JP2009079186A - Production method for alkyd resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method for an alkyd resin whereby the content of an aromatic hydrocarbon in the alkyd resin can largely be lowered by using a reflux solvent substituted for an aromatic hydrocarbon which enables the content of an aromatic hydrocarbon to lower into at most 100 ppm when the resin is turned into a coating. <P>SOLUTION: The production method for the resin comprises reacting a later-described raw material component (II) in the presence of suitably 0.5-5 pts.wt. of the reflux solvent (I) on the basis of 100 pts.wt. of the raw material component (II) described below. The reflux solvent (I) contains a 7-13C aliphatic and/or alicyclic hydrocarbon, preferably, a 9-11C aliphatic and/or alicyclic hydrocarbon. The content of aromatic hydrocarbon is at most 100 ppm, preferably, at most 10 ppm. The raw material component (II) contains (A) animal and vegetable oils or fatty acids therefrom, (B) a polyhydric alcohol, (C) a polycarboxylic acid, and (D) an optional phenolic resin. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to animal and vegetable oils or their fatty acids and polyhydric acids in the presence of a refluxing solvent containing aliphatic hydrocarbons and / or hydrocarbons having 7 to 13 carbon atoms and having an aromatic hydrocarbon content of 100 ppm or less. The present invention relates to a method for producing an alkyd resin in which an alcohol and a polycarboxylic acid, or animal and vegetable oils or fatty acids thereof, a polyhydric alcohol, a polycarboxylic acid and a raw material component containing a phenol resin are reacted.

  One method for producing alkyd resins is a solvent method. In this solvent method, a reflux solvent (solvent that can be azeotroped with water) is added to the reaction system in order to efficiently discharge condensed water generated by the esterification reaction of carboxylic acid and alcohol. The condensed water and the reflux solvent are separated by a solvent-water separator called a decanter after being evaporated and condensed in a cooling tower (see, for example, Patent Document 1). When an alkyd resin is produced, an esterification reaction is carried out at a high temperature of 180 to 250 ° C. However, if the solvent method is not used, a thermal reaction of animal or vegetable oil or fatty acid, which is a side reaction, occurs, and the molecular weight tends to be higher. It is in. Therefore, generally, when manufacturing an alkyd resin, a solvent method is used. As the reflux solvent used in this solvent method, aromatic hydrocarbons such as xylene and toluene that can azeotrope with water are generally used.

  Due to recent environmental problems, paints using alkyd resin as a main raw material, particularly architectural paints or construction machine paints, are required to reduce the aromatic hydrocarbon contained in the paint to 100 ppm or less. However, as long as xylene, toluene, or the like is used as the reflux solvent for the solvent method, it is difficult to reduce the aromatic hydrocarbon contained in the paint to 100 ppm or less even if a method of distilling off under reduced pressure is used. For this reason, there has been an urgent need to find a method for producing an alkyd resin that can easily produce an alkyd resin with a significantly reduced content of aromatic hydrocarbons.

Japanese Patent Publication No. 01-022287

  An object of the present invention is to provide a method for producing an alkyd resin in which the aromatic hydrocarbon content is remarkably reduced, and the aromatic hydrocarbon content in the paint can be easily reduced to 100 ppm or less.

  As a result of intensive studies to solve the above problems, the present inventor has found a solvent containing an aliphatic hydrocarbon and / or an alicyclic hydrocarbon having 7 to 13 carbon atoms and having an aromatic hydrocarbon of 100 ppm or less. When used as a reflux solvent, the alkyd resin can be produced without any problems by the solvent method, and the content of aromatic hydrocarbons can be significantly reduced. By using this, the aromatic hydrocarbons in the paint can be easily reduced to 100 ppm or less. As a result, the present invention has been completed.

  That is, the present invention contains an aliphatic hydrocarbon having 7 to 13 carbon atoms and / or an alicyclic hydrocarbon (hereinafter abbreviated as an aliphatic hydrocarbon), and has an aromatic hydrocarbon content. In the presence of 100 ppm or less of refluxing solvent (I), reacting animal and vegetable oil or fatty acid (A) thereof, polyhydric alcohol (B), and raw material component (II) containing polyvalent carboxylic acid (C). The present invention provides a method for producing an alkyd resin.

