JPS6154813B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to 3-pentadiene obtained by Diers-Alder addition of 1,3-pentadiene and maleic anhydride.
-One of the four stereoisomers of methyltetrahydrophthalic anhydride. This invention relates to a method for producing an alkyd resin that effectively takes advantage of the air curing properties of 1,2,3,6-tetrahydro-cis-3-methyl-cis-cis-phthalic anhydride (hereinafter abbreviated as PMAA). . It is generally known that PMAA has air curing properties. In addition, at temperatures above 200℃,
It is also known that air curing properties are lost because the cis structure of PMAA is rearranged to a trans structure. Therefore, in order to take advantage of PMAA's ability to provide air curing, it is necessary to carry out the reaction at a temperature of 200°C or lower, preferably 180°C or lower. However, production of alkyd resin generally requires a temperature of 200°C or higher, and a reaction temperature of 180°C or lower takes a long time and is not economical. Therefore, we investigated various ways to economically produce alkyd resin in a short time by taking advantage of the air curing properties of PMAA, and found that the carboxylic acid raw material and the alcohol raw material, which do not contain PMAA, are heated at a temperature of 200°C or higher, preferably 220 to 260°C. After precondensation at a temperature of 180 °C, the precondensate
Cool down to a temperature below 180°C and then heat the PMAA to 180°C.
We have discovered that by completing the condensation reaction at the following temperature (preferably 150 to 180°C), it is possible to significantly shorten the reaction time and to effectively utilize the unique reactivity of the unsaturated groups in PMAA. . Medium-length oil alkyd resins are used in paints that dry at room temperature by taking advantage of the air-curing properties of oil, but PMAA
By introducing this, an alkyd resin with even higher air curability and excellent drying properties can be produced. Short oil alkyd resin ~
When used in baking amino alkyd resin paints such as oil-free alkyd resins, the hardness and flexibility of the paint film can be improved by introducing PMAA. In order to further shorten the reaction time and more effectively retain the reactivity of the unsaturated groups in PMAA, it is possible to further shorten the reaction time by adding a compound that has one or more epoxy groups in one molecule. Moreover, by selecting the compound having an epoxy group to be used, it is possible to impart the characteristics of an epoxy compound (for example, if a bisphenol type epoxy resin is used, the corrosion resistance, adhesion, water resistance, etc. of the coating film will be improved). I can do it. The method for producing the alkyd resin of the present invention is not limited to any other method except that it must contain PMAA; pure alkyd resin containing oil, modified alkyd resin (phenol modification, rosin modification, urethane modification, etc.), oil content It is used for oil-free alkyd resins that do not contain any Therefore, commonly used raw materials can be used. Further, the reaction may be carried out by either a solvent method or a melt method, but the solvent method is advantageous in terms of reaction time. The amount of PMAA used is 0.1% by weight or more, preferably 0.5-10% by weight in the alkyd resin. The precondensation reaction before adding PMAA is preferably carried out at a temperature of 200°C or higher, preferably 220 to 260°C, and the reaction is preferably allowed to proceed until the acid value reaches 20 or lower. Epoxy compounds that are reacted together with PMAA at temperatures below 180°C are substances that have one or more epoxy groups in one molecule, such as Cardiura E10.
(manufactured by Ciel Chemical Co., Ltd., glycidyl ester of versatile acid), bisphenol A type epoxy resin (manufactured by Dainippon Ink and Chemicals Co., Ltd., Epiclon)
840, Epiclon 1050, Epiclon 4050, etc.), styrene oxide, allyl glycidyl ether,
Ethylene oxide, propylene oxide, allocimene dioxide, AOE (manufactured by Daicel Corporation, long-chain monoepoxide obtained by reaction with α-olefin), and the like can be used. EXAMPLES Next, the content of the present invention will be specifically explained using examples, but the present invention is not limited to these examples. Note that the blended parts of raw materials used in the examples are parts by weight unless otherwise specified. Comparative Example 1 650 parts of soybean oil, 135 parts of pentaerythritol, and 0.3 parts of lithium hydroxide were placed in a reaction vessel equipped with a thermometer, a stirrer, a water separator, and an inert gas introduction tube, and the mixture was heated in an inert gas atmosphere. Raise the temperature while stirring
After maintaining the temperature at 250°C for 1 hour to carry out the transesterification reaction, the temperature was lowered to 200°C. Next, 245 parts of phthalic anhydride and 30 parts of xylene were charged, and the temperature was raised to 240°C over 2 hours while removing condensed water. The reaction was kept at that temperature for 7 hours to complete the reaction.
