KR101219174B1 - Urethane modified unsaturated acrylic resin, method for preparing the same and coating composition comprising the same - Google Patents

Abstract

The present invention relates to a urethane-modified unsaturated acrylic resin, a method for manufacturing the same and a coating composition comprising the same, and more particularly, to prepare a urethane-modified unsaturated acrylic resin from a polyhydroxy acrylic resin and a terminal unsaturated urethane oligomer and to paint such as flooring The present invention relates to a urethane-modified unsaturated acrylic resin capable of securing excellent workability, weather resistance, water resistance and elongation, a method of manufacturing the same, and a coating composition including the same.

Description

Urethane-modified unsaturated acrylic resin, a manufacturing method thereof, and a coating composition including the same TECHNICAL FIELD

The present invention relates to a urethane-modified unsaturated acrylic resin, a method for manufacturing the same and a coating composition comprising the same, and more particularly, to prepare a urethane-modified unsaturated acrylic resin from a polyhydroxy acrylic resin and a terminal unsaturated urethane oligomer and to paint such as flooring The present invention relates to a urethane-modified unsaturated acrylic resin capable of securing excellent workability, weather resistance, water resistance and elongation, a method of manufacturing the same, and a coating composition including the same.

Flooring materials, such as for automobile roads and bicycle roads, cannot be closed for a long time due to their characteristics, and since they are mostly applied outdoors, the coating formed therefrom is exposed to the external environment. Therefore, in the flooring materials such as automobile roads and bicycle roads, there is a need for fast construction and weather resistance to withstand the external environment. However, current flooring using epoxy and urethane polymers that are currently commercialized will be discolored by various external stimuli such as sunlight. This prevents discoloration by applying a top coat using an acrylic polymer, but the construction time is long due to the additional top coat.

To solve this problem, polyvinylacetate, polyvinylchloride (PVC), polyvinylchloride-vinylacetate, thermoplastic acrylate copolymer, unsaturated polyester are used as binders, and (meth) acrylate monomers are introduced as reactive diluents. Attempts have been made to improve workability and weatherability.

For example, Korean Patent Publication No. 1990-0008426 uses polyvinyl chloride as a binder for a main body, methyl methacrylate, 2-ethylhexyl acrylate, etc. as a reactive diluent, and benzoyl peroxide as a curing agent. The configuration is disclosed. However, polyvinyl chloride, which is a binder disclosed and used in the patent document, has a problem in that deformation occurs due to heat accompanying radical reaction, and swelling occurs severely within several minutes after stirring of the curing agent.

In addition, Korean Laid-Open Patent Publication No. 2008-0061421 discloses a configuration in which a thermoplastic acrylic resin is used as a binder of a main body, an acrylate monomer is used as a reactive diluent, and benzoyl peroxide is used as a curing agent. The preparation of the binder in the patent document is carried out by applying and bulk polymerizing an initiator capable of generating radicals by heat to the acrylic monomer and a molecular weight controlling agent capable of controlling the molecular weight and leaving 30 to 50 parts by weight of unreacted monomer, such a reaction The use of a non-reactive organic solvent in the manufacture of the binder can be excluded, there is an advantage that can contribute to the solidification of the final product. However, the bulk polymerization method has a disadvantage in that it is difficult to control heat generation and has a non-uniform polymerization conversion rate at every production route, and the mechanical properties of the coating film are deteriorated because the binder is not combined with the reactive diluent in the final floor coating film.

In addition, Korean Patent Laid-Open Publication No. 2009-0128748 discloses a configuration in which an unsaturated polyester resin is used as a binder of a main body, an acrylate monomer is used as a reactive diluent, and benzoyl peroxide is used as a curing agent. However, in the above patent document, since unsaturated polyester is used as the binder, when the expensive acid monomer and the alcohol monomer are not used, discoloration becomes severe due to external stimulation such as sunlight, and there is a disadvantage in that weather resistance decreases due to hydrolysis.

Thus, while maintaining the basic coating properties, there is a need for the development of a floor covering paint that can secure excellent workability, weather resistance and water resistance.