  The method for producing an alkyd resin of the present invention can produce an alkyd resin without hindrance by the solvent method even though aromatic hydrocarbons such as xylene and toluene are not used as a reflux solvent, In order to produce an alkyd resin in the presence of a reflux solvent containing 7 to 13 aliphatic hydrocarbons and 100 ppm or less of aromatic hydrocarbons, an alkyd resin having a significantly reduced content of aromatic hydrocarbons is obtained. There is an advantage that it is easy to produce and can be suitably used for paints which are required to reduce the aromatic hydrocarbon contained in the paint to 100 ppm or less, particularly architectural paints or construction machinery paints.

  The refluxing solvent (I) containing an aliphatic hydrocarbon having 7 to 13 carbon atoms and having an aromatic hydrocarbon of 100 ppm or less used in the present invention includes an aliphatic hydrocarbon and / or carbon having 7 to 13 carbon atoms. If it is an aliphatic hydrocarbon solvent containing 90% by weight or more, preferably 95% by weight or more of the alicyclic hydrocarbon of formula 7 to 13, and the content of aromatic hydrocarbon is 100 ppm or less Well, for example, aliphatic hydrocarbons such as isooctane and isodecane, and alicyclic hydrocarbons such as 1,2,4-trimethylcyclohexane, 1,2-dimethyl-4-ethylcyclohexane, 1,3,5-trimethylcyclohexane, etc. And an aliphatic hydrocarbon solvent which is a mixture of these and has an aromatic hydrocarbon content of 100 ppm or less. Among them, the boiling point is 100 to 140. Is suitable for the reflux conditions, and the condensed water can be easily removed from the reaction system. Therefore, a reflux solvent containing an aliphatic hydrocarbon having 9 to 11 carbon atoms and an aromatic hydrocarbon content of 10 ppm or less is provided. preferable. As a specific example of a preferable refluxing solvent, a trade name “Swaclean 150” (manufactured by Maruzen Petrochemical Co., Ltd .; containing a total of 95% by weight or more of aliphatic hydrocarbons and alicyclic hydrocarbons having 9 to 11 carbon atoms, And an aliphatic hydrocarbon solvent having an aromatic hydrocarbon content of 10 ppm or less), trade name “Isopar G” (manufactured by ExxonMobil Co., Ltd .; containing 95% by weight or more of an aliphatic hydrocarbon having 9 to 11 carbon atoms) And an aliphatic hydrocarbon solvent having an aromatic hydrocarbon content of 10 ppm or less.

  When a solvent containing aliphatic hydrocarbons having 6 or less carbon atoms in excess of 10% by weight is used as the reflux solvent (I), the boiling point becomes low, so it is difficult to remove condensed water from the reaction system. Therefore, it is not preferable. Further, when a solvent containing aliphatic hydrocarbons having 14 or more carbon atoms in excess of 10% by weight is used as the refluxing solvent (I), the boiling point becomes high, so that it is difficult to reflux, and the condensed water is Is difficult to remove from the reaction system.

  Further, as the reflux solvent (I), an aliphatic hydrocarbon having 7 to 13 carbon atoms is contained in an amount of 90% by weight or more, but a solvent having an aromatic hydrocarbon content exceeding 100 ppm, for example, an aromatic hydrocarbon is 1 to When a normal commercially available aliphatic hydrocarbon solvent containing about 5% by weight is used, it is difficult to reduce the aromatic hydrocarbon to 100 ppm or less.

  Examples of the animal and vegetable oils or fatty acids (A) contained in the raw material component (II) used in the present invention include linseed oil, soybean oil, safflower oil, Chinese paulownia oil, asami oil, enamel oil, tall oil, rice bran Oil, castor oil, dehydrated castor oil, rapeseed oil, cottonseed oil, palm oil, fish oil, animal and vegetable oils such as squid liver oil and their fatty acids, dehydrated castor oil fatty acid, high diene fatty acid, etc. Examples include fatty acids having a mass (g)] of 100 or more. These various animal and vegetable oils or fatty acids thereof can be used in combination.