When diluted with mineral turpentine to a non-volatile content of 70%, the acid value was 4.0 and the Gardner viscosity (hereinafter abbreviated as viscosity) was Z-Z. To the obtained alkyd resin solution, 25% lead naphthenate and 5% cobalt naphthenate were added to the alkyd resin solid content at 1% each.
Table 1 shows the coating film performance of clear paints containing 2% and 2%. Comparative Example 2 A condensation reaction was carried out in the same manner as in Comparative Example 1, except that 245 parts of phthalic anhydride was replaced with 50 parts of PMAA and 199.6 parts of phthalic anhydride at a temperature of 240°C for 7 hours. The resulting resin contains mineral turpentine and non-volatile content.
When diluted to 70%, the acid value was 4.5 and the viscosity was YZ. A paint made using the obtained resin solution in the same manner as in Comparative Example 1 had slightly poorer drying properties than Comparative Example 1. The results are shown in Table-1. Comparative Example 3 Using the same raw material composition as Comparative Example 2, only xylene was increased to 100 parts and the condensation reaction was carried out at a temperature of 180°C.
It took 45 hours. When this resin was diluted with mineral turpentine to a non-volatile content of 70%, it had an acid value of 5.0 and a viscosity of W. Comparative Example 1 using the obtained resin solution
A paint made in the same manner as Comparative Example 1 had better drying properties. The results are shown in Table-1. Example 1 The same raw material composition as Comparative Example 2 was used, but a precondensation reaction was performed in the same manner as in Comparative Example 2 except that PMAA was added. The reaction time at 240°C was 3 hours. The acid value at that time was 9.5. After that, the temperature dropped to 180℃.
Add 50 parts of PMAA and 70 parts of xylene at a temperature of 170°C.
The condensation reaction was continued for 10 hours and diluted with mineral turpentine to a non-volatile content of 70%. The result is acid value 6.5, viscosity V
It was hot. A paint made using this resin solution in the same manner as Comparative Example 1 had better drying properties than Comparative Examples 2 and 3. The results are shown in Table-1. Example 2 600 parts of soybean oil, 158 parts of pentaerythritol, and 0.3 parts of lithium hydroxide were charged into the same equipment as in Comparative Example 1, and the temperature was raised while stirring in an inert gas atmosphere.
The temperature was maintained at 250°C for 1 hour to carry out the transesterification reaction, and then the temperature was lowered to 200°C. Then phthalic anhydride 230
The mixture was heated to 240° C. over 2 hours while adding 30 parts of xylene and removing condensation water, and the condensation reaction was carried out at that temperature for 3 hours. The acid value at that time is
It was 8.5. After the temperature was lowered to 180℃, 150 parts of Cursula E10 and 50 parts of PMAA were added, and the reaction was carried out for 3 hours at a temperature of 170℃.
When diluted to 70%, the acid value was 5.2 and the viscosity was V-W. A paint made using the obtained resin solution in the same manner as in Comparative Example 1 had excellent drying properties. The results are shown in Table 1. Example 3 750 parts of soybean oil, 87 parts of pentaerythritol, and 0.35 parts of lithium hydroxide were charged into the same apparatus as in Comparative Example 1, and the temperature was raised while stirring in an inert gas atmosphere.
