KR20040061167A - 2 component amine curing modified epoxy resin composition and method for preparing the same - Google Patents

Abstract

PURPOSE: A two-pack type amine curing acryl modified epoxy resin composition and its preparation method are provided to improve hardness, impact resistance, pigment dispersion and color stability. CONSTITUTION: The two-pack type amine curing acryl modified epoxy resin composition is obtained by graft polymerizing 10-30 wt% of an acryl monomer to 70-90 wt% of a bisphenol A-type epoxy resin having an epoxy equivalence of 180-240 with an initiator. Preferably the bisphenol A-type epoxy resin is represented by the formula 1, wherein n is 0.5-12. Preferably the graft polymerization is carried out at a temperature of 100-130 deg.C. The obtained resin composition has an acid value less than 1 mg KOH/g, an epoxy value of 2202-260 mg KOH/g, a glass transition temperature of 0-60 deg.C and a number average molecular weight of 440-550.

Description

2-component amine curing modified epoxy resin composition and method for preparing the same

The present invention relates to an acrylic modified epoxy resin composition for producing a high concentration colorant and a method for manufacturing the same. More specifically, a two-component amine cured acrylic modified resin having excellent chemical resistance and color stability, such as corrosion resistance and water resistance, compared to conventional epoxy resins. It relates to an epoxy resin composition and a method for producing the same.

At present, consumers' demands are gradually being advanced and diversified with income increase, and it is also becoming more sophisticated and diversified in the flooring products among the medium-sized products. In particular, the epoxy flooring material which does not contain an organic solvent has been widely used because there is no volatilization of the organic solvent, and it is possible to coat the thick film with an advantage for environmental pollution. It has the disadvantage that a bad color occurs when diluting with non-reactive diluent. If the diluent is not used, the diluent is not bad for the discoloration, but if the worker has a high viscosity of the paint itself or otherwise, the diluent is mixed and used for the purpose of increasing workability. However, as described above, the higher the mixing ratio of the non-reactive diluent, the poorer the color stability, thereby providing a cause of the claims. In addition, the higher the mixing ratio of the diluent provides a cause of failure because the hardness of the coating film occurs.

In the conventional epoxy resin, color stability and paint viscosity were adjusted by adjusting experiments on additives such as dispersing agents in the mixing of paints, but it could satisfy the needs of consumers due to workability and color stability and hardness degradation when mixing diluents. There was no problem.

The first object of the present invention for solving the above problems is to provide a two-component amine cured acrylic modified epoxy resin composition which can improve high hardness, chemical resistance and color stability by graft reaction of acrylic resin to epoxy resin. have.

In addition, a second object of the present invention is to provide a method for producing a two-component amine-curable acrylic modified epoxy resin composition which can improve high hardness, chemical resistance and color stability by graft reacting an acrylic resin to an epoxy resin.

The present invention for achieving the first object is a two-component amine cured acrylic modified epoxy resin obtained from 70 to 90% by weight of bisphenol A epoxy resin having an epoxy equivalent of 180 to 240 and an acrylic monomer and 10 to 30% by weight of an initiator. To provide a composition.

Herein, the two-component amine curable acrylic modified epoxy resin composition has an acid value of less than 1 mgKOH / g, an epoxy value of 220 to 260 mgKOH / g, a glass transition temperature of 0 to 60 ° C, and a number average molecular weight of 440 to 550. It has a phosphorus characteristic value.

In addition, the present invention for achieving the second object provides a bisphenol A epoxy resin having an epoxy equivalent of 220 to 260. Subsequently, graft polymerization of the acrylic monomer to the bisphenol A epoxy resin by adding an acrylic monomer and an initiator 10 to 30% by weight at a uniform rate to 70 to 90% by weight of the bisphenol A epoxy resin. It is to provide a method for producing a liquid amine curable acrylic modified epoxy resin composition.

The two-component amine curable acrylic modified epoxy resin composition of the present invention obtained by the above method is a crosslinking agent resin, which is cured and reacted with an amino resin to provide excellent mechanical properties such as hardness and scratch resistance of the coating film, as well as color stability and It can be applied to thick film type anticorrosive coating which requires dispersibility.

Hereinafter, the present invention will be described in detail.

The two-component amine curable acrylic modified epoxy resin composition corresponding to the present invention is obtained from 70 to 90% by weight of bisphenol A epoxy resin having an epoxy equivalent of 180 to 240, and an acrylic monomer and 10 to 30% by weight of an initiator.