Republic of Korea Patent Publication No. 1990-0008426 Republic of Korea Patent Publication No. 2008-0061421 Republic of Korea Patent Publication No. 2009-0128748

The present invention is to solve the problems of the prior art as described above, while maintaining the basic coating film properties in paints (for example, floor coatings for automobiles), urethane-modified unsaturated acrylic that can secure excellent workability, weather resistance and water resistance It is a technical subject to provide resin and the coating composition using the same.

In order to achieve the above technical problem, the present invention (A) polyhydroxy acrylic resin; And (B) a terminal unsaturated urethane oligomer; to provide a urethane-modified unsaturated acrylic resin, characterized in that the urethane reaction.

In addition, in another aspect of the present invention, a) the alkyl (meth) acrylate monomer having 1 to 12 carbon atoms, the (meth) acrylate monomer containing a hydroxy group and the ethylenically unsaturated monomer are copolymerized by solution polymerization to obtain a solid content. Preparing a polyhydroxy acrylic resin (A) that is at least 80%; b) 0.6 to 0.8 molar equivalents of a (meth) acrylate monomer containing a hydroxy group relative to 1 molar equivalent of a monomer containing an isocyanate group, independently of this, using an alkyl (meth) acrylate monomer having 1 to 12 carbon atoms as a solvent. And urethane-reacting 0.05 to 0.15 molar equivalents of the polyol containing a hydroxyl group at both ends to prepare a terminal unsaturated urethane oligomer (B) having a solid content of 20 to 50%; And c) mixing and urethane-reacting the polyhydroxyacrylic resin (A) and the terminal unsaturated urethane oligomer (B), respectively, which are prepared. .

In still another aspect, the present invention provides a coating composition comprising the urethane-modified unsaturated acrylic resin.

The coating composition using the urethane-modified unsaturated acrylic resin of the present invention has excellent weather resistance and water resistance as well as basic coating properties such as crack resistance (elongation), and for automobile roads, bicycle roads, and walking floors requiring fast construction. It is especially preferable to apply to paints.

Hereinafter, the present invention will be described in detail.

(A) Polyhydroxy  Acrylic resin

Polyhydroxy acrylic resin is one of the reactants for producing the urethane-modified unsaturated acrylic resin of the present invention, is a polymer component that contributes to improving weather resistance and water resistance.

Specifically, the polyhydroxy acrylic resin may be a copolymer of an alkyl (meth) acrylate monomer having 1 to 12 carbon atoms, a (meth) acrylate monomer containing a hydroxy group, and an ethylenically unsaturated monomer.

In one embodiment, the polyhydroxy acrylic resin has 20 to 30 parts by weight of an alkyl (meth) acrylate monomer having 1 to 12 carbon atoms (meth) containing a hydroxy group, based on 100 parts by weight of the monomer composition (total sum of monomers). It may be prepared by mixing 10 to 20 parts by weight of the acrylate monomer and 50 to 70 parts by weight of the ethylenically unsaturated monomer. Preferably, the monomer mixture is copolymerized by solution polymerization, but a polyhydroxy acrylic resin is prepared such that the final solids content is maintained at 80% or more, such as 80 to 85% by weight. If the solid content is less than 80% may cause problems such as uncured by the solvent at room temperature curing of the final flooring material.

The initiator in solution polymerization of the monomer mixture is dibenzoyl peroxide, t-butyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, t-acyl peroxybenzoate, t-amyl peroxy-2 One or more selected from the group consisting of ethylhexanoate, t-butyl peroxyacetate, di-t-butyl peroxide, cumene hydroperoxide and azobis-iso-butylonitrile may be used, but It is not limited. In terms of implementing a high solidification resin (high solid resin), it is advantageous to use liquid initiators such as t-butyl peroxybenzoate, t-butyl peroxyacetate, di-t-butyl peroxide, etc., rather than solid phase initiators. .

As the solvent, one or more selected from toluene, xylene, butyl acetate, and dimethyl carbonate may be used, but is not necessarily limited thereto.