The temperature was maintained at 250°C for 1 hour to carry out the transesterification reaction, and then the temperature was lowered to 200°C. Then phthalic anhydride
117.5 parts and 30 parts of xylene were added, and the temperature was raised to 240° C. over 2 hours while removing condensed water, and maintained at that temperature for 3 hours. The acid value at this time was 8.0. After that, the temperature dropped to 180℃,
75 parts of PMAA, Epicron 1050 (bisphenol type epoxy resin manufactured by Dainippon Ink & Chemicals KK)
150 parts and 100 parts of xylene were added, a condensation reaction was carried out at 170°C for 10 hours, and the nonvolatile content was diluted to 70% with mineral turpentine. The results were an acid value of 6.5 and a viscosity of _Z2 - _Z3 . A paint made using the obtained resin solution in the same manner as in Comparative Example 1 had excellent drying properties and corrosion resistance. The results are shown in Table-1. Comparative Example 4 400 parts of soybean oil, 161 parts of methylbenzoic acid, 207 parts of pentaerythritol, and 0.2 parts of lithium hydroxide were placed in the same equipment as in Comparative Example 1, and heated to 250°C while stirring in an inert gas atmosphere. After keeping it for 1 hour, the temperature was lowered to 200°C. Then phthalic anhydride 288
35 parts of xylene was added and the temperature was raised to 230°C over 2 hours while removing condensed water, and the condensation reaction was continued at that temperature for 5 hours and diluted to 50% non-volatile content with Swazol 310 (solvent manufactured by Maruzen Sekiyu). . The result is the acid value
7.3, viscosity W-X. Table 1 shows the performance of a paint made using the obtained resin solution in the same manner as in Comparative Example 1. Example 4 The same equipment as Comparative Example 1 was used, except that 288 parts of phthalic anhydride was replaced with 30 parts of PMAA and 260.8 parts of phthalic anhydride.
250℃ as in Comparative Example 4 with the composition excluding PMAA.
After keeping the temperature at 1 hour, the temperature was lowered to 180°C, 260.8 parts of phthalic anhydride and 35 parts of xylene were added, the temperature was raised to 230°C over 2 hours, and a precondensation reaction was carried out at that temperature for 3 hours. . The acid value at that time was 15.0. Thereafter, the temperature was lowered to 180°C, 30 parts of PMAA and 100 parts of xylene were added, and the mixture was reacted at a temperature of 170°C for 5 hours, and diluted with Swasol 310 to a non-volatile content of 50%. The results were an acid value of 8.5 and a viscosity of R-S. A paint made using the obtained resin solution in the same manner as Comparative Example 1 had better drying properties than Comparative Example 4. The results are shown in Table-1. Comparative Example 5 423 parts of isophthalic acid was added to the same apparatus as in Comparative Example 1.
Adipic acid 227 parts, trimethylolpropane 256 parts
1 part, 299 parts of neopentyl glycol, and 0.25 part of di-n-butyltin oxide were charged, and the temperature was raised to 150° C. with stirring in an inert gas atmosphere. While removing condensation water, the temperature was raised to 220°C over 5 hours, kept at that temperature for 10 hours to perform condensation retention, and Swazol 1500 (solvent manufactured by Maruzen Sekiyu) / Cellosolve Acetate = 9/1 (weight ratio) Non-volatile content in solvents of 60
diluted to %. The results were an acid value of 3.0 and a viscosity of _Z2 . For comparison with Example 5, the performance of an aminoalkyd resin paint using a mixture of 16.7 parts of Epiclon 1050 diluted to 60% non-volatile content with xylene per 100 parts of the solid content of this resin solution is shown in Table 2. Shown below. Example 5 In Comparative Example 5, 423 parts of isophthalic acid was replaced with 25 parts of PMAA.
The composition was the same except that 400 parts of isophthalic acid was substituted, and first the temperature was raised from 150 °C to 220 °C over 5 hours with stirring in an inert gas atmosphere, and at that temperature 8 A precondensation reaction was carried out for a certain period of time. The acid value at that time was 9.0. After the temperature was lowered to 180°C, 25 parts of PMAA and 110 parts of Epiclon 1050 were added, and after reacting at 170°C for 3 hours, the mixture was diluted to a non-volatile content of 50% with a solvent of Swazol 1500/Cellosolve Acetate = 9/1. The result is the acid value
4.5, and the viscosity was _Z4 . The amino alkyd resin paint using the obtained resin solution was superior to Comparative Example 5 in corrosion resistance, hardness, and flexibility. The results are shown in Table-2.

【table】

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1 1,2,3,6-tetrahydro-cis-3-
When producing an alkyd resin using methyl-cis-cis-phthalic anhydride as part of the carboxylic acid raw material,
After precondensing a carboxylic acid raw material that does not contain 1,2,3,6tetrahydro-cis-3-methyl-cis-cis-phthalic anhydride and an alcohol raw material, 1. 2・3・6
A method for producing an alkyd resin, which comprises adding -tetrahydro-cis-3-methyl-cis-cis phthalic anhydride to carry out a condensation reaction.