In order to obtain the two-component amine curable acrylic modified epoxy resin composition, a bisphenol A epoxy resin having an epoxy equivalent of 220 to 260, which is known to have excellent chemical performance, is applied. Such a bisphenol A epoxy resin is as shown in the following structural formula (1).

[Formula 1]

In Structural Formula 1, n represents 0.5 to 12.

When the epoxy equivalent of the bisphenol A epoxy resin is less than 220, the hardness of the final coating film is too weak. If the epoxy equivalent is more than 260, the viscosity of the resin composition is so high that a highly viscous paint is produced. Not desirable for sex. Therefore, the epoxy equivalent of the said bisphenol A epoxy resin is 220-260, Preferably it is 240-250.

Specific examples of the bisphenol A epoxy resin having an epoxy equivalent of 220 to 260 are YD-128, YD-011, YD-014, YD-017, and YD-019 (of bisphenol A epoxy resin manufactured by Kukdo Chemical. And bisphenol A epoxy resins manufactured by LG Chemical and Shell Chemical may also be used. Here, YD-series products of Kukdo Chemical Co., Ltd. were used as bisphenol A type epoxy resins applied in the present invention.

In this case, when the amount of the bisphenol A epoxy resin having an epoxy equivalent of 220 to 260 is less than 70% with respect to the solid content of the two-component amine curable acrylic modified epoxy resin composition, chemical performance such as adhesion and chemical resistance may not be sufficient. Therefore, it is not preferable, and when it exceeds 90%, the graft amount of the acrylic monomer is too small, so that the color stability is poor, which is not preferable for dichroism. Therefore, the amount of the bisphenol A epoxy resin is 70 to 90% by weight, preferably 80 to 90% by weight.

In order to form the two-component amine curable acrylic modified epoxy resin composition, an acrylic monomer and an initiator are used, and the amount thereof is 10 to 30% by weight based on the solid content of the two-component amine curable acrylic modified epoxy resin composition.

Here, when the usage-amount of the said acryl monomer and an initiator is less than 10 weight% with respect to solid content of the said two-component amine curable acrylic modified epoxy resin composition, since the graft efficiency of an acryl monomer falls, it is unpreferable and exceeds 30 weight% It is not preferable because the residual initiator and the low molecular acrylic resin composition may adversely affect the cured coating film. Therefore, the usage-amount of the said acrylic monomer and initiator is 10-30 weight%, Preferably it is 1-5 weight%.

As the acrylic monomer, a nonfunctional acrylic monomer, an acrylic monomer having a hydroxy group, an acrylic monomer having a carboxylic acid group, and the like are used, but these may be used alone or in combination of two or more thereof.

Here, the non-functional acrylic monomers include methyl methacrylate, ethyl acrylate, normal-butyl acrylate, 2-ethylnuclear acrylate, normal-butyl methacrylate, and the like. Hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and the like. And the acrylic monomer which has the said carboxylic acid group contains acrylic acid and methacrylic acid. At least 1 sort (s) or Preferably it can mix and use suitably. These can be used individually or in mixture of 2 or more types.

In addition, the initiator is used 1 to 10% by weight based on 100% by weight of the acrylic monomer. At this time, if the amount of the initiator is less than 1%, the amount of the initiator is less than that of the acrylic monomer, so the efficiency of the graft polymerization is lowered, which is not preferable, and the two-component type obtained when the amount of the initiator exceeds 10% is used. Since the initiator remains in the amine-curable acryl-modified epoxy resin composition, the final cured coating film is affected, which is not preferable. Therefore, the amount of the initiator to the acrylic monomer is 1 to 10% by weight, preferably 1 to 5% by weight.

As the initiator used in the present invention, peroxide-based benzoyl peroxide, tertiary butyl peroxy benzoate, tertiary butyl peroxy 2-ethyl hexanate and azo azobisisobutyronitrile may be used.

When the azo-based azobisisobutyronitrile is used to form the two-component amine-curable epoxy resin composition of the present invention, the graft polymerization efficiency of the acrylic monomer with respect to the bisferol-type epoxy resin is inferior to that of the acrylic homopolymer. Since only a mixture is produced, it is not preferable. Moreover, the compatibility of epoxy and an acrylic homopolymer is not good, and the said resin composition becomes turbid.

