Amine-amide resin composition and method for producing the same
阅读说明：本技术 胺-酰胺树脂组合物及其制备方法 (Amine-amide resin composition and method for producing the same ) 是由 赵珍 金载孝 朴真熙 全智勳 于 2020-01-06 设计创作，主要内容包括：本发明涉及一种胺-酰胺树脂组合物以及其制备方法,更具体而言,涉及与水溶性环氧固化表现出优异的物性的胺-酰胺树脂组合物以及其制备方法。本发明的胺-酰胺树脂组合物是通过混合环氧改性胺树脂及酰胺类树脂而制备的,该环氧改性胺树脂是由包含以下化学式1表示的聚烷氧基二胺的反应混合物制备的。[化学式1]<Image he="106" wi="492" file="1.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention relates to an amine-amide resin composition and a method for preparing the same, and more particularly, to an amine-amide resin composition exhibiting excellent physical properties with water-soluble epoxy curing and a method for preparing the same. The amine-amide resin composition of the present invention is prepared by mixing an epoxy-modified amine resin prepared from a reaction mixture containing polyalkoxy diamine represented by the following chemical formula 1 with an amide resin. [ chemical formula 1])
1. An amine-amide resin composition comprising:
an epoxy-modified amine resin prepared from a reaction mixture comprising polyalkoxy diamine represented by the following chemical formula 1; and
an amide-based resin which is capable of forming a resin,
[ chemical formula 1]
In chemical formula 1, R is independently selected from C1To C60At least one of alkyl groups of (a).
2. The amine-amide resin composition of claim 1, wherein the reaction mixture comprises an epoxy resin.
3. The amine-amide resin composition according to claim 1, wherein the mixing ratio of the epoxy-modified amine resin and the amide-based resin is 0.4: 1 to 1.6: 1.
4. a method of preparing an amine-amide resin composition, comprising:
a step of preparing an epoxy-modified amine resin from a reaction mixture comprising a polyalkoxydiamine represented by the following chemical formula 1; and
a step of mixing the epoxy-modified amine resin prepared in the above step with an amide-based resin,
[ chemical formula 1]
In chemical formula 1, R is independently selected from C1To C60At least one of alkyl groups of (a).
5. The method of making an amine-amide resin composition of claim 4, wherein the reaction mixture comprises an epoxy resin.
6. The method for producing an amine-amide resin composition according to claim 4, wherein the mixing ratio of the epoxy-modified amine resin and the amide-based resin is 0.4: 1 to 1.6: 1.
Technical Field
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 cured with a water-soluble epoxy resin to exhibit excellent physical properties, and a method for preparing the same.
Background
The amine-based resin and/or the amide-based resin are resins that easily react with an epoxy resin at room temperature to exhibit a tough cured structure. In particular, amine-based resins and/or amide-based resins are used as a main component of cured resins such as protective coatings, vegetable coatings, and the like in the field of coatings, and exhibit very good coating properties when used together with bisphenol-type epoxy resins. Specifically, bisphenol a epoxy resins are cured resins that have characteristics that greatly affect the physical properties of resins cured using amine-based resins and amide-based resins, and more specifically, are used in various industries as curable resins that can be cured at room temperature.
Recently, due to continuous environmental regulations, the field using conventional oil-soluble resins is rapidly changed to water-soluble ones, and according to such changes, epoxy resins are also used after being dissolved in water, and thus, research on resins used together with water-soluble epoxy resins has become widespread.
Many studies have been made on the use of water-soluble amine resins, but because of the characteristic that amines have a small molecular weight and cause skin rash and dermatitis when they come into contact with the skin, the industrial use of these resins is very harmful to the health of workers. Further, amide resins have a higher molecular weight than amine resins, and therefore, are less harmful to the skin, but are more difficult to be dissolved in water than amine resins, and therefore, are difficult to be used in water-soluble coating systems.
Accordingly, the present inventors have made extensive studies to solve the problems of water-soluble amine-amide resins, namely, skin irritation and water solubility, and have found that when polyalkoxydiamines are used instead of aromatic or alicyclic amines, which are irritant components of water-soluble amine resins generally commercially available, the amide resins are used to achieve surprising results that the skin irritation can be reduced while maintaining the conventional properties with respect to insufficient properties, and have completed the present invention.
Disclosure of Invention
The present invention is directed to a water-soluble epoxy resin-based amine-amide resin, and more particularly, to a water-soluble epoxy resin-based amine-amide resin having improved skin irritation problems, and a method for preparing the same.
