KR20220074322A - Alkid emulsion with reactive self-emulsifier - Google Patents

Abstract

The present invention relates to an alkyd resin to which a reactive self-emulsifying agent is applied and an alkyd emulsion containing the same, wherein the self-emulsifying agent-applied alkyd emulsion resin of the present invention is an emulsifier used in preparing an alkyd emulsion by reacting a self-reactive emulsifier with the alkyd resin backbone. The amount can be significantly reduced, and at the same time, the coating film performance of the resin backbone can be improved. In addition, the reactive self-emulsifying agent-applied alkyd emulsion resin according to the present invention can prevent deterioration of the performance of the resin backbone while having excellent emulsion stability, thereby facilitating the production of an alkyd emulsion resin suitable for performance.

Description

Alkyd emulsion with reactive self-emulsifier {ALKID EMULSION WITH REACTIVE SELF-EMULSIFIER}

The present invention relates to an alkyd resin and an alkyd emulsion, and more particularly, to an alkyd resin to which a reactive self-emulsifying agent is applied, and an alkyd emulsion comprising the same.

Alkyd resins containing polybasic acids, polyols, and fatty acids are widely used resins in coating and paint industries. The traditional method of preparing alkyd emulsions is to emulsify the alkyd resin through an emulsifier.

In this regard, Korean Patent Application Laid-Open No. 10-2014-0099192 relates to an alkyd surfactant for preparing a stable alkyd emulsion, at least one monomer including a hydrophilic group, at least one ethylenically unsaturated fatty acid or ester, and optionally, at least at least An alkyd surfactant formed by copolymerization of one polyol is presented.

However, single use of the emulsifier reduces price competitiveness due to an increase in the amount of the emulsifier used, and at the same time has a problem in that it may adversely affect the coating film due to the defects of the emulsifier itself.

Accordingly, as another method for preparing an alkyd emulsion, there has been research and development on a method for dispersing the alkyd resin by introducing a hydrophilic substituent.

In this regard, Korea Patent No. 10-1904776 relates to a self-emulsifying polyurethane alkyd emulsion resin containing an ethylene oxide group that enables emulsification in the main chain, and a compound having an isocyanate group is added to the alkyd resin to induce a urethane reaction. Thus, after forming a polyurethane alkyd resin, it is dispersed in water to prepare an alkyd emulsion resin.

However, the water-soluble alkyd resin using a hydrophilic substituent also has a problem in that the hydrophilic substituent acts as a weak ring in the resin structure and acts as a cause of weakening the final coating film properties.

Therefore, it is required to develop an alkyd emulsion that has excellent emulsion stability and does not deteriorate the performance of the resin backbone.

Korean Patent Publication No. 10-2014-0099192 (published on August 11, 2014) Korean Patent Registration No. 10-1904776 (Registered on September 28, 2018)

The reactive self-emulsifying agent of the present invention has been devised to solve the above problems, and an object of the present invention is to provide a reactive self-emulsifying agent represented by the following formula (1).

[Formula 1]

In Formula 1, R ^a is methyl or ethyl, and m:n is 1:1 to 10:1.

Another object of the present invention is to provide an alkyd resin to which the reactive self-emulsifying agent of the present invention is introduced.

Another object of the present invention is to provide a reactive self-emulsifying agent applied alkyd emulsion resin comprising 100 parts by weight of a reactive self-emulsifying agent applied alkyd resin and 1 to 20 parts by weight of an emulsifier to which the reactive self-emulsifying agent of the present invention is introduced. .

The present invention may also have the object of achieving these objects and other objects that can be easily derived by a person skilled in the art from the general description of the present specification in addition to the above clear objects.

The reactive self-emulsifying agent of the present invention in order to achieve the above object,

It is characterized in that it is represented by the following formula (1).

[Formula 1]

In Formula 1, R ^a is methyl or ethyl, and m:n is 1:1 to 10:1.

And, m:n may be 2:1 to 7:1 or 3:1 to 5:1.

In addition, the number average molecular weight of the reactive self-emulsifying agent may be 500 to 5000, 700 to 3000, or 1000 to 2000.