That is, when the influence of the initiator azobis isobutyronitrile is specifically shown, the acryl monomer is graft polymerization reaction by resonance stabilization of 2-cyano-2-propyl radicals generated from the azobis isobutyronitrile. Suppress your participation in Therefore, in the present invention, it is preferable to use peroxide-based benzoyl peroxide (Benzoyl peroxide) capable of obtaining a graft copolymer having a relatively high yield as an initiator for advancing the graft polymerization reaction of an acrylic monomer.

In addition, after preparing a bisphenol A epoxy resin having an epoxy equivalent of 220 to 260, the following structural formula 1, 10 to 30% by weight of a reaction additive including an acrylic monomer and an initiator in 70 to 90% by weight of the bisphenol A epoxy resin is uniform. A two-component amine curable acrylic modified epoxy resin composition was obtained by graft polymerization of the acrylic monomer to the bisphenol A epoxy resin at a rate. Subsequently, an initiator is further added to completely graft polymerize the acrylic monomers remaining in the two-component amine curable acrylic modified epoxy resin composition. In the following [Formula 1] n represents 0.5 to 12.

[Formula 1]

The two-component amine cured acrylic modified epoxy resin composition obtained by the above method has a glass transition temperature of 0 to 60 ° C, an epoxy value of 220 to 260 mg KOH / g, a number average molecular weight of 440 to 550, and an acid value. Has a characteristic of less than 1 mg KOH / g, the coating film formed of the composition is excellent in physical performance, such as hardness and scratch resistance, and chemical performance such as corrosion resistance, water resistance, alkali resistance.

Here, when the glass transition temperature of the two-component amine curable acrylic modified epoxy resin composition is less than 0 ° C., physical properties such as hardness and scratch resistance of the cured coating film are not preferable, and thus, they are not preferable. In this case, the physical properties are improved, but the adhesion of the cured coating film is poor, and not only the chemical performance such as water resistance is lowered, but also the interlayer adhesion between the top and bottom is poor. Therefore, the glass transition temperature of the two-component amine curable acrylic modified epoxy resin composition is 0 to 60 ° C, preferably 40 to 50 ° C.

If the epoxy of the two-component amine curable acrylic modified epoxy resin composition is less than 220 mg KOH / g, the crosslinking density of the cured coating film is low, and thus the physical performance such as hardness and impact resistance and chemical resistance of water resistance cannot be sufficiently exhibited. In addition, when the epoxy value of the said composition exceeds 260 mg KOH / g, since the graft polymerization amount of an acrylic monomer becomes small and color stability becomes poor, it is unpreferable. Therefore, the epoxy value of the two-component amine curable acrylic modified epoxy resin composition is 220 to 260 mg KOH / g, preferably 240 to 250 mg KOH / g.

If the number average molecular weight of the two-component amine curable acrylic modified epoxy resin composition is less than 440, the graft polymerization ratio of the acrylic monomer of the cured coating film is lowered and color stability becomes poor, and the number average molecular weight of the composition is 550. If it is above, since the density of an epoxy functional group is low, workability defects due to the hardness fall phenomenon and the viscosity increase of a cured coating film generate | occur | produce, it is unpreferable. Therefore, the number average molecular weight of the two-component amine curable acrylic modified epoxy resin composition is 440 to 550, preferably 480 to 500.

In addition, when the acid value of the two-component amine curable acrylic modified epoxy resin composition is 1 mg KOH / g or more, the curing reactivity of the oxirane ring of the bisphenol A epoxy resin and the crosslinking agent may be poor, and thus sufficient performance may not be exhibited. It is not preferable because hardness also becomes poor. Therefore, it is preferable that the acid value of the said two-component amine curable acrylic modified epoxy resin composition is less than 1 mg KOH / g.

The composition obtained with the above characteristics is excellent in physical performances such as hardness and impact resistance, pigment dispersibility and color stability compared to conventional epoxy resins, and in the production of thicker colorants and thick coats which require particularly excellent color stability. It can be used easily also on the subject of a type | mold solventless epoxy resin.

Hereinafter, a two-component amine-curable acrylic modified epoxy resin composition and a method for preparing the same of the present invention will be described in more detail with reference to the following examples.

