JPH0410492B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a synthetic resin and a method for producing the same, and more specifically, a novel synthetic resin that, when used in conjunction with a crosslinking agent, provides a cured product with excellent physical and chemical properties and good adhesion to materials. This invention relates to synthetic resins and their manufacturing methods. Conventionally, synthetic resins used in paints, adhesives, etc. for wood, metal, and plastic have good adhesion to materials, and have chemical resistance, moisture resistance, water resistance, antibacterial properties,
It is required that the physical and chemical properties of the coating film, such as hardness and gloss, can be maintained over a long period of time. As such synthetic resins, unsaturated polyester resins, aminoalkyd resins, polyurethane resins, acrylic resins, epoxy resins, and the like are known, and are used as appropriate depending on the purpose. On the other hand, synthetic resins derived from hydroxyaryl compounds having unsaturated hydrocarbon groups are known. This resin is synthesized by utilizing the reactivity of the benzene nucleus of a hydroxyaryl compound, and among them, the resin obtained by addition condensation reaction with aldehydes has particularly good coating workability, aesthetic appearance, etc. It is widely used as a lacquer-like paint. However, paints using the above resins are
When forming a cured coating film, the curing reaction depends on the oxidative polymerization reaction of unsaturated hydrocarbon groups, so it takes a long time, and there are also problems in that bromination occurs due to oxidation. . Furthermore, there is a problem in that the adhesion of the cured film to the material is not necessarily good due to selectivity that is thought to be caused by the resin structure. The purpose of the present invention is to provide a new synthetic resin that solves the above-mentioned problems and provides a cured product that has excellent physical and chemical properties and has good adhesion to materials, and a method for producing the same. It is to be. As a result of extensive research into synthetic resins derived from hydroxyaryl compounds having unsaturated hydrocarbon groups, the present inventors discovered that hydroxyaryl compounds having unsaturated hydrocarbon groups and α,β unsaturated dibasic acids or The present inventors have discovered that the above object can be achieved by a polymer compound obtained by condensation polymerization of the addition product with the anhydride and, if necessary, half-esterification with a monohydric alcohol, and have completed the present invention. That is, the synthetic resin of the present invention has the following formula []: (In the formula, is an unsaturated aliphatic substituted phenol residue based on cashew shell oil, clay-treated cashew shell oil or distilled cashew shell oil,
R ¹ and R ² may be the same or different, respectively,
Further, each unit may be the same or different and represents a hydrogen atom, a hydroxyl group, or a saturated hydrocarbon group having 1 to 5 carbon atoms, and R ³ is a carbon number having 1 to 3 unsaturated double bonds. Represents 15 to 20 hydrocarbon groups, A
teeth

[Formula] or

[Formula] (wherein, R ⁴ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 5 carbon atoms), m is an integer of 0 to 2, and n is 2 to 10 is an integer. However, multiple A
may be the same or different. ) It is characterized by having a main chain shown in the following. The synthetic resin represented by the formula [] of the present invention contains a phenyl ester bond in its skeleton structure and has a reactive functional group in its side chain. In the above formula, R ¹ and R ² are a hydrogen atom, a hydroxyl group, or a linear or branched hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Also, R ³ is, for example, Represents a divalent to tetravalent unsaturated hydrocarbon group having 15 to 20 carbon atoms and having 1 to 3 unsaturated double bonds.
pieces are used. Furthermore, the A added to R ³ is

[Formula] or

[Formula], multiple A's may be the same or different, and R ⁴ is a linear or branched hydrocarbon group such as a methyl group, ethyl group, propyl group, butyl group, or pentyl group. be. When m is 0, that is, even when A is substituted with a hydrogen atom, a cured product with appropriate flexibility can be obtained, but in order to obtain a cured product with sufficient crosslink density, m must be 1. It is preferable that it is -2.
Further, the number n of repeating units must be in the range of 2 to 10. By using a resin having a molecular weight within this range, a cured product with excellent physical and chemical properties and good adhesion to the material can be obtained. When n exceeds 10, the viscosity becomes high and workability such as fluidity deteriorates, causing poor adhesion. When using the above resin, for example, it is possible to use an epoxy resin as a crosslinking agent and to obtain a cured product by mixing appropriate amounts of both. The curing reaction is
For example, it can be carried out using 1 PHR of tridimethylaminomethylphenol as a catalyst under heating conditions of 100° C. for 30 minutes. Epoxy resins used as crosslinking agents include, for example, bisphenol A, bisphenol F, or polyfunctional glycidyl ethers such as glycerin, polyoxyethylene glycol, and polyoxypropylene glycol; epoxy resins such as acrylic acid or methacrylic acid; Glycidyl ester type epoxy resin such as glycidyl ester copolymer,
Examples include alicyclic epoxy resin, epoxidized oil, and epoxidized polybutadiene. The method for producing a synthetic resin having a main chain represented by the formula [] of the present invention includes: (a) adding cashew shell oil, clay-treated cashew shell oil, or distilled cashew shell oil to maleic acid, maleic anhydride, or fumaric acid; (c) The reaction product formed is the formula []: (In the formula, R ¹ , R ² , R ³ , A, and m have the same meanings as above.) The compound represented by It is characterized by half-esterification with a saturated alcohol. The condensation polymerization is preferably carried out at a temperature in the range of 80°C to 240°C, and more preferably in the presence of