The preparation of polyhydroxy acrylic resin through solution polymerization is generally performed at 100 to 150 ° C.

Examples of the (meth) acrylate monomer containing a hydroxy group include hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl acrylate, hydroxy propyl methacrylate, hydroxy butyl acrylate and hydroxy butyl methacryl. One or more selected from the group consisting of latex, hydroxy pentyl acrylate, hydroxy pentyl methacrylate, hydroxy hexyl acrylate and hydroxy hexyl methacrylate may be used, but is not necessarily limited thereto.

As the ethylenically unsaturated monomer, a compound generally used in the polymerization of acrylic resin can be used without particular limitation. For example, Acrylic ester, such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate; And methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate Methacrylic acid ester, such as these, can be used individually or in mixture of 2 or more types. In terms of implementing a solidifying resin, styrene, 2-ethylhexyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate, t-butyl methacrylate, etc. having complex side chain structures may be used alone or in combination of two or more thereof. It is preferable to use.

The polyhydroxy acrylic resin is preferably prepared so that the weight average molecular weight is 10,000 to 40,000, the viscosity measured by a Gardner bubble viscometer is Z3 to Z5, and the polymerization conversion is 99% or more. When the weight average molecular weight and viscosity are within the above range, the resin is easily handled, and when the polymerization conversion rate is less than 99%, defects in the final coating may occur due to low reactivity monomers.

(B) terminal unsaturated urethane Oligomer

Terminally unsaturated urethane oligomer is one of the reactants for the production of urethane-modified unsaturated acrylic resin of the present invention, by adding a structure in which the urethane bond with flexibility and durability is modified to the final resin to impart elongation and crack resistance that acrylic structure does not have It is a polymer component.

Specifically, the terminal unsaturated urethane oligomer is a polymer of an alkyl (meth) acrylate monomer having 1 to 12 carbon atoms, a monomer containing an isocyanate group, a (meth) acrylate monomer containing a hydroxy group and a polyol containing a hydroxyl group at both terminals. As one, it may have an unsaturated double bond capable of radical addition polymerization at one end.

In one embodiment, the terminal unsaturated urethane oligomer has 65 to 80 parts by weight of an alkyl (meth) acrylate monomer having 1 to 12 carbon atoms, 10 to 20 parts by weight of a monomer containing an isocyanate group, and a hydroxy group based on 100 parts by weight of the monomer composition. It can be prepared by mixing 5 to 15 parts by weight of the containing (meth) acrylate monomer and 2 to 5 parts by weight of a polyol containing a hydroxyl group at both ends.

Preferably, from 0.6 to 0.8 molar equivalents and amounts of (meth) acrylate monomers containing a hydroxy group, relative to 1 molar equivalent of a monomer containing an isocyanate group, using an alkyl (meth) acrylate monomer having 1 to 12 carbon atoms as a solvent. A terminal unsaturated urethane oligomer is prepared such that the final solid content is 20 to 50% (preferably 20 to 30%) by weight by urethane reaction of 0.05 to 0.15 molar equivalents of the polyol containing a hydroxyl group at the end. If too many (meth) acrylate monomers containing hydroxy groups are added out of the above ranges, there is a high possibility of remaining as unreacted substances, and if the polyols containing hydroxy groups at both ends are added out of the above ranges, the final resin will be Isocyanate groups are formed at both ends in the synthesis, which may lead to gelation.

Hydroquinone, hydroquinone monomethylether, mono-t-butylhydroquinone, methylhydroquinone, p-benzoquinone and 2,5-di-t-butyl as polymerization inhibitors in the preparation of terminal unsaturated urethane oligomers via reaction of monomer mixtures At least one selected from the group consisting of hydroquinones may be used, for example, in an amount of 50 to 1,000 ppm. In addition, the terminal unsaturated urethane oligomer production is preferably carried out at 70 ~ 90 ℃. If the reaction temperature is less than 70 ℃ can be a long reaction time, if it exceeds 90 ℃ it may be difficult to track the appropriate NCO%.