  Examples of the polyhydric alcohol (B) contained in the raw material component (II) used in the present invention include ethylene glycol, polyethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, polypropylene glycol, 1,3-butanediol, 2 , 3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 2,2-dimethyl-1,3-propanediol (neopentyl) Glycol), 2,2-dialkyl-1,3-propanediol, 2,4,4-trimethyl-1,3-pentanediol, butylene glycol, hydrogenated bisphenol A, an adduct of bisphenol A with ethylene oxide, bisphenol A Of propylene oxide And dihydric alcohols such as adducts, triglycol, trimethylolethane, trimethylolpropane, pentaerythritol, tris- (2-hydroxyethyl) isocyanurate and the like. Alcohol is usually used alone or in admixture of two or more. Among these polyhydric alcohols (B), it is preferable to use a dihydric alcohol as an essential polyhydric alcohol component, and to use a trihydric or higher polyhydric alcohol as necessary.

  In addition, for the polyhydric alcohol (B), a polyhydric alcohol containing a carboxylic acid group may be used as the polyhydric alcohol, if necessary. As a typical example, dimethylolpropionic acid, Examples include dimethylol butanoic acid and diphenolic acid.

  Examples of the polyvalent carboxylic acid (C) contained in the raw material component (II) used in the present invention include phthalic acid, isophthalic acid, terephthalic acid, succinic acid, maleic acid, itaconic acid, fumaric acid, tetrahydrophthalic acid, Hexahydrophthalic acid, methyltetrahydrophthalic acid, adipic acid, sebacic acid, azelaic acid, “hymic anhydride” (manufactured by Hitachi Chemical Co., Ltd., 5-noribornene-2,3-dicarboxylic anhydride), trimellitic acid, Examples include methylcyclohexentricarboxylic acid, pyromellitic acid, dimer acids derived from unsaturated fatty acids, or anhydrides thereof. Of course, these polycarboxylic acids are usually used alone or in combination of two or more. Used. Among these polyvalent carboxylic acids (C), it is particularly preferable to use a divalent carboxylic acid as an essential polyvalent carboxylic acid component and to use a trivalent or higher polyvalent carboxylic acid in combination as necessary.

  Further, the polyvalent carboxylic acid (C) may be used in combination with a monovalent carboxylic acid such as benzoic acid, para-tertiary butyl benzoic acid, or rosin, if necessary. Examples of rosins used here include gum rosin, wood rosin, tall oil rosin, polymerized rosin, acid-modified rosin, and those obtained by purifying these rosins by distillation or the like.

  In the production method of the present invention, for the purpose of improving the hardness, chemical resistance, etc. of the coating film using the alkyd resin obtained, as a raw material component (II), animal and vegetable oils or their fatty acids (A), polyhydric alcohols (B ) And the polyvalent carboxylic acid (C), a raw material component containing the phenol resin (D) can be used. The amount of the phenol resin (D) used in this case is as follows: animal or vegetable oil or its fatty acid (A), polyhydric alcohol (B), and polyhydric carboxylic acid (C), considering the molecular weight or viscosity of the alkyd resin obtained. And a range of 1 to 10 parts by weight with respect to 100 parts by weight of the raw material component containing the phenol resin (D) is preferable, and a range of 3 to 7 parts by weight is more preferable.

  The phenol resin (D) that can be used here is not particularly limited, but among them, a resol type phenol resin is preferable. For example, phenols and formaldehyde are sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide. And a resol type phenol resin obtained by reacting in the presence of an alkali catalyst such as an ammonia aqueous solution, a resol product of a novolac type phenol resin, and the like.

  Among these resol-type phenol resins, phenols (P) and formaldehyde (F) are obtained by reacting in the presence of an alkali catalyst within a range of F / P (molar ratio) of 1.5 to 3.0. A resol type phenol resin is preferred. As the average number of nuclei of these resol type phenol resins, those having an average of 1 to 10 nuclei are usually used, and among them, those having an average of 3 to 6 nuclei as the main component are preferred. Examples of the weight average molecular weight include 200 to 1,600, with 700 to 1,300 being preferred.

  Examples of the phenols include phenol, cresol, amylphenol, p-tertiary butylphenol, p-octylphenol, p-nonylphenol, p-dodecylphenol, bisphenol A, and among them, p-tertiarybutylphenol. Alkylphenol having a substituent having 4 to 12 carbon atoms in the para position, such as p-octylphenol, p-nonylphenol, and p-dodecylphenol.

  In addition, the formaldehyde includes a formaldehyde supply substance, and examples thereof include formaldehyde and rose formaldehyde.