Example 1

To apply the composition of the material described in Table 1 to prepare a two-component amine cured acrylic modified epoxy resin composition of the present invention.

ingredient Weight (g) Bisphenol A epoxy resin YD-128 ^{(Note 1)} 225 Mixed additives Styrenemethyl methacrylate 2-acrylate 2-hydroxyethyl methacrylate 2-ethylhexyl acrylate benzoyl peroxide 1044130.6

Note 1) YD-128 (trade name): Bisphenol A type epoxy resin (manufactured by Kukdo Chemical Co., Ltd.) having an epoxy equivalent of 180 to 240.

225 g of YD-128 ^{(Note 1) was} added to a flask equipped with a thermometer, a condenser, and a stirrer, and the temperature was increased to about 120 ° C. Subsequently, the mixture was added dropwise at a uniform rate to the flask in which the mixed additive YD-128 ^{(Note 1)} was present for about 1 hour to carry out the graft polymerization reaction. Subsequently, in order to completely react the acrylic monomer remaining in the flask, after 1 hour, 0.1 g of the benzoyl peroxide was added to the flask, and further maintained for 2 hours, followed by cooling to obtain a two-component amine curable acrylic modified epoxy resin composition. It was.

The two-component amine cured acrylic modified epoxy resin composition thus obtained has an acid value of 0.3 mgKOH / g, a Gardner viscosity (25 ° C) of Z 5, a number average molecular weight of 500, a weight average molecular weight of 1500, and a solid content of the resin composition. Having a characteristic value of 242 mgKOH / g epoxy.

Example 2

A mixed additive comprising 10 g of styrene, 4 g of methyl methacrylate, 4 g of methacrylic acid, 1 g of 2-hydroxyethyl methacrylate, 3 g of 2-ethylhexyl acrylate, and 0.6 g of benzoyl peroxide in the same manner as in Example 1 Instead of using 225 g of YD-128 ^{(Note 1)} , a mixed additive containing 4 g of methyl methacrylate, 6 g of 2-ethylhexyl acrylate, and 0.3 g of benzoyl peroxide and 100 g of YD-115CA ^{(Note 2)} were used. To obtain a two-component amine cured acrylic modified epoxy resin composition.

The two-component amine curable acrylic modified epoxy resin composition thus obtained has an acid value of 0.1 mg KOH / g, an epoxy value of 248 mg KOH / g, a Gardner viscosity (25 ° C.) of Y, and a solid content of the resin composition. The number average molecular weight is 450 and the weight average molecular weight is 1400.

Note 2) YD-115CA is epoxy resin of Kukdo Chemical.

Example 3

Performed in the same manner as in Example 1, but mixed with 10 g of styrene, 4 g of methyl methacrylate, 4 g of methacrylic acid, 1 g of 2-hydroxyethyl methacrylate, 3 g of 2-ethylhexyl acrylate, and 0.6 g of benzoyl peroxide Instead of using additives and 225 g of YD-128 ^{(Note 1)} , a mixed additive containing 2 g of methyl methacrylate, 5 g of methacrylic acid, 3 g of butyl acrylate, and 0.3 g of benzoyl peroxide, and 100 g of YD-115CA ^{(Note 2)} A two-component amine curable acrylic modified epoxy resin composition was obtained.

The two-component amine-curable acrylic modified epoxy resin composition thus obtained has an acid value of 0.5 mg KOH / g, a epoxy value of 238 mg KOH / g, a Gardner viscosity (25 ° C) of X, and a solid content of the resin composition. The number average molecular weight is 470 and the weight average molecular weight has a characteristic value of 1500.

Comparative Example 1

YD-128 ^{(Note 1)} was prepared as an epoxy resin.

Comparative Example 2

YD-115CA ^{(Note 2)} was prepared as an epoxy resin.

Experimental Example 1

15 g of ethylenediamine, an amino resin, is added to g corresponding to the epoxy equivalent of each of the epoxy resins disclosed in Examples 1-3 and Comparative Examples 1-2 of the present invention as a crosslinker resin, and then 10 g of triethylamine is diluted. Prepared. The paint thus prepared was applied to a slate plate and left to dry for about 24 hours at room temperature to form a coating film as a test specimen. The hardness of the coating film was tested and evaluated according to ASTM D 2240 (hardness measurement method defined by the American Society for Testing and Materials), and the color stability was tilted on a slate plate (about 15 degrees) to form a coating film. It was evaluated as to whether or not color separation occurred after formation. The test results are shown in Table 2 below.