To achieve the above object, the present invention provides an amine-amide resin composition comprising: an epoxy-modified amine resin prepared from a reaction mixture comprising polyalkoxy diamine represented by the following chemical formula 1; and an amide resin.
Further, the present invention provides a method for preparing an amine-amide resin composition, comprising: a step of preparing an epoxy-modified amine resin from a reaction mixture comprising a polyalkoxydiamine represented by the following chemical formula 1; and a step of mixing the epoxy-modified amine resin and the amide-based resin prepared in the above step.
[ chemical formula 1]
In chemical formula 1, R is independently selected from C1To C60At least one of alkyl groups of (a).
Effects of the invention
The amine-amide resin composition of the present invention can be used as a cured resin of a water-soluble epoxy resin, which has physical properties equivalent to those of an amine-based cured resin used in combination with a conventional water-soluble epoxy resin while improving the problem of skin irritation.
Further, when the method for producing an amine-amide resin composition of the present invention is used, a cured resin of a water-soluble epoxy resin having physical properties equivalent to or higher than those of an amine-based cured resin used in a mixture with a conventional water-soluble epoxy resin can be provided while improving the problem of skin irritation.
Detailed Description
The weight average molecular weight used in the present invention is measured by a conventional method well known in the art, for example, by a Gel Permeation Chromatograph (GPC) method.
The present invention provides an amine-amide resin composition comprising: an epoxy-modified amine resin prepared from a reaction mixture comprising polyalkoxy diamine represented by the following chemical formula 1; and an amide resin.
[ chemical formula 1]
The amine-amide resin composition of the present invention can be prepared by first reacting a reaction mixture containing an epoxy resin and a polyalkoxydiamine to prepare an epoxy-modified amine resin, and then mixing the epoxy-modified amine resin with an amide resin. The amine-amide resin composition of the present invention prepared as described above may exhibit excellent water solubility. In one example, it was confirmed that an amine-amide resin composition prepared by mixing an amide resin with an epoxy-modified amine resin, which is obtained by reacting an amide resin with a polyamine resin and then adding an epoxy resin, has a significantly improved water solubility, is easily available as a water solubility, and has improved skin irritation, compared to a resin exhibiting oil solubility.
In the present invention, the polyalkoxydiamine may be a compound represented by the above chemical formula 1, and in the above chemical formula 1, R may be at least one independently selected from alkyl groups of C1 to C60. Here, the alkyl group is exemplified by methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethylpropyl, 1-dimethylpropyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but is not limited thereto. Specifically, the R may be at least one independently selected from ethyl and isopropyl. The polyalkoxydiamines may be block copolymers, random copolymers or mixtures of these. By using the polyalkoxydiamine represented by the above chemical formula 1, an effect of improving skin irritation can be exhibited as compared with conventional aromatic amines or alicyclic amines.
The weight average molecular weight (Mw) of the polyalkoxydiamine may vary depending on the structure of R, but is not limited thereto, and may be, for example, 100 to 3,000g/mol, for example, 150 to 1,000g/mol, 200 to 500 g/mol.
Additionally, in preparing the epoxy-modified amine resin, the reaction mixture may include an epoxy resin.
As the epoxy resin used for preparing the epoxy-modified amine resin, a commonly used epoxy resin can be used.
In one embodiment, a bisphenol-type epoxy resin, a polyalkoxydiglycidyl ether (POLYALKOXY DIGLYCIDYL ETHER), or a mixture of these may be used as the epoxy resin.
As the bisphenol type epoxy resin, a bisphenol A type epoxy resin having an epoxy equivalent of 190 to 500eq/g can be used. For example, a bisphenol A type epoxy resin having equivalent physical properties to that of YD-128 (epoxy equivalent 190eq/g), YD-011 (epoxy equivalent 475eq/g) or other commercially available national chemical products can be used. When a specific epoxy equivalent between two epoxy resins is required, it is used by preparation, or the two resins may be mixed in an appropriate ratio and used.
The polyalkoxy diglycidyl ether may be represented by the following chemical formula 2.
[ chemical formula 2]
In the chemical formula 2, R' may be at least one independently selected from C1 to C60 alkyl groups, respectively. Here, the alkyl group is exemplified by methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethylpropyl, 1-dimethylpropyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but is not limited thereto. Specifically, the R' may be at least one independently selected from ethyl and isopropyl. In the chemical formula 2, n may be different according to the structure of R'.
May have an n value for the weight average molecular weight (Mw) of the polyalkoxydidylether of 200 to 1,000 g/mol. The compound represented by the chemical formula 2 may use a block copolymer, a random copolymer, or a mixture thereof.
