylate, isobornyl acrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate.

As described above, the urethane acrylate oligomer may increase the flexibility and adhesion of the coating film.

Hereinafter, a urethane acrylate oligomer and a method for preparing the same according to an embodiment of the present invention will be described with reference to Examples.

Urethane acrylate oligomer

The urethane acrylate oligomer according to one embodiment of the present invention is obtained by reacting about 1 equivalent of isocyanate, about 0.2 to about 0.3 equivalents of polyether polyol, and about 0.85 to about 0.95 equivalents of hydroxy monomer containing hydroxy group. The molecular weight of the urethane acrylate oligomer is about 500 to 5000.

Examples of the isocyanate include 1,6-hexamethylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, hexamethylene isocyanate trimer , Hexamethylene biuret type trimer, 2,6-toluene disocyanate and the like, and preferably, an unyellowed type aliphatic isocyanate may be used. These may each be used alone or in combination.

Moreover, in order to improve the chemical-resistance and stain resistance of a coating film, it is preferable to mix the isocyanate trimer which has a trifunctional group, and the diisocyanate which has a bifunctional group in an appropriate ratio. Specifically, the molar ratio of the isocyanate trimer and diisocyanate is preferably about 55:45 to about 60:40. When the content of the isocyanate trimer exceeds the above range, the viscosity of the coating composition may be excessively increased, and when the content of the diisocyanate exceeds the above range, the overall physical properties of the coating film may decrease.

The polyether polyol is for imparting flexibility to a coating film formed by using the urethane acrylate oligomer, and may be represented by the following Chemical Formula 1.

<Formula 1>

R 1 and R 2 in Formula 1 are each aliphatic alkylene having 2 to 10 carbon atoms, and n is a natural number of 1 to 20.

For example, the polyether polyol may be obtained by ether condensation of ethylene glycol, tetrahydrofuran, or the like having one or two hydroxy groups or by polymerizing ethylene oxide. Specifically, the PLACCEL monomer series of DAICEL (Japan) (Placcel M, 205, 208, FM2D, etc.) and the BASF (Germany) polytetrahydrofuran series (Polytetrahydrofuran 650, 1000, 1800, 2000, 2900, or more) Product names) and the like, and these may each be used alone or in combination. Considering the degree of cure and physical properties of the coating film, the molecular weight of the polyether polyol is preferably about 300 to about 3000.

Examples of the hydroxy group-containing acrylate include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, and the like, which may be used alone or in combination.

Method for producing a urethane acrylate oligomer according to an embodiment of the present invention is as follows. First, an isocyanate, a polyether polyol, an acryl monomer for controlling viscosity, a catalyst, and a polymerization inhibitor are added to a reaction vessel such as a four-necked flask equipped with a thermometer and reacted while maintaining the reaction temperature at about 40 to about 60 ° C. Next, a hydroxy-containing acrylate monomer is added and reacted while maintaining the reaction temperature at about 50 to about 70 ° C. A catalyst is added to the mixture, and when the isocyanate group in the mixture disappears, the reaction is terminated to obtain a urethane acrylate oligomer.

As the catalyst, a general catalyst used for urethane polymerization may be used, for example, dibutyltindilaurylate may be used.

Examples of the acrylic monomer for viscosity control include tripropylene glycol diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate, isobornyl acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and the like. They can each be used alone or in combination. In addition, whether or not to use should be selected in consideration of the price, coating properties after curing, the amount is preferably about 10 to about 30% by weight of the total weight of the polyol and isocyanate combined.

Photocurable coating composition comprising a urethane acrylate oligomer according to an embodiment of the present invention can form a coating film excellent in flexibility, adhesion, stain resistance, photocurability, chemical resistance and the like.

Hereinafter, the urethane acrylate oligomer according to an embodiment of the present invention will be described through specific examples, comparative examples, and experimental examples.

Example 1

In a four-necked flask equipped with a thermometer, about 1.1 equivalents of hexamethylene isocyanate trimer, about 0.9 equivalents of isophorone diisocyanate, about 0.5 equivalents of Polytetrahydrofuran 1000, a catalyst, and tripropylene glycol diacrylate were added and reacted at about 50 ° C. The content of tripropylene glycol diacrylate was about 20% by weight of the total weight of the isocyanate and the polyol. Next, about 1.8 equivalents of hydroxyethyl acrylate was added, and the temperature was raised to about 60 ° C to react. When the catalyst was gradually added and the isocyanate group disappeared, the reaction was terminated to obtain a urethane acrylate oligomer.