  In the conventional method for producing an alkyd resin by the solvent method, after the alcohol exchange reaction between the animal and vegetable oil and the polyhydric alcohol, a step of esterifying the polyhydric carboxylic acid and, if necessary, the polyhydric alcohol and / or phenol resin, or Fatty acid, polyhydric carboxylic acid and polyhydric alcohol of animal and vegetable oils, and if necessary, in the step of esterification reaction of phenol resin, 5 to 10 weights with respect to a total of 100 parts by weight of raw material components used for producing alkyd resin Part of the aromatic hydrocarbon is added as refluxing solvent.

  However, in the method for producing an alkyd resin of the present invention, a reflux solvent (I) containing an aliphatic hydrocarbon having 7 to 13 carbon atoms and having an aromatic hydrocarbon content of 100 ppm or less has been conventionally used. Higher than the aniline point of the aromatic hydrocarbon (xylene: 10.3 ° C.) [The aniline point of “Swaclean 150” preferred as the reflux solvent (I) used in the present invention is 55 ° C., and the aniline of “Isopar G” The point is 78 ° C. ]. Thus, in the production method of the present invention using a solvent having a high aniline point as the reflux solvent for the solvent method, the compatibility between the alkyd resin and the reflux solvent (I) and the condensed water generated by the esterification reaction between the carboxylic acid and the alcohol are used. Considering efficient discharge from the reaction system, the addition amount of the reflux solvent (I) is 0.5 to 5 parts by weight with respect to 100 parts by weight of the raw material component (II) used for the production of the alkyd resin. It is preferably 1 to 3.5 parts by weight.

  The alkyd resin obtained by the method for producing alkyd resin of the present invention can be used not only for paints such as architectural paints or construction machine paints, but also for inks and adhesives.

  Hereinafter, the present invention will be described more specifically with reference to Reference Examples, Examples and Comparative Examples, but the present invention is not limited thereto. In the examples, “part” and “%” are based on weight unless otherwise specified.

Example 1
A four-necked flask equipped with a stirrer, thermometer, reflux condenser with dehydration trap and nitrogen gas introduction device was charged with 505 parts of soybean oil, 0.13 parts of lithium hydroxide and 152 parts of pentaerythritol, and alcohol at 250 ° C. for 1 hour. After performing the exchange reaction, it was cooled to 180 ° C. Next, after adding 42 parts of ethylene glycol, 349 parts of phthalic anhydride and 31 parts of “Swclean 150” manufactured by Maruzen Petrochemical Co., Ltd., the temperature was gradually raised to 220 ° C. over 3 hours. The dehydration reaction was carried out for 10 hours, and then the non-volatile content was adjusted to 50% with butyl acetate. The acid value was 5.0 mgKOH / g, the hydroxyl value was 35.0 mgKOH / g, the weight average molecular weight was 35,400, and the number average molecular weight was 5,200. [Measured GPC using GPC “HLC-8220” manufactured by Tosoh Corporation.] Subsequent GPC was measured using the same apparatus. A 2,000 part solution of the alkyd resin (1) was obtained.

  The aromatic hydrocarbon content of the obtained alkyd resin solution (1) was determined by quantitative analysis using GC-MASS [GCMS “QP2010” manufactured by Shimadzu Corporation] (hereinafter quantitative determination of aromatic hydrocarbons). The analysis was also performed using the same apparatus.] However, it was 5 ppm.

Example 2
A four-necked flask equipped with a stirrer, thermometer, reflux condenser with dehydration trap and nitrogen gas introducing device was charged with 380 parts of linseed oil, 132 parts of tall oil fatty acid, 181 parts of trimethylolpropane and 0.20 part of lithium hydroxide. Then, after alcohol exchange reaction at 260 ° C. for 1 hour, the mixture was cooled to 180 ° C. Next, 300 parts of resol type phenolic resin “Beccasite M-342” (solid content 75.0%) manufactured by Dainippon Ink and Chemicals, Ltd., 232 parts of phthalic anhydride and 57 parts of “Isopar G” manufactured by ExxonMobil Co., Ltd. Then, the temperature was gradually raised to 220 ° C. over 5 hours, followed by a dehydration reaction at 240 ° C. for 10 hours, and then the non-volatile content was adjusted to 60% with butyl acetate to give an acid value of 15.0 mgKOH 2,000 parts of a solution of the alkyd resin (2) having a weight average molecular weight of 165,000 and a number average molecular weight of 3,200 was obtained. It was 4 ppm when aromatic hydrocarbon content of the obtained alkyd resin solution (2) was measured by GC-MASS.

Comparative Example 1
A four-necked flask equipped with a stirrer, thermometer, reflux condenser with dehydration trap and nitrogen gas introduction device was charged with 505 parts of soybean oil, 0.13 parts of lithium hydroxide and 152 parts of pentaerythritol, and alcohol at 250 ° C. for 1 hour. After performing the exchange reaction, it was cooled to 180 ° C. Next, after adding 46 parts of ethylene glycol, 349 parts of phthalic anhydride and 31 parts of xylene, the temperature was gradually raised to 220 ° C. over 3 hours, followed by a dehydration reaction at 220 ° C. for 8 hours. A solution of an alkyd resin (1 ') having an acid value of 5.0 mgKOH / g, a hydroxyl value of 35.0 mgKOH / g, a weight average molecular weight of 32,000, and a number average molecular weight of 5,000, with a nonvolatile content adjusted to 50% 000 parts were obtained. When the aromatic hydrocarbon content of the obtained alkyd resin solution (1 ′) was measured by GC-MASS, it was 50.2%.

Comparative Example 2
A four-necked flask equipped with a stirrer, thermometer, reflux condenser with dehydration trap and nitrogen gas introduction device was charged with 505 parts of soybean oil, 0.13 parts of lithium hydroxide and 152 parts of pentaerythritol, and alcohol at 250 ° C. for 1 hour. After performing the exchange reaction, it was cooled to 180 ° C. Next, 42 parts of ethylene glycol, 349 parts of phthalic anhydride and “Napper11” manufactured by ExxonMobil Co., Ltd. (containing 90 wt% or more of aliphatic hydrocarbons having 7 to 13 carbon atoms, but about 1 wt% of aromatic hydrocarbons) After adding 31 parts of the aliphatic hydrocarbon solvent to be contained, the temperature was gradually raised to 220 ° C. over 3 hours, followed by a dehydration reaction at 220 ° C. for 8 hours, and then 50% of non-volatile content with butyl acetate. %, An acid value of 5.0 mgKOH / g, a hydroxyl value of 35.0 mgKOH / g, a weight average molecular weight of 40,000, and a number average molecular weight of 5,500, 2,000 parts of an alkyd resin (2 ′) solution was obtained. It was. When the aromatic hydrocarbon content of the obtained alkyd resin solution (2 ′) was measured by GC-MASS, it was 600 ppm.

  If the alkyd resin obtained by the method for producing an alkyd resin of the present invention is used in a paint, the aromatic hydrocarbon contained in the paint can be reduced to 100 ppm or less, and the PRTR method (ascertainment of chemical substance emission) Because it becomes a non-target substance of the Management Promotion Act), it can greatly contribute to recent chemical substance management or environmental problems.

Claims (5)

In the presence of refluxing solvent (I) containing an aliphatic hydrocarbon and / or an alicyclic hydrocarbon having 7 to 13 carbon atoms and an aromatic hydrocarbon content of 100 ppm or less, animal or vegetable oil or its fatty acid ( A method of producing an alkyd resin, comprising reacting A), a polyhydric alcohol (B), and a raw material component (II) containing a polyvalent carboxylic acid (C). The method for producing an alkyd resin according to claim 1, wherein the reflux solvent (I) is an aliphatic hydrocarbon and / or an alicyclic hydrocarbon having 9 to 11 carbon atoms. The method for producing an alkyd resin according to claim 1 or 2, wherein the content of the aromatic hydrocarbon in the reflux solvent (I) is 10 ppm or less. Any of Claims 1-3 in which the said raw material component (II) contains a phenol resin (D) with animal and vegetable oil or its fatty acid (A), a polyhydric alcohol (B), and a polyhydric carboxylic acid (C). A method for producing the alkyd resin according to claim 1. The method for producing an alkyd resin according to any one of claims 1 to 4, wherein the amount of the reflux solvent (I) used is 0.5 to 5 parts by weight with respect to 100 parts by weight of the raw material component (II). .