Coating film performance evaluation test result of an Example and a comparative example Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Hardness 85 83 83 83 81 Color stability ◎ ◎ ○ ○ ○ Butyl cellosolve ^{Note 3} Color stability when diluted 3% ◎ ◎ ○ ○ △ Butyl Cellosolve Color stability when diluted 6% ◎ ○ ○ × × Butyl Cellosolve Color stability when diluted 9% ○ △ △ × ×

Note 3) Butyl cellosolve: Ethylene glycol monobutyl ether, a diluting solvent.

(Evaluation criteria; ◎: excellent, ○: good, △: normal, ×: poor)

As can be seen in Table 2, the acrylic modified epoxy resin composition of Example 1 has the same or superior hardness as that of the epoxy resins of Comparative Examples 1 and 2, in particular, in color stability and color stability when diluting butyl cellosolve. It was also very good.

As described above, the two-component amine-curable acrylic modified epoxy resin composition according to the present invention has excellent physical properties such as hardness and the like, as compared with conventional epoxy resins, and greatly improves performance such as color stability. In addition, the acrylic modified epoxy resin composition of the present invention can be easily used as a subject resin of the thick film type solvent-free epoxy paint that requires particularly excellent color stability and high hardness.

Although described above with reference to a preferred embodiment of the present invention, those skilled in the art will be variously modified and changed within the scope of the invention without departing from the spirit and scope of the invention described in the claims below I can understand that you can.

Claims (11)

A two-component amine cured acrylic modified epoxy resin composition obtained from 70 to 90% by weight of a bisphenol A epoxy resin having an epoxy equivalent of 180 to 240, and an acrylic monomer and 10 to 30% by weight of an initiator. The two-component amine curable acrylic modified epoxy resin composition according to claim 1, wherein the bisphenol A epoxy resin is represented by the following Structural Formula (1), wherein n is 0.5 to 12. [Formula 1] The method of claim 1, wherein the acrylic monomer is methyl methacrylate, ethyl acrylate, normal-butyl acrylate, 2-ethylnuclear acrylate, normal-butyl methacrylate, 2-hydroxyethyl methacrylate, 2- Two-component amine curable acrylic modified epoxy, characterized in that it comprises at least one of the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, acrylic acid and methacrylic acid Resin composition. The two-component amine curable acrylic modified epoxy resin composition according to claim 1, wherein the initiator uses a peroxide-based initiator, and the amount of the initiator is 1 to 10% by weight based on 100% by weight of the acrylic monomer. According to claim 1, The obtained product is a two-component amine curable acrylic modified epoxy resin composition, the properties of the acid value is less than 1 mgKOH / g, epoxy value of 220 to 260 mgKOH / g, the glass transition temperature is 0 A two-component amine cured acrylic modified epoxy resin composition, characterized in that the number average molecular weight is 440 to 550 to 60 ℃. Preparing a bisphenol A epoxy resin having an epoxy equivalent of 220 to 260; And Graft polymerization of the acrylic monomer to the bisphenol A-type epoxy resin by injecting the acrylic monomer and 10 to 30% by weight of the initiator at a uniform rate to 70 to 90% by weight of the bisphenol A-type epoxy resin Method for producing an amine cured acrylic modified epoxy resin composition. The method of claim 6, wherein the bisphenol A epoxy resin is represented by the following Structural Formula (1), and n is 0.5 to 12 in the Structural Formula. [Formula 1] The method of claim 6, wherein the acrylic monomer is methyl methacrylate, ethyl acrylate, normal-butyl acrylate, 2-ethylnuclear acrylate, normal-butyl methacrylate, 2-hydroxyethyl methacrylate, 2- Two-component amine curable acrylic modified epoxy, characterized in that it comprises at least one of the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, acrylic acid and methacrylic acid Method for producing a resin composition. The method of claim 6, wherein the graft polymerization is performed at 100 to 130 ° C. 7. The method of claim 6, wherein after the graft polymerization, an initiator is further added to react both of the unreacted acrylic monomers with the bisphenol A-type epoxy. Way. The obtained product is a two-component amine cured acrylic modified epoxy resin composition, the acid value is less than 1 mgKOH / g, the epoxy value is 220 to 260 mgKOH / g, the glass transition temperature is It is 0-60 degreeC, and number average molecular weights are 440-550, The manufacturing method of the 2-component amine hardening type acrylic modified epoxy resin composition characterized by the above-mentioned.