As a C1-C12 alkyl (meth) acrylate monomer used as a solvent at the time of manufacture of terminal unsaturated urethane oligomer, Acrylic ester, such as n-butyl acrylate and 2-ethylhexyl acrylate; And methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate Methacrylic acid esters, such as these, can be used individually or in mixture of 2 or more types. Specifically, in application to a flooring material, a monomer having a high glass transition temperature such as methyl methacrylate is used when a high hardness is required, and a glass transition temperature such as n-butyl acrylate or 2-ethylhexyl acrylate when a soft is required. It is preferable to mix and use a low monomer.

In general, since the monomer containing a carboxyl group has the property of promoting the reaction, it is preferable to use an alkyl (meth) acrylate monomer having an acid value in the range of 5 to 10 mgKOH / g. If the acid value is less than 5 mgKOH / g, the reactivity may be lowered and the reaction time may be too long. If the acid value is more than 10 mgKOH / g, the viscosity may be very high due to incompatibility during the subsequent polymerization of unsaturated acrylic resin.

Monomers containing isocyanate groups include monomers containing two isocyanate groups in a molecule such as isophorone diisocyanate, 4,4-dicyclo hexylmethane diisocyanate, 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 2 , 4,4-trimethyl 1,6-hexamethylene diisocyanate, octadecylene diisocyanate, 1,4-cyclohexylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and their One or more types selected from the group consisting of derivatives can be used. Preferably, by using toluene diisocyanate, such as 2,4-toluene diisocyanate, polyhydroxy acrylic resin containing a hydroxyl group and leaving one of the functional groups at both ends of the diisocyanate in the preparation of the unsaturated acrylic resin and May be polymerized. This is because when the reactivity of both ends is the same, the probability of isocyanate group being present at both ends increases, so that the hydroxy group-containing polyhydroxy acrylic resin can be crosslinked to cause gelation of the final resin.

When 2,4-toluene diisocyanate is used, 2,4-toluene diisocyanate is preferably included in an amount of 10 to 20% by weight based on the total weight of the monomer composition. If the content is less than 10% by weight, the toughness of the coating film may be lowered due to the low degree of crosslinking, and when the content is more than 20% by weight, discoloration due to sunlight may be increased.

As the (meth) acrylate monomer containing a hydroxy group, the compounds described in the preparation of the polyhydroxy acrylic resin may be used. Preferably, hydroxy ethyl acrylate or hydroxy ethyl methacrylate is used. This is because a monomer having a simple side chain structure reacts quickly with isocyanate.

As a polyol containing a hydroxyl group at both ends, one or more selected from the group consisting of polypropylene glycol, polyethylene glycol, neopentyl glycol, triethylene glycol, and propylene glycol alginate may be used, but is not necessarily limited thereto. Preferably, by using polypropylene glycol, the elasticity and flexibility of the coating film can be improved. The preferred molecular weight of the polyol containing a hydroxyl group at both ends is 1,000 to 4,000, more preferably 1,000 to 2,000. If the molecular weight is less than 1,000, the coating film properties may be reduced. If the molecular weight is more than 4,000, the oligomer may be precipitated because the oligomer is polymerized under the weak acrylate monomer. Most preferably, polypropylene glycol having a molecular weight of 1,000 to 2,000 is used.

Urethane Modified Unsaturated Acrylic Resin

The urethane-modified unsaturated acrylic resin of the present invention is prepared by urethane reaction of a polyhydroxy acrylic resin and a terminal unsaturated urethane oligomer independently prepared as described above. By providing a modified urethane bond with excellent flexibility and durability to an acrylic resin having excellent weather resistance and water resistance, it is possible to secure weather resistance, water resistance, elongation and crack resistance at the same time. In addition, there is no need for an additional top coat to prevent discoloration. Specifically, when the urethane-modified unsaturated acrylic resin of the present invention is mixed with a reactive diluent and cured, it is possible to provide a floor coating having excellent construction properties, weather resistance, and coating film properties.