Example 2

In a four-necked flask equipped with a thermometer, about 1.2 equivalents of hexamethylene isocyanate trimer, about 0.8 equivalent of isophorone diisocyanate, about 0.6 equivalent of Polytetrahydrofuran 650, a catalyst, and tripropylene glycol diacrylate were added and reacted at about 50 ° C. The content of tripropylene glycol diacrylate was about 20% by weight of the total weight of the isocyanate and the polyol. Next, about 1.7 equivalents of hydroxyethyl acrylate was added, and the temperature was raised to about 60 ° C to react. When the catalyst was gradually added and the isocyanate group disappeared, the reaction was terminated to obtain a urethane acrylate oligomer.

Example 3

In a four-necked flask equipped with a thermometer, about 1.2 equivalents of hexamethylene isocyanate trimer, 0.8 equivalents of isophorone diisocyanate, 0.5 equivalents of Placcel FM2D, a catalyst, and tripropylene glycol diacrylate were added and reacted at about 50 ° C. The content of tripropylene glycol diacrylate was about 20% by weight of the total weight of the isocyanate and the polyol. Next, about 1.8 equivalents of hydroxyethyl acrylate was added, and the temperature was raised to about 60 ° C to react. When the catalyst was gradually added and the isocyanate group disappeared, the reaction was terminated to obtain a urethane acrylate oligomer.

Example 4

In a four-necked flask equipped with a thermometer, about 2 equivalents of hexamethylene isocyanate trimer, about 0.5 equivalents of Placcel FM2D, a catalyst, and tripropylene glycol diacrylate were added and reacted at about 50 ° C. The content of tripropylene glycol diacrylate was about 20% by weight of the total weight of the isocyanate and the polyol. Next, about 1.8 equivalents of hydroxyethyl acrylate was added, and the temperature was raised to about 60 ° C to react. When the catalyst was gradually added and the isocyanate group disappeared, the reaction was terminated to obtain a urethane acrylate oligomer.

Example 5

In a four-necked flask equipped with a thermometer, about 2 equivalents of isophorone diisocyanate, about 0.5 equivalents of Polytetrahydrofuran 1000, a catalyst, and tripropylene glycol diacrylate were added and reacted at about 50 ° C. The content of tripropylene glycol diacrylate was about 20% by weight of the total weight of the isocyanate and the polyol. Next, about 1.8 equivalents of hydroxyethyl acrylate was added, and the temperature was raised to about 60 ° C to react. When the catalyst was gradually added and the isocyanate group disappeared, the reaction was terminated to obtain a urethane acrylate oligomer.

Experimental Example

About 20 parts by weight of polyethylene glycol 400 diacrylate, about 20 parts by weight of 1,6-hexanediol diacrylate, tripropylene glycol triacryl, in 20 parts by weight of each urethane acrylate oligomer prepared according to Examples 1 to 5 About 17 parts by weight, about 5 parts by weight of dipentaerythritol hexaacrylate, about 4 parts by weight of Irgacure 184 (product name) from Ciba Chemical (Switzerland) as a photoinitiator, Tego RAD 2700 (product name) by Tego Chemie (Germany) as an additive About 1 part by weight, about 7 parts by weight of TS-100 (product name) of Degussa (Germany) as a matting agent was mixed to prepare a photocurable coating composition. Each photocurable coating composition was applied to a polyvinyl chloride (PVC) substrate with a bar coater (bar coater No. 16) and irradiated with ultraviolet light of about 1500 mJ / cm ² to form a coating film. The thickness of each coating film was about 15 micrometers.

Curability, adhesiveness, fouling resistance and gloss of each coating film were measured, and these were evaluated by a four-step evaluation method (◎: excellent ○: good Δ: normal ×: poor) and are shown in Table 1 below.

In order to evaluate the curability of each coating film, the curability of the surface of each coating film was measured using POWER PUCK (Product name, USA EIT Inc., USA) which is a UV photometer.