In addition, the reactive self-emulsifying agent may be prepared by reacting an ethylene oxide/propylene oxide copolymer with trimellitic anhydride.

And, the copolymer may include a methoxy group or an ethoxy group at the terminal.

In addition, the reactive self-emulsifying agent is mixed with 100 parts by weight of an ethylene oxide/propylene oxide copolymer including a methoxy group at the terminal and 1 to 20 parts by weight, 5 to 15 parts by weight, or 8 to 12 parts by weight of the trimellitic anhydride. can be manufactured.

And, the reaction may be carried out at 120 to 180 ℃, 130 to 160 ℃, or 140 to 160 ℃.

Meanwhile, the reactive self-emulsifying agent applied alkyd resin according to the present invention is characterized in that the reactive self-emulsifying agent represented by the following formula (1) is introduced into the alkyd resin.

[Formula 1]

In Formula 1, R ^a is methyl or ethyl, and m:n is 1:1 to 10:1.

And, m:n may be 2:1 to 7:1 or 3:1 to 5:1.

In addition, the alkyd resin may be a resin formed through polymerization of fatty acids, phthalic anhydride, glycerin, and pentaerythritol.

And, the fatty acid may be soybean fatty acid.

In addition, the reactive self-emulsifying agent applied alkyd resin may be represented by the following formula (2).

[Formula 2]

In Formula 2,

Wherein R ¹ is a saturated or unsaturated hydrocarbon having 1 to 30 carbon atoms,

wherein A is the reactive self-emulsifying agent,

wherein p is 1 to 30.

And, R ¹ may be a saturated or unsaturated hydrocarbon having 1 to 24 carbon atoms, or 1 to 20 carbon atoms.

And, p may be 1 to 24, or 1 to 20.

In addition, the reactive self-emulsifying agent applied alkyd resin may be formed through the reaction of a carboxyl group of the reactive self-emulsifying agent with a functional group of the alkyd resin backbone.

And, the functional group of the alkyd resin backbone may be a hydroxyl group.

In addition, the number average molecular weight of the reactive self-emulsifying agent applied alkyd resin may be 10000 to 40000, 14000 to 32000, or 20000 to 25000.

And, the reactive self-emulsifying agent applied alkyd resin,

100 parts by weight of the reactive self-emulsifier,

1 to 20 parts by weight, 5 to 18 parts by weight, or 10 to 16 parts by weight of glycerin;

30 to 70 parts by weight, 40 to 60 parts by weight, or 45 to 55 parts by weight of pentaerythritol;

50 to 100 parts by weight, 60 to 90 parts by weight, or 70 to 80 parts by weight of phthalic anhydride;

5 to 30 parts by weight, 10 to 25 parts by weight, or 12 to 20 parts by weight of benzoic acid; and

1 to 20 parts by weight, 3 to 16 parts by weight, or 5 to 10 parts by weight of xylene; It can be prepared by mixing at least one of them.

In addition, the reactive self-emulsifying agent applied alkyd resin may be prepared at 140 to 380 °C, 160 to 300 °C, or 180 to 240 °C.

On the other hand, the reactive self-emulsifying agent applied alkyd emulsion resin according to the present invention contains 100 parts by weight of the reactive self-emulsifying agent applied alkyd resin to which the reactive self-emulsifying agent represented by the following formula (1) is introduced, and 1 to 20 parts by weight of the emulsifier. .

[Formula 1]

In Formula 1, R ^a is methyl or ethyl, and m:n is 1:1 to 10:1.

And, 2 to 10 parts by weight, or 4 to 8 parts by weight of the emulsifier may be included.

And, the emulsifier may include two or more emulsifiers.

In addition, the emulsifier may include an alkylaryl sulphonate (Alkylaryl sulphonate).

In addition, the reactive self-emulsifying agent applied alkyd emulsion resin,

mixing 100 parts by weight of the alkyd resin to which the reactive self-emulsifying agent is introduced, and 1 to 20 parts by weight, 2 to 10 parts by weight, or 4 to 8 parts by weight of an emulsifier; and

It can be prepared by a manufacturing method comprising a; dropwise dispersion of deionized water to emulsify.

The dropwise dispersion of the deionized water may be performed for 2 to 6 hours, 3 to 5 hours, and 3.5 to 4.5 hours.

In addition, the dropwise dispersion of deionized water may be 50 to 200 parts by weight, 70 to 150 parts by weight, or 80 to 12 parts by weight based on 100 parts by weight of the alkyd resin to which the reactive self-emulsifying agent is introduced.

And, further comprising the step of stirring after dumping deionized water before the emulsification step, wherein the stirring is at 40 to 80 ℃, 45 to 75 ℃, or 50 to 70 ℃, 5 to 40 minutes, 10 to 30 minutes, For 15 to 25 minutes, 500 to 1100 rpm, 600 to 1000 rpm, or 700 to 900 rpm.

The amount of the dumped deionized water may be 1 to 20 parts by weight, 5 to 15 parts by weight, or 8 to 12 parts by weight based on 100 parts by weight of the alkyd resin to which the reactive self-emulsifying agent is introduced.

In addition, the average particle diameter of the reactive self-emulsifying agent applied alkyd emulsion resin may be 300 to 800 nm, 400 to 700 nm, or 500 to 600 nm.

In addition, the nonvolatile content of the reactive self-emulsifying agent applied alkyd emulsion resin may be 35 to 70%, 40 to 60%, or 45 to 55%.

The present invention can help emulsify a polymer alkyd resin having relatively excellent properties by applying a reactive self-emulsifying agent to the alkyd resin to reduce the amount of emulsifier used and to facilitate the production of an alkyd emulsion resin suitable for performance.

The reactive self-emulsifying agent applied alkyd emulsion resin according to the present invention has excellent emulsion stability and can prevent deterioration of the resin backbone performance.

The self-emulsifier-applied alkyd emulsion resin of the present invention can significantly reduce the amount of emulsifier used in manufacturing the alkyd emulsion by reacting the self-reacting emulsifier with the alkyd resin backbone, and at the same time can improve the coating film performance of the resin backbone.

Hereinafter, preferred embodiments of the present invention will be described in detail.

However, the present invention is not limited to the specific exemplary embodiments, since the following is merely a detailed description by exemplifying specific embodiments, and since the present invention may be variously changed and may have various forms. It should be understood that the present invention includes all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

In addition, in the following description, many specific details such as specific components are described, which are provided to help a more general understanding of the present invention, and it is common in the art that the present invention can be practiced without these specific details. It will be self-evident to those who have the knowledge of And, in describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

And, the terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. Unless defined otherwise, all terms used herein, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

In this application, the singular expression includes the plural expression unless the context clearly dictates otherwise.

In the present application, terms such as 'comprise', 'contain' or 'have' are intended to refer to the presence of a feature, component (or component), etc. described in the specification, but one or more other features or It does not mean that the component or the like is not present or cannot be added.

The reactive self-emulsifying agent of the present invention is characterized in that it is represented by the following formula (1).

In Formula 1, R ^a may be methyl or ethyl, and m:n may be 1:1 to 10:1, 2:1 to 7:1, or 3:1 to 5:1. m:n is a ratio of polyoxyethylene and polyoxypropylene, and when m and n are within the above range, emulsion stability is excellent, and when it is out of the above range, a problem of poor stability occurs.

The reactive self-emulsifying agent of the present invention, which can be represented by Formula 1, reacts polyethylene glycol/polypropylene glycol with polybasic acid to finally form an acid-functional intermediate and reacts with the alkyd backbone to assist in the emulsification of the resin.

The number average molecular weight of the reactive self-emulsifying agent may be 500 to 5000, 700 to 3000, or 1000 to 2000. If the number average molecular weight is less than the above range, it may affect the reactive groups of the entire resin and affect the functional group portion of the backbone of the resin. If the number average molecular weight exceeds the above range, emulsion stability may be reduced.

In addition, the reactive self-emulsifying agent may be prepared by reacting trimellitic anhydride with an ethylene oxide/propylene oxide copolymer containing an alkoxy group such as an ethoxy group or a methoxy group at the terminal, preferably a methoxy group. The ethylene oxide/propylene oxide copolymer may be a block copolymer or a random copolymer.

In addition, the reactive self-emulsifying agent is mixed with 100 parts by weight of an ethylene oxide/propylene oxide copolymer including a methoxy group at the terminal and 1 to 20 parts by weight, 5 to 15 parts by weight, or 8 to 12 parts by weight of the trimellitic anhydride. can be manufactured.

And, the reaction may be carried out at 120 to 180 ℃, 130 to 160 ℃, or 140 to 160 ℃.

The reactive self-emulsifying agent represented by Formula 1 has one or more, or two or more carboxyl groups to have a reaction site capable of reacting with the alkyd resin.

On the other hand, the reactive self-emulsifying agent applied alkyd resin according to the present invention is characterized in that a reactive self-emulsifying agent represented by the following formula (1) is introduced.

[Formula 1]

In Formula 1, R ^a may be methyl or ethyl, and m:n may be 1:1 to 10:1, 2:1 to 7:1, or 3:1 to 5:1. In addition, the methoxy group of Formula 1 may be replaced with an alkoxy group such as an ethoxy group.

Alkyd resin is one of the resins mainly used in paints, and is produced by the esterification reaction of fatty acids, polyhydric alcohols, and polybasic acids. As an emulsifier introduced, it is characterized in that a reactive self-emulsifying agent is grafted onto the backbone of an alkyd resin.

In the present invention, the alkyd resin may be a resin formed through polymerization of fatty acids, phthalic anhydride, glycerin, and pentaerythritol. The alkyd resin thus formed has a plurality of hydroxyl groups.

Specifically, as an embodiment of the present invention, the reactive self-emulsifying agent applied alkyd resin may be represented by the following formula (2).

In Formula 2, R ¹ is a saturated or unsaturated hydrocarbon having 1 to 30, 1 to 24, or 1 to 20 carbon atoms, A is the reactive self-emulsifying agent or a derivative derived therefrom, and p is 1 to 30 , 1 to 24, or 1 to 20. And, R ¹ may be preferably an unsaturated hydrocarbon.

The aspect in which the alkyd resin and the reactive self-emulsifier of the present invention are grafted can be confirmed through Formula 2 above. Specifically, the reactive self-emulsifying agent applied alkyd resin may be formed through the reaction of a carboxyl group present in the reactive self-emulsifying agent of the present invention and a functional group present on the backbone of the alkyd resin. The functional group present on the backbone of the alkyd resin may be a functional group including oxygen. In addition, it is preferable that the hydroxyl group of the alkyd resin reacts with the carboxyl group of the reactive self-emulsifier to bond.

In particular, the alkyd resin of the present invention has a large amount of hydroxyl groups by including pentaerythritol as a monomer. Grafting to alkyd resins is advantageous.

In addition, the number average molecular weight of the reactive self-emulsifying agent applied alkyd resin may be 10000 to 40000, 14000 to 32000, or 20000 to 25000. If the number average molecular weight is less than the above range, mechanical and chemical properties of the coating film may be reduced, and if the number average molecular weight is greater than the range, emulsion stability may be deteriorated.

And, the reactive self-emulsifying agent applied alkyd resin, 100 parts by weight of the reactive self-emulsifying agent, 1 to 20 parts by weight, 5 to 18 parts by weight, or 10 to 16 parts by weight of glycerin; 30 to 70 parts by weight, 40 to 60 parts by weight, or 45 to 55 parts by weight of pentaerythritol; 50 to 100 parts by weight, 60 to 90 parts by weight, or 70 to 80 parts by weight of phthalic anhydride; 5 to 30 parts by weight, 10 to 25 parts by weight, or 12 to 20 parts by weight of benzoic acid; and 1 to 20 parts by weight, 3 to 16 parts by weight, or 5 to 10 parts by weight of xylene; It can be prepared by mixing at least one of them.

In the preparation of the reactive self-emulsifying agent applied alkyd resin, the molecular weight can be controlled and gelation can be prevented by adding the benzoic acid.

In addition, the reactive self-emulsifying agent applied alkyd resin may be prepared at 140 to 380 °C, 160 to 300 °C, or 180 to 240 °C.

On the other hand, the reactive self-emulsifying agent applied alkyd emulsion resin according to the present invention is 100 parts by weight of the reactive self-emulsifying agent applied alkyd resin to which the reactive self-emulsifying agent represented by the following formula (1) is introduced, and 1 to 20 parts by weight, 2 to 10 parts by weight of the emulsifier , or 4 to 8 parts by weight. If the emulsifier content is less than the above range, the emulsion stability may be deteriorated, and if it exceeds the range, the mechanical and chemical properties of the coating film may be deteriorated.

[Formula 1]

In Formula 1, R ^a may be methyl or ethyl, and m:n may be 1:1 to 10:1, 2:1 to 7:1, or 3:1 to 5:1.

The emulsifier may include one type of emulsifier or two or more emulsifiers, and the emulsifier may include an alkylaryl sulphonate-based emulsifier.

In addition, the reactive self-emulsifying agent applied alkyd emulsion resin is prepared by mixing 100 parts by weight of the alkyd resin to which the reactive self-emulsifying agent is introduced, and 1 to 20 parts by weight, 2 to 10 parts by weight, or 4 to 8 parts by weight of the emulsifier; and dropwise dispersing and emulsifying deionized water.

In the emulsification step, dropwise dispersion of deionized water may be performed for 2 to 6 hours, 3 to 5 hours, and 3.5 to 4.5 hours, and the dropwise dispersion of deionized water is 100 weight of the alkyd resin to which the reactive self-emulsifying agent is introduced. It may be 50 to 200 parts by weight, 70 to 150 parts by weight, or 80 to 12 parts by weight based on parts.

And, after the step of mixing the alkyd resin and the emulsifier, before the emulsification step, dumping deionized water and stirring further comprises the step of stirring, wherein the stirring is at 40 to 80 ° C, 45 to 75 ° C, or 50 to 70 ° C, 5 to 40 minutes, 10 to 30 minutes, 15 to 25 minutes, 500 to 1100 rpm, 600 to 1000 rpm, or 700 to 900 rpm.

The amount of the dumped deionized water may be 1 to 20 parts by weight, 5 to 15 parts by weight, or 8 to 12 parts by weight based on 100 parts by weight of the alkyd resin to which the reactive self-emulsifying agent is introduced.

The average particle diameter of the reactive self-emulsifying agent applied alkyd emulsion resin according to the present invention may be 300 to 800 nm, 400 to 700 nm, or 500 to 600 nm.

The nonvolatile content of the reactive self-emulsifying agent applied alkyd emulsion resin according to the present invention may be 35 to 70%, 40 to 60%, or 45 to 55%.

Hereinafter, an embodiment of the present invention will be described.

[Example]

Example 1: Emulsifier Synthesis

In a 2-liter 4-neck flask equipped with a thermometer, condenser, and stirrer, 350 g of MPEG2000 (Hannong-Hwaseong) and 34 g of trimellitic anhydride were added, and the temperature was gradually raised to 150 ℃, and the acid value was 50 - 53 at the same temperature. A self-reactive emulsifier was synthesized by reacting as much as possible.

Example 2: Alkyd Resin Synthesis

400 g of soybean fatty acid (mono acid), 54 g of glycerin, 205 g of pentaerythritol, 300 g of phthalic anhydride, and benzoic acid in the emulsifier prepared in Example 1 acid) 60 g and xylene 30 g, reacted at 220 ° C., and the reaction was terminated at an acid value of 11-15 and Gardner viscosity V (50% in xylene) to prepare an alkyd resin with an average molecular weight of 20000 to 25000.

Example 3: Alkyd Emulsion Synthesis

400 g of the alkyd resin prepared in Example 2 was put into a 1 liter high-speed stirring device equipped with a thermometer, a condenser, and a stirrer, and 12 g of croda's M7201 emulsifier and 12 g of M7101 emulsifier were added at 70 ° C. After dumping 40 g of ionized water, the mixture was stirred for 20 minutes. An alkyd emulsion resin having an average particle size of 550 nm and a nonvolatile content of 51% was obtained by emulsifying by dropwise dispersing 400 g of deionized water at 60° C. while stirring at high speed (800 rpm) for 4 hours.

In the above, preferred embodiments of the present invention have been described, but the present invention is not limited to the specific embodiments described above, and those skilled in the art can implement various modifications without departing from the gist of the present invention. Of course it is possible. Accordingly, the scope of the present invention should not be construed as limited to the above embodiments, and should be defined by the claims described below as well as the claims and equivalents.

Claims (13)

A reactive self-emulsifying agent represented by the following formula (1):
[Formula 1]

In Formula 1, R ^a is methyl or ethyl, and m:n is 1:1 to 10:1. The method according to claim 1,
The reactive self-emulsifier has a number average molecular weight of 500 to 5000, 700 to 3000, or 1000 to 2000. The method according to claim 1,
The reactive self-emulsifier, characterized in that it is prepared through the reaction of an ethylene oxide / propylene oxide copolymer and trimellitic anhydride, a reactive self-emulsifier. A reactive self-emulsifying agent applied alkyd resin in which a reactive self-emulsifying agent represented by the following formula (1) is introduced into an alkyd resin:
[Formula 1]

In Formula 1, R ^a is methyl or ethyl, and m:n is 1:1 to 10:1. 5. The method according to claim 4,
The alkyd resin is a reactive self-emulsifying agent applied alkyd resin, characterized in that it is a resin formed through polymerization of fatty acids, phthalic anhydride, glycerin, and pentaerythritol. 5. The method according to claim 4,
The reactive self-emulsifying agent applied alkyd resin is characterized in that represented by the following formula (2), the reactive self-emulsifying agent applied alkyd resin:
[Formula 2]

In Formula 2,
Wherein R ¹ is a saturated or unsaturated hydrocarbon having 1 to 30 carbon atoms,
A is the reactive self-emulsifying agent,
wherein p is 1 to 30. 5. The method according to claim 4,
The reactive self-emulsifying agent applied alkyd resin is characterized in that it is formed through the reaction of the carboxyl group of the reactive self-emulsifying agent with the functional group of the alkyd resin backbone, the reactive self-emulsifying agent applied alkyd resin. 5. The method according to claim 4,
The reactive self-emulsifying agent applied alkyd resin, characterized in that the number average molecular weight of the reactive self-emulsifying agent applied alkyd resin is 10000 to 40000, 14000 to 32000, or 20000 to 25000. A reactive self-emulsifying agent applied alkyd emulsion resin comprising 100 parts by weight of a reactive self-emulsifying agent applied alkyd resin, and 1 to 20 parts by weight of an emulsifier, into which a reactive self-emulsifying agent represented by the following formula (1) is introduced:
[Formula 1]

In Formula 1, R ^a is methyl or ethyl, and m:n is 1:1 to 10:1. 10. The method of claim 9,
The emulsifier is a reactive self-emulsifying agent applied alkyd emulsion resin, characterized in that it comprises an alkylaryl sulphonate (Alkylaryl sulphonate). 10. The method of claim 9,
The reactive self-emulsifying agent applied alkyd emulsion resin,
mixing 100 parts by weight of the alkyd resin to which the reactive self-emulsifying agent is introduced, and 1 to 20 parts by weight, 2 to 10 parts by weight, or 4 to 8 parts by weight of an emulsifier; and
A reactive self-emulsifying agent applied alkyd emulsion resin, characterized in that it is prepared by a manufacturing method comprising the step of emulsifying by dropwise dispersing deionized water. 10. The method of claim 9,
The alkyd emulsion resin, characterized in that the average particle diameter of the reactive self-emulsifying agent applied alkyd emulsion resin is 300 to 800 nm, 400 to 700 nm, or 500 to 600 nm. 10. The method of claim 9,
The alkyd emulsion resin, characterized in that the non-volatile content of the reactive self-emulsifying agent applied alkyd emulsion resin is 35 to 70%, 40 to 60%, or 45 to 55%.