In one preferred embodiment, the urethane-modified unsaturated acrylic resin of the present invention contains the polyhydroxy acrylic resin and the terminal unsaturated urethane oligomer prepared in the polyhydroxyacrylic resin relative to the equivalent of isocyanate groups (containing in the terminal unsaturated urethane oligomer), respectively. Can be prepared by mixing and urethane reaction with a hydroxyl group equivalent ratio of 1.0 to 1.5, more preferably 1.2 to 1.5. If the equivalent ratio of hydroxy groups to isocyanate groups is less than 1.0, gelation may proceed due to unreacted (di) isocyanate, and if the equivalent ratio of hydroxy groups to isocyanate groups exceeds 1.5, the uncoated hydroxyl groups will be added to the final coating. It may cause a defect.

Hydroquinone, hydroquinone monomethyl ether, mono-t-butylhydroquinone, methylhydroquinone, p- as polymerization inhibitors in preparing the urethane-modified unsaturated acrylic resin of the present invention through the reaction of a polyhydroxy acrylic resin and a terminal unsaturated urethane oligomer. One or more selected from the group consisting of benzoquinone and 2,5-di-t-butylhydroquinone can be used, for example, in an amount of 50 to 1,000 ppm. In addition, the urethane-modified unsaturated acrylic resin is preferably carried out at 70 ~ 90 ℃. If the reaction temperature is excessively out of the above range, the final unsaturated double bond may be broken to cause gelation of the resin.

Paint composition

According to another aspect of the present invention, there is provided a coating composition comprising the urethane-modified unsaturated acrylic resin of the present invention as described above. The method for preparing the coating composition including the urethane-modified unsaturated acrylic resin of the present invention is not particularly limited, and may be prepared by components, formulations, and methods generally used in the art. For example, in the mill base step, the resin (binder) of the present invention is stirred, a pigment, a dispersant, an antifoaming agent, and the like, and then a catalyst, a reactive diluent, a colorant, and the like are added and stirred in a finishing step, and then a curing agent that enables radical reaction is added. It can manufacture by doing. In addition, if necessary, additives commonly used in the field of radically curable flooring materials such as curing accelerators, preservatives, and leveling agents may be optionally included. In one embodiment, with respect to 100 parts by weight of the urethane-modified unsaturated acrylic resin of the present invention, 0.2 to 1.0 parts by weight of promoter, 0.1 to 0.5 parts by weight of paraffin wax and an appropriate amount of initiator can be mixed to prepare a coating material for flooring have.

The urethane-modified unsaturated acrylic resin of the present invention is particularly useful as a resin for producing exterior flooring materials requiring fast curing properties and high water resistance and weather resistance, such as for automobile roads, bicycle roads, and walking floors.

Hereinafter, the present invention will be described more specifically by way of examples. However, these examples are provided only for the understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.

Example

In order to synthesize a polyhydroxy acrylic resin as an intermediate resin, a thermocouple, a stirrer and a reflux condenser were mounted in a 5 L volume four-necked round flask, and 452 g of toluene was added thereto, and the temperature was raised to a reflux temperature of 112 ° C. At reflux temperature, a mixture of 1132 g of styrene monomer, 414 g of 2-ethylhexyl acrylate, 335 g of hydroxy ethyl acrylate, and 94 g of di-t-butyl peroxide was added dropwise uniformly for 3 hours, and then maintained for 2 hours. Then, a mixture of 38 g of toluene and 19 g of di-t-butyl peroxide was added dropwise for 10 minutes, and then maintained for 3 hours. After the holding reaction, the mixture was cooled to 80 ° C and packaged while filtering with an 80 SUS mesh filter to complete the synthesis of an intermediate resin (polyhydroxy acrylic resin). The weight average molecular weight of the synthesized polyhydroxy acrylic resin was 21540, the Gardner bubble viscosity was Z4, and the polymerization conversion was 99.8%.

Next, in order to synthesize the terminal unsaturated urethane oligomer which is an intermediate resin, the thermocouple, the stirrer, and the reflux machine were attached to the 5-liter four-necked round flask, 1833 g of methyl methacrylates were put therein, and it heated up at 80 degreeC. Subsequently, 437 g of 2,4-toluene diisocyanate was added to the flask using a separate container. Next, a mixture of 377 g of hydroxyethyl acrylate, 0.24 g of hydroquinone and 131 g of polypropylene glycol (molecular weight 1,000) was added to the flask using a separate container. After input, the remaining NCO% was tracked and maintained until the final NCO% was less than 2.5%. When NCO% was 2.5% or less, the mixture was cooled to 50 ° C., diluted with 735 g of methyl methacrylate, and packaged while filtering with an 80 SUS mesh filter to complete the synthesis of an intermediate resin (terminated unsaturated urethane oligomer).

Next, in order to synthesize a urethane-modified unsaturated acrylic resin, a 5-liter four-necked round flask was equipped with a thermocouple, agitator and reflux, and the intermediate resin (terminal unsaturated urethane oligomer) was added at 58.5% by weight based on the total weight and 80 ° C. The temperature was raised to. Subsequently, an intermediate resin (polyhydroxy acrylic resin) was added at 41.5 wt% based on the total weight. After input, the remaining NCO% was tracked and maintained until the final NCO% was less than 0.3%. When the NCO% was 0.3% or less, the mixture was cooled to 50 ° C. and filtered with an 80 SUS mesh filter to complete a urethane-modified unsaturated acrylic resin synthesis.

When the final physical properties of the obtained urethane-modified unsaturated acrylic resin was measured, the solid content was 49.53% by weight, the viscosity was T-U as the Gardner bubble viscosity, and the final NCO% was 0.21%.

Comparative example  One

A 2-liter four-necked round flask was equipped with a thermocouple, a stirrer and a reflux machine, and 501 g of methyl methacrylate was added thereto, and the temperature was raised to 55 to 60 ° C. Subsequently, 402 g of PVC resin CP-450 (Hanhwa Petrochemical Co., Ltd.) was added and stirred until the resin was completely dissolved. When dissolution was completed, a mixture of 268 g of epoxide soya bean oil, 14.9 g of trimethyl propane triacrylate and 1 g of KENREACT KR-55, a PVC stabilizer, was added, cooled to 50 ° C. or lower, and filtered with an 80 SUS mesh filter. The synthesis was completed by packaging.

When the final physical properties of the composite were measured, the solid content was 49.00% and the viscosity was measured from 0 to P as a Gardner bubble viscosity.

Comparative example  2

A 2-liter four-necked round flask was equipped with a thermocouple, a stirrer and a reflux machine, and 1000 g of unsaturated polyester resin CBP-325L (Chembase Co., Ltd.) was added thereto, and the temperature was raised to 40 ° C. Subsequently, 300 g of methyl methacrylate was added thereto, stirred for 30 minutes, and then packaged while filtering with an 80 SUS mesh filter to complete synthesis.

When the final physical properties of the composite were measured, the solid content was 49.55% and the viscosity was measured from J to K as a Gardner bubble viscosity.

Property evaluation test

Using the resins prepared according to Examples and Comparative Examples as a binder, the paint was prepared according to the following steps with the ingredients and the formulations shown in Table 1 below.

First, in the mill base step, the resin, the dispersant, the antifoaming agent, the antisettling agent and the extender pigment were stirred in advance, and stirred for 30 minutes with HSD (high shear dispersion). Next, while stirring at a low speed in the finishing step, the catalyst, the reactive diluent, the colorant and the like were sequentially added and stirred for 10 minutes. After applying 27% benzoyl peroxide as a curing agent in an amount of 4.0% by weight to 100 g of the prepared subject matter, and then stirring at a low speed for 2 minutes, the physical properties such as weather resistance and water resistance were evaluated, and are shown in Table 2 below.

[Table 1] Components and Mixtures of Paints

[Table 2] Property evaluation results

As shown in Table 2, when using the urethane-modified unsaturated acrylic resin of the present invention, while implementing a tensile strength, hardness and elongation equivalent to the case of using a conventional general-purpose unsaturated polyester resin, a solid PVC binder, weather resistance and water resistance It is excellent.

Claims (14)

(A) 20-30 weight part of C1-C12 alkyl (meth) acrylate monomers with respect to 100 weight part of monomer compositions, 10-20 weight part of (meth) acrylate monomers containing a hydroxyl group, and ethylenically unsaturated monomer Polyhydroxy acrylic resin prepared from monomer compositions comprising 50 to 70 parts by weight; And
(B) 65-80 weight part of C1-C12 alkyl (meth) acrylate monomers, 10-20 weight part of monomers containing an isocyanate group, and (meth) acrylate containing a hydroxyl group with respect to 100 weight part of monomer compositions. Terminal unsaturated urethane oligomers prepared from monomer compositions comprising 5 to 15 parts by weight of monomers and 2 to 5 parts by weight of polyols containing hydroxyl groups at both ends;
Urethane-modified unsaturated acrylic resin, characterized in that the urethane reaction. The urethane-modified unsaturated acrylic resin according to claim 1, wherein the polyhydroxy acrylic resin (A) has a weight average molecular weight of 10,000 to 40,000 and a viscosity Z3 to Z5 and a polymerization conversion rate of 99% or more as measured by a Gardner bubble viscometer. The urethane modification according to claim 1, wherein the ethylenically unsaturated monomer is at least one selected from styrene, 2-ethylhexyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate and t-butyl methacrylate. Unsaturated acrylic resins. The monomer of claim 1, wherein the monomer containing an isocyanate group is isophorone diisocyanate, 4,4-dicyclo hexylmethane diisocyanate, 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 2,4,4-trimethyl At least one member selected from the group consisting of 1,6-hexamethylene diisocyanate, octadecylene diisocyanate, 1,4-cyclohexylene diisocyanate, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate Urethane modified unsaturated acrylic resin characterized by the above-mentioned. The polyol having a hydroxyl group at both ends thereof is at least one member selected from the group consisting of polypropylene glycol, polyethylene glycol, neopentyl glycol, triethylene glycol and propylene glycol alginate having a molecular weight of 1,000 to 4,000. Urethane modified unsaturated acrylic resin. a) a polyhydroxy acrylic resin having a solid content of 80% or more by copolymerizing an alkyl (meth) acrylate monomer having 1 to 12 carbon atoms, a (meth) acrylate monomer containing a hydroxy group and an ethylenically unsaturated monomer by solution polymerization method ( Preparing A);
b) 0.6 to 0.8 molar equivalents of a (meth) acrylate monomer containing a hydroxy group relative to 1 molar equivalent of a monomer containing an isocyanate group, independently of this, using an alkyl (meth) acrylate monomer having 1 to 12 carbon atoms as a solvent. And urethane-reacting 0.05 to 0.15 molar equivalents of the polyol containing a hydroxyl group at both ends to prepare a terminal unsaturated urethane oligomer (B) having a solid content of 20 to 50%; And
c) mixing and urethane-reacting each of the prepared polyhydroxy acrylic resins (A) and terminally unsaturated urethane oligomers (B);
Method for producing a urethane-modified unsaturated acrylic resin according to any one of claims 1 to 5, characterized in that it comprises a. The method according to claim 6, wherein the polyhydroxyacrylic resin (A) and the terminal unsaturated urethane oligomer (B) prepared in step c) are mixed with an equivalent ratio of isocyanate groups to a hydroxyl group equivalent ratio of 1.0 to 1.5 to perform a urethane reaction. Method of producing a urethane-modified unsaturated acrylic resin. The method for preparing a urethane-modified unsaturated acrylic resin according to claim 6, wherein step a) is performed at 100 to 150 ° C, and steps b) and c) are performed at 70 to 90 ° C. A coating composition comprising the urethane-modified unsaturated acrylic resin according to any one of claims 1 to 5. The floor coating composition according to claim 9, for automobile roads, bicycle roads or walking. delete delete delete delete