When the bisphenol-type epoxy resin and the polyalkoxydi-glycidyl ether are used as the epoxy resin in a mixture, the mixing molar ratio is not particularly limited, but is preferably 7:3 to 3: 7. for example, when the number of moles of the bisphenol type epoxy resin is increased, water-solubility is difficult, and when the bisphenol type epoxy resin is mixed with an epoxy resin, flexibility is reduced and mechanical properties are improved, and when the number of moles of the polyalkoxydi glycidyl ether is increased, there occurs a problem of the contrary.
The epoxy-modified amine resin can be prepared by mixing and stirring the polyalkoxydiamine and the epoxy resin, and in this case, the ratio of the epoxy resin to the polyalkoxydiamine is preferably 1: 1 to 3:1, e.g. 1.5: 1 to 2.5: 1, mixing the mixed polyalkoxy diamine and the epoxy resin. Specifically, if the molar ratio exceeds the above range, the viscosity of the resin composition may become high, the resin may be gelled and may not be usable, or when the resin composition is mixed with an epoxy resin, problems such as decrease in miscibility, hardness, and the like may occur.
The amine-amide resin of the present invention is prepared by mixing the epoxy-modified amine resin with an amide resin.
The amide-based resin can be prepared by reacting polyvinylamine with fatty acid and/or fatty acid dimer.
As the polyethyleneamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc. which are generally used for epoxy curing can be used, but as the molecular weight of the ethyleneamine is higher, water solubility is better, and therefore, one or more selected from the group consisting of triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine can be preferably used in combination.
The fatty acid may be one or more selected from the group consisting of soybean oil fatty acid, tall oil fatty acid, castor oil fatty acid, rice bran oil fatty acid, linseed oil fatty acid, coconut oil fatty acid, lauric acid, and linoleic acid, and preferably tall oil fatty acid may be used. In addition, as the fatty acid dimer, soybean oil fatty acid dimer, tall oil fatty acid dimer, or the like can be used.
The amide-based resin is not limited thereto, and can be produced by adding polyvinylamine dropwise to the fatty acid or fatty acid dimer, and heating to 150 to 250 ℃ until the acid value of the product becomes 1 to 5. Specifically, the reaction can be carried out until the equivalent ratio of the entire amine groups to the carboxylic acid groups is 1.7:1 to 2.3: 1. When the equivalent ratio of the amine group and the carboxylic acid group is within the above range when the amide-based resin is prepared, skin irritation and water solubility of the finally prepared amine-amide resin may be preferable.
The amine-amide resin of the present invention can be prepared by mixing the amide resin as described above with the epoxy-modified amine resin as described above. At this time, the mixing ratio of the epoxy-modified amine resin and the amide-based resin may be 0.4: 1 to 1.6: 1. when the mixing weight ratio is within the above range, it is preferable in terms of water solubility and physical properties of the amine-amide resin.
As described above, the amine-amide resin prepared by mixing the epoxy-modified amine resin and the amide-based resin may have a solid content of 60 to 70% by weight, an active hydrogen equivalent of 70 to 300g/eq, and a viscosity of 600 to 30,000cPs, which is measured using a brookfield viscometer.
The epoxy-modified amine resin and the amide-based resin may be mixed and then diluted with water or other solvents to reduce the viscosity, and the other solvents are not limited thereto, and for example, methanol, ethanol, n-propanol, isopropanol, 1-methoxypropanol, 1-ethoxypropanol, etc. may be used, and the amount of the other solvents used for dilution is not generally limited.
In another aspect, the present invention provides a method for preparing an amine-amide resin composition, comprising: a step of preparing an epoxy-modified amine resin from a reaction mixture comprising the polyalkoxydiamine represented by chemical formula 1; and a step of mixing the prepared epoxy-modified amine resin and the amide-based resin. The reaction mixture may include an epoxy resin, and the components of the polyalkoxydiamine, reaction mixture, amide-based resin, and the like 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.
in addition, the epoxy-modified amine resin may be prepared as follows: the polyalkoxydiamine is put into a flask capable of stirring, heated to 70 to 90 ℃, and then the mixture of the epoxy resin, for example, bisphenol epoxy resin and polyalkoxydi-glycidyl ether in the reaction mixture is added dropwise for 1 to 5 hours, for example, 3 hours for reaction, and then kept for 1 to 10 hours, for example, 5 hours for complete reaction.
The following examples and the like are described in detail to aid understanding of the present invention. However, embodiments according to the present invention may be deformed into various other forms. The scope of the invention should not be construed as limiting the invention. Embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art to which the present invention pertains.