In order to evaluate the adhesiveness of each coating film, the adhesiveness of each coating film and a base material was measured according to JISD0202.

In order to evaluate the stain resistance of each coating film, each coating film was contaminated with an oil-based magic pen, and after 10 minutes / 24 hours, each coating film was wiped off with a tissue to observe the presence of traces.

In order to evaluate the glossiness of each coating film, the glossiness of each coating film was measured (60 microseconds) by the Gloss meter by BYK. (The gloss of a typical PVC floor is between 60 and 5 to 10.)

Table 1

Example 1 Example 2 Example 3 Example 4 Example 5 Curable ○ ○ ○  ◎ △ Adhesion ◎ ◎ ◎ × ◎ Pollution resistance ◎ ◎ ◎ ◎ × Polish 6.5 6.8 7.0 8.0 6.6 ◎: Excellent ○: Good △: Normal ×: Poor

Referring to Table 1, the coating films formed using the urethane acrylate oligomers of Examples 1 to 3 were generally excellent or good in curability, adhesion, stain resistance, and gloss, but the urethane acrylate oligomer of Example 4 was used. The formed coating film was poor in adhesion, and it can be seen that the coating film formed using the urethane acrylate oligomer of Example 5 was poor in stain resistance.

According to the present invention as described above, flexibility and adhesion of the coating film can be increased.

In the detailed description of the present invention described above with reference to a preferred embodiment of the present invention, those skilled in the art or those skilled in the art having ordinary knowledge in the scope of the invention described in the claims to be described later It will be understood that various modifications and variations can be made in the present invention without departing from the scope of the present invention.

Claims (8)

A urethane acrylate oligomer having a molecular weight of 500 to 5000 obtained by reacting 1 equivalent of isocyanate, 0.2 to 0.3 equivalent of polyether polyol of formula (1) below and 0.85 to 0.95 equivalent of hydroxy monomer containing hydroxy group. <Formula 1>

(R 1 and R 2 in Formula 1 are each aliphatic alkylene having 2 to 10 carbon atoms, and n is a natural number of 1 to 20.) The method of claim 1, wherein the isocyanate is 1,6-hexamethylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, A urethane acrylate oligomer comprising at least one selected from the group consisting of hexamethylene isocyanate trimer, hexamethylene biuret type trimer and 2,6-toluene disocyanate. The urethane acrylate oligomer according to claim 1, wherein the isocyanate includes trifunctional isocyanate and difunctional isocyanate, and the molar ratio of the trifunctional isocyanate and difunctional isocyanate is 55:45 to 60:40. According to claim 1, wherein the hydroxy group-containing acrylate monomer comprises at least one selected from the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxybutyl acrylate Urethane acrylate oligomer, characterized in that. Reacting the isocyanate and the polyether polyol at 40 to 60 ° C. by adding 1 equivalent of isocyanate and 0.2 to 0.3 equivalent of the polyether polyol of Formula 1, a catalyst, and an acrylic monomer for viscosity adjustment to a reaction vessel; Adding 0.85 to 0.95 equivalents of a hydroxyl group-containing acrylate monomer to the reaction vessel and reacting at 50 to 70 ° C; And Method of producing a urethane acrylate oligomer comprising the step of adding a catalyst to terminate the reaction. <Formula 1>

(R 1 and R 2 in Formula 1 are each aliphatic alkylene having 2 to 10 carbon atoms, and n is a natural number of 1 to 20.) The method of claim 5, wherein the isocyanate includes a trifunctional isocyanate and a bifunctional isocyanate, and a molar ratio of the trifunctional isocyanate and the difunctional isocyanate is 55:45 to 60:40. . The method of claim 5, wherein the isocyanate is 1,6-hexamethylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, A method for producing a urethane acrylate oligomer comprising at least one selected from the group consisting of hexamethylene isocyanate trimer, hexamethylene biuret type trimer and 2,6-toluene disocyanate. According to claim 5, wherein the content of the acrylic monomer for viscosity control is 10 to 30% by weight of the total weight of the polyether polyol and isocyanate combined, the viscosity monomer acrylic monomer is tripropylene glycol diacrylate, hexanediol diacrylate And at least one selected from the group consisting of trimethylolpropane triacrylate, isobornyl acrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate.