KR102273807B1 - Amine-amide resin composition and method for preparing thereof - Google Patents

Abstract

The present invention relates to an amine-amide resin composition and a preparation method thereof, and more particularly, to an amine-amide resin composition exhibiting excellent physical properties by curing with a water-soluble epoxy, and a preparation method thereof. The amine-amide resin composition of the present invention includes an epoxy-modified amine resin prepared from a reaction mixture containing a polyalkoxy diamine represented by the following Chemical Formula 1; And it is prepared by mixing an amide-based resin.
[Formula 1]

Description

Amine-amide resin composition and method for preparing the same {Amine-amide resin composition and method for preparing thereof}

The present invention relates to an amine-amide resin composition and a method for preparing the same, and more particularly, to a water-soluble amine-amide resin composition exhibiting excellent physical properties by curing with a water-soluble epoxy resin and a method for preparing the same.

An amine-based resin and/or an amide-based resin is a resin that can easily react with an epoxy resin at room temperature to exhibit a strong cured structure. In particular, amine-based resins and/or amide-based resins are used as a main component of cured resins such as heavy-duty anticorrosive paints and plant paints in the paint field, and they are used together with bisphenol-based epoxy resins to show very good performance as paints. Specifically, as a cured resin of bisphenol-A epoxy resin, it has a characteristic that greatly influences the physical properties of the resin cured using it, and more specifically, it is applied in many industries as it can be cured at room temperature.

Recently, due to continuous environmental regulations, the field where the existing oil-soluble resins were used is rapidly changing to water-soluble, and with this change, epoxy resins are also water-soluble and used. Accordingly, there are many researches on resins that can be used with water-soluble epoxy resins. is becoming

In many previous studies, a lot of water-soluble amine type resins were used, but due to the small molecular weight of the amines, it causes rashes and dermatitis when in contact with the skin, and when used in industry, it creates an environment that is very harmful to the health of workers. . In addition, the amide-type resin has a higher molecular weight than the amine-type resin and is therefore less harmful to the skin.

Accordingly, the present inventors have been researching and trying to solve the above problems of water-soluble amine-amide resin, skin irritation and water solubility, polyalkoxy diamine instead of aromatic and cycloaliphatic amines, which are irritating components of commercially available water-soluble amine resins. The present invention was completed by discovering the surprising fact that the insufficient physical properties during use can reduce skin irritation while maintaining the existing physical properties by using an amide resin.

The present invention intends to provide a water-soluble epoxy resin-based amine-amide resin, and specifically provides a water-soluble epoxy resin-based amine-amide resin with improved skin irritation and a method for preparing the same.

In order to achieve the above object, the present invention is an epoxy-modified amine resin prepared from a reaction mixture containing a polyalkoxy diamine represented by the following formula (1); and an amine-amide resin composition comprising an amide-based resin.

In addition, an amine-amide resin composition comprising the steps of preparing an epoxy-modified amine resin from a reaction mixture comprising a polyalkoxy diamine represented by the following Chemical Formula 1 and mixing the prepared epoxy-modified amine resin with an amide-based resin It provides a manufacturing method of

[Formula 1]

In Formula 1, each R is independently at least one selected from a _{C 1} to C _{60 alkylene group.}

The amine-amide resin composition of the present invention can be used as a water-soluble epoxy resin cured resin having physical properties equal to or higher than that of an amine-type cured resin used by mixing with a conventional water-soluble epoxy resin while improving the skin irritation problem.

In addition, by using the method for producing the amine-amide resin composition of the present invention, while improving the problem of skin irritation, curing of a water-soluble epoxy resin having physical properties equal to or higher than that of an amine-type cured resin used by mixing with a conventional water-soluble epoxy resin resin can be provided.

The weight average molecular weight used herein is measured by a conventional method known in the art, for example, it can be measured by a GPC (gel permeation chromatograph) method.

The present invention relates to an epoxy-modified amine resin prepared from a reaction mixture containing a polyalkoxy diamine represented by the following Chemical Formula 1; and an amine-amide resin composition comprising an amide-based resin.

[Formula 1]

The amine-amide resin composition of the present invention may be prepared by first reacting a reaction mixture containing an epoxy resin and polyalkoxy diamine to prepare an epoxy-modified amine resin, and then mixing the amide-based resin thereto. The amine-amide resin composition of the present invention prepared as described above may exhibit excellent water solubility. In one embodiment, the resin prepared by adducting the epoxy after reacting the amide-based resin with the polyamine resin is an amine-amide resin composition prepared by mixing the epoxy-modified amine resin with the amide-based resin compared to that showing usefulness It was confirmed that the water solubility of silver was greatly improved, and it was easy to use due to its water solubility and improved skin irritation.

In the present invention, the polyalkoxy diamine may be a compound represented by Formula 1, wherein R in Formula 1 may each independently be at least one selected from a C1 to C60 alkylene group. Here, the alkylene group is, for example, a methylene group, ethylene group, n-propylene group, iso-propylene group, n-butylene group, iso-butylene group, tert-butylene group, sec-butylene group, 1-methylbutylene group , 1-ethylbutylene group, n-pentylene group, iso-pentylene group, neo-pentylene group, tert-pentylene group, n-hexylene group, 1-methylpentylene group, 2-methylpentylene group, 3,3-dimethyl Butylene group, 2-ethylbutylene group, n-heptylene group, 1-methylhexylene group, cyclopentylmethylene group, cyclohexylmethylene group, n-octylene group, tert-octylene group, 1-methylheptylene group, 2-ethyl Hexylene group, 2-propylpentylene group, n-nonylene group, 2,2-dimethylheptylene group, 1-ethylpropylene group, 1,1-dimethylpropylene group, isohexylene group, 2-methylpentylene group, 4- a methylhexylene group, a 5-methylhexylene group, and the like, but is not limited thereto. Specifically, R may each independently be at least one selected from an ethylene group and an iso-propylene group. The polyalkoxy diamine may be a block copolymer, a random copolymer, or a mixture thereof. By using the polyalkoxy diamine represented by Formula 1, it is possible to exhibit the effect of improving the skin irritation problem compared to the conventional aromatic amine or alicyclic amine.

The weight average molecular weight (Mw) of the polyalkoxy diamine may vary depending on the structure of R, but is not limited thereto, but may be, for example, 100 to 3,000 g/mol, for example, 150 to 1,000 g/mol, 200 to 500 g/mol.

In addition, in the preparation of the epoxy-modified amine resin, the reaction mixture may include an epoxy resin.

As the epoxy resin for preparing the epoxy-modified amine resin, a commonly used epoxy resin may be used.

In one embodiment, as the epoxy resin, a bisphenol-type epoxy resin, poly alkoxy diglycidyl ether, or a mixture thereof may be used.

As the bisphenol-type epoxy resin, a bisphenol-A-type epoxy resin having an epoxy equivalent of 190 to 500 eq/g may be used. For example, commercially available Kukdo Chemical's YD-128 (epoxy equivalent: 190 eq/g), YD-011 (epoxy equivalent: 475 eq/g), or other companies' equivalent bisphenol-A type epoxy resin can be used. If a specific epoxy equivalent between the epoxies is required, it can be prepared and used, or the two resins can be mixed in an appropriate ratio.

As the polyalkoxy diglycidyl ether, one represented by the following Chemical Formula 2 may be used.

[Formula 2]

In Formula 2, R' may be each independently at least one selected from a C1 to C60 alkylene group. Here, the alkylene group is, for example, a methylene group, ethylene group, n-propylene group, iso-propylene group, n-butylene group, iso-butylene group, tert-butylene group, sec-butylene group, 1-methylbutylene group , 1-ethylbutylene group, n-pentylene group, iso-pentylene group, neo-pentylene group, tert-pentylene group, n-hexylene group, 1-methylpentylene group, 2-methylpentylene group, 3,3-dimethyl Butylene group, 2-ethylbutylene group, n-heptylene group, 1-methylhexylene group, cyclopentylmethylene group, cyclohexylmethylene group, n-octylene group, tert-octylene group, 1-methylheptylene group, 2-ethyl Hexylene group, 2-propylpentylene group, n-nonylene group, 2,2-dimethylheptylene group, 1-ethylpropylene group, 1,1-dimethylpropylene group, isohexylene group, 2-methylpentylene group, 4- a methylhexylene group, a 5-methylhexylene group, and the like, but is not limited thereto. Specifically, R' may each independently be at least one selected from an ethylene group and an iso-propylene group. In Formula 2, the value of n may vary depending on the structure of R'.

The weight average molecular weight (Mw) of the poly alkoxy diglycidyl ether may have a value of n used in the range of 200 to 1,000 g/mol. The compound represented by Formula 2 may be a block copolymer, a random copolymer, or a mixture thereof.

In the case of using a mixture of the bisphenol-type epoxy resin and polyalkoxy diglycidyl ether as the epoxy resin, the mixing molar ratio thereof is not particularly limited, but considering the physical properties of the epoxy-modified amine resin to be prepared, 7:3 to 3:7 may be desirable. For example, when the number of moles of the bisphenol-type epoxy resin increases, water solubility becomes difficult, flexibility decreases when mixed with epoxy, and mechanical properties are improved. When the number of moles of polyalkoxy diglycidyl ether increases, the The opposite problem may occur, but is not limited thereto.

An epoxy-modified amine resin may be prepared by mixing the polyalkoxydiamine and the epoxy resin and then stirring, and at this time, the polyalkoxydiamine and the epoxy resin to be mixed are 1:1 to 3:1, for example 1.5 Mixing in a molar ratio of :1 to 2.5:1 may be preferable in terms of curing and physical properties of the epoxy resin. Specifically, when the molar ratio is out of the range, the viscosity of the resin composition is high, the resin is gelled, and thus cannot be used, or when mixed with epoxy, problems of compatibility, hardness, etc. may be deteriorated.

The amine-amide resin of the present invention is prepared by mixing an amide-based resin with the epoxy-modified amine resin.

The amide-based resin may be prepared by reacting polyethylene amine with fatty acids and/or fatty acid dimers.

As the polyethylene amine, diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, pentaethylenehexaamine, etc., which are commonly used for epoxy curing, can be used, but the higher the molecular weight of ethyleneamine, the better the water solubility. It may be preferable to use a mixture of at least one selected from the group consisting of triethylenetetraamine, tetraethylenepentaamine, and pentaethylenehexaamine.

The fatty acid may be a mixture of at least one selected from the group consisting of soybean oil fatty acid, tall oil fatty acid, castor oil fatty acid, rice bran oil fatty acid, flax oil fatty acid, coconut oil fatty acid, lauryl acid and linoleic acid, preferably tall oil fatty acid can be used In addition, as the fatty acid dimer, a soybean oil fatty acid dimer, a tall oil fatty acid dimer, or the like may be used.

The amide-based resin is not limited thereto, but it may be prepared by adding the polyethylene amine dropwise to the fatty acid and the fatty acid dimer, and reacting it until the acid value of the product becomes 1 to 5 by raising the temperature to 150 to 250 ° C. . Specifically, it may be prepared by reacting so that the equivalent ratio of all amine groups to carboxylic acid groups is 1.7:1 to 2.3:1. When the amide-based resin is prepared, when the equivalent ratio of the amine group and the carboxylic acid group is within the above range, it may be preferable for improving skin irritation and water solubility of the finally prepared amine-amide resin.

The amine-amide resin of the present invention may be prepared by mixing the amide-based resin as described above with the above-described epoxy-modified amine resin. In this case, the mixing ratio of the epoxy-modified amine resin and the amide-based resin may be 0.4:1 to 1.6:1 by weight. When the mixing weight ratio is within the above range, it may be preferable in terms of water solubility and physical properties of the amine-amide resin.

The amine-amide resin prepared by mixing the epoxy-modified amine resin and the amide-based resin as described above may have a solid content of 60 to 70 wt%, an active hydrogen equivalent of 70 to 300 g/eq, and a viscosity of 600 to 30,000 cPs, Viscosity is measured using a Brookfild viscometer.

After mixing the epoxy-modified amine resin and the amide-based resin, it can be diluted with water or other solvent to lower the viscosity, and the other solvent is not limited thereto, for example, methanol, ethanol, n-propanol , iso-propanol, 1-methoxy propanol, 1-ethoxy propanol, etc. may be used, and the amount of other solvents used for dilution is not usually limited.

In one aspect, the present invention comprises the steps of preparing an epoxy-modified amine resin from a reaction mixture containing the polyalkoxy diamine represented by Formula 1 and mixing the prepared epoxy-modified amine resin with an amide-based resin Provided is a method for preparing an amine-amide resin composition, wherein the reaction mixture may include an epoxy resin, and components such as the polyalkoxy diamine, the reaction mixture, and the amide-based resin are as described above.

In addition, the mixing ratio of the epoxy-modified amine resin and the amide-based resin may be 0.4:1 to 1.6:1 by weight.

In addition, the epoxy-modified amine resin is an epoxy resin in the reaction mixture, for example, a bisphenol-type epoxy resin and a polyalkoxy diamine, after the polyalkoxydiamine is put in a stirrable flask and the temperature is raised to 70 to 90°C. A mixture of glycidyl ethers is added dropwise for 1 to 5 hours, for example, 3 hours, and then reacted for an additional 1 to 10 hours, for example, 5 hours.

Hereinafter, examples and the like will be described in detail to help the understanding of the present invention. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the following examples. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art to which the present invention pertains.

Example 1. Preparation of epoxy-modified amine resin

Put 100 g of polyethoxydiamine having a molecular weight of 240 g/mol in a four-necked round flask, install a nitrogen gas tube, H-type separation tube, stirrer, thermometer, and heater, and then raise the temperature to 80 °C at a rate of 20 °C per hour. 40 g of YD-128, a bisphenol-A type epoxy resin of Kukdo Corporation, and 25 g of polyethoxydiglycidyl ether having a molecular weight of 240 g/mol are mixed and uniformly added dropwise over 3 hours. After completion of the dropwise addition, the reaction was further carried out for an additional 5 hours to complete the reaction, and then the reaction was terminated. After cooling, a transparent resin with high viscosity was obtained.

Example 1-1. Preparation of amine-amide resin composition

Put 615 g of tall fatty acid dimer, 40 g of tall fatty acid, and 390 g of tetraethylenepentaamine in a 4-neck round flask, install a nitrogen gas tube, H-type separator, stirrer, thermometer, and heater, and then heat to 180 ° C at a rate of 20 ° C per hour. warm up After the temperature was raised and maintained for 3 hours, the dehydration reaction was carried out, and the reaction was terminated and cooled.

Then, 670 g of the epoxy-modified amine resin synthesized in Example 1 was mixed and maintained at 70° C. for 1 hour. 70 g of isopropyl alcohol and 650 g of deionized water are mixed with the mixed resin, mixed for 30 minutes, and then cooled to complete the reaction. The amine-amide resin composition prepared at this time had a solid content of 63%, an active hydrogen equivalent of 132, and a viscosity of 2,700 cps.

At this time, the solid content was indicated by measuring the weight of the remaining solid content after drying 1 g of the resin in a convection oven at 150° C. for 15 minutes, and the active hydrogen equivalent was expressed as a theoretical value that can be represented by a conventional method. The viscosity was measured using a Brookfield viscometer (Brookfield viscometer, LVT) at 25 ℃.

Example 1-2. Preparation of amine-amide resin composition

Put 615 g of tall fatty acid dimer, 40 g of tall fatty acid, and 390 g of tetraethylenepentaamine in a 4-neck round flask, install a nitrogen gas tube, H-type separator, stirrer, thermometer, and heater, and then heat to 180 ° C at a rate of 20 ° C per hour. warm up After the temperature was raised and maintained for 3 hours, the dehydration reaction was carried out, and the reaction was terminated and cooled. Then, 800 g of the epoxy-modified amine resin synthesized in Example 1 is mixed and maintained at 70° C. for 1 hour. 75 g of isopropyl alcohol and 700 g of deionized water are mixed with the mixed resin, mixed for 30 minutes, and then cooled to complete the reaction. The amine-amide resin composition prepared at this time had a solid content of 63%, an active hydrogen equivalent of 140, and a viscosity of 3,500 cps.

Examples 1-3. Preparation of amine-amide resin composition

Put 615 g of tall fatty acid dimer, 40 g of tall fatty acid, and 347 g of triethylenetetraamine in a 4-necked round flask, install a nitrogen gas pipe, H-type separator, stirrer, thermometer, and heater, and then heat to 180°C at a rate of 20°C per hour. warm up After the temperature was raised and maintained for 3 hours, the dehydration reaction was carried out, and the reaction was terminated and cooled. Then, 670 g of the epoxy-modified amine resin synthesized in Example 1 was mixed and maintained at 70° C. for 1 hour. 70 g of isopropyl alcohol and 650 g of deionized water are mixed with the mixed resin, mixed for 30 minutes, and then cooled to complete the reaction. The amine-amide resin composition prepared at this time had a solid content of 64%, an active hydrogen equivalent of 132, and a viscosity of 3,500 cps.

Example 2. Preparation of epoxy-modified amine resin

Put 100 g of polypropoxydiamine with a molecular weight of 240 g/mol in a four-necked round flask, install a nitrogen gas tube, H-type separator, stirrer, thermometer, and heater, and then raise the temperature to 80°C at a rate of 20°C per hour. 40 g of YD-128, a bisphenol-A type epoxy resin of Kukdo Corporation, and 25 g of polyethoxydiglycidyl ether having a molecular weight of 240 g/mol are mixed and uniformly added dropwise over 3 hours. After completion of the dropwise addition, the reaction was further carried out for an additional 5 hours to complete the reaction, and then the reaction was terminated. After cooling, a transparent resin with high viscosity was obtained.

Example 2-1. Preparation of amine-amide resin composition

Put 615 g of tall fatty acid dimer, 40 g of tall fatty acid, and 390 g of tetraethylenepentaamine in a 4-neck round flask, install a nitrogen gas tube, H-type separator, stirrer, thermometer, and heater, and then heat to 180 ° C at a rate of 20 ° C per hour. warm up After the temperature was raised and maintained for 3 hours, the dehydration reaction was carried out, and the reaction was terminated and cooled. Then, 670 g of the epoxy-modified amine resin synthesized in Example 2 was mixed and maintained at 70° C. for 1 hour. 70 g of isopropyl alcohol and 650 g of deionized water are mixed with the mixed resin, mixed for 30 minutes, and then cooled to complete the reaction. The amine-amide resin composition prepared at this time had a solid content of 62%, an active hydrogen equivalent of 121, and a viscosity of 2,900 cps.

Comparative Example 1. Preparation of amide-amine epoxy adduct resin (change of epoxy modification reaction sequence in Example 1-1)

Put 615 g of tall fatty acid dimer, 40 g of tall fatty acid, and 390 g of tetraethylenepentaamine in a 4-neck round flask, install a nitrogen gas tube, H-type separator, stirrer, thermometer, and heater, and then heat to 180 ° C at a rate of 20 ° C per hour. warm up After the temperature was raised and maintained for 3 hours, the dehydration reaction was carried out, and the reaction was terminated and cooled.

Then, 406 g of polyethoxy diamine having a molecular weight of 240 g/mol is mixed and maintained at 70° C. for 1 hour. 162 g of YD-128, a bisphenol-A type epoxy resin of Kukdo Corporation, and 102 g of polyethoxydiglycidyl ether having a molecular weight of 240 g/mol are mixed and uniformly added dropwise over 3 hours. After completion of the dropwise addition, the reaction was further carried out for an additional 5 hours to complete the reaction, and then the reaction was terminated. 70 g of isopropyl alcohol and 650 g of deionized water are mixed with the mixed resin and mixed for 30 minutes. When about 200 g of deionized water was added dropwise, the resin did not mix with water and was separated into a water layer and a resin layer.

Comparative Examples 2 and 3. Evaluation of physical properties including commercial products

One water-soluble epoxy mixed paint made using Example 1 above, one water-soluble epoxy mixed paint prepared using commercially available cured resin (cured resin, Comparative Example 2), commercially available water-soluble epoxy mixed paint 1 The basic paint properties and rabbit skin irritation were evaluated using the species (Comparative Example 3), and the results are as follows.

division Example 1-1 Example
1-2 Example
1-3 Example
2-1 comparative example
One Comparative Example 2 ¹⁾ Comparative Example 3 ²⁾ rust prevention Rust ³⁾ 10 8 10 10 not measurable 9 9 Creep ⁴⁾ 2.58 3.12 2.54 2.48 not measurable 2.52 2.53 Blister ⁵⁾ 10 8 10 10 not measurable 10 10 Base adhesion ⁶⁾ 3B 3B 3B 3B not measurable 3B 3B Impact resistance ⁷⁾ Front 60 Ibs inch pass pass Fail Fail not measurable Fail Fail Rear 5 Ibs inch pass pass pass pass not measurable Fail Fail Rabbit Patch Test ⁸⁾ erythema Level 1 Level 1 Level 1 Level 2 not measurable Level 3 Level 2 edema Level 0 Level 0 Level 0 Level 1 not measurable Level 2 Level 1

1) Cured resin of Comparative Example 2: Contains aromatic amine (MPCA, Mixed polycycloaromatic amine) and amide

2) Comparative Example 3: Aliphatic amine (IPDA, Isophorone diamine) and epoxy cured resin contained

3) Observe the state of the coating film after 1000 hours of salt spray

4) Salt spray 1000 hours after cross-cutting, measure the length of rust from the cutting part

5) Observe the state of the coating film after 1000 hours of salt spray

6) Measurement of adhesion after 1000 hours of salt spray

7) Check for cracks after impact under the applicable conditions

8) Skin reaction evaluation (Rabbit Patch Test): Each paint composition is applied to the skin of the sterilized laboratory rabbit for the same time and then visually checked for skin rashes when washed (Evaluation criteria: Level 0 (not at all) <Level 4 (severe occurrence))

From the results of Table 1 above, when the hypoallergenic water-soluble amine-amide resin composition of the present invention is mixed with a water-soluble epoxy, it has less skin irritation and excellent impact resistance, and has the same or equivalent superiority to existing products, such as other rust prevention properties and adhesion to substrates. It was found that the results of

Claims (6)

Including an epoxy-modified amine resin and an amide-based resin,
The epoxy-modified amine resin is prepared from a reaction mixture comprising an epoxy resin and a polyalkoxy diamine represented by the following Chemical Formula 1,
The epoxy resin includes a bisphenol-type epoxy resin and polyalkoxy diglycidyl ether,
The weight average molecular weight of the polyalkoxy diamine is 100 to 3,000 g / mol,
The amide-based resin is prepared by reaction with polyethylene amine; and at least one of fatty acids and fatty acid dimers;
The mixing ratio of the epoxy-modified amine resin and the amide-based resin is 0.4:1 to 1.6:1 by weight of the amine-amide resin composition.
[Formula 1]

In Formula 1, each R is independently at least one selected from a _{C 1} to C _{60 alkylene group.}
delete delete A step of preparing an epoxy-modified amine resin from a reaction mixture comprising a polyalkoxy diamine represented by the following Chemical Formula 1 and an epoxy resin, and mixing the prepared epoxy-modified amine resin with an amide-based resin,
The epoxy resin includes a bisphenol-type epoxy resin and polyalkoxy diglycidyl ether,
The weight average molecular weight of the polyalkoxy diamine is 100 to 3,000 g / mol,
The amide-based resin is prepared by reaction with polyethylene amine; and at least one of fatty acids and fatty acid dimers;
The method for preparing an amine-amide resin composition, wherein the epoxy-modified amine resin and the amide-based resin are mixed in a mixing ratio of 0.4:1 to 1.6:1 by weight.
[Formula 1]

In Formula 1, each R is independently at least one selected from a _{C 1} to C _{60 alkylene group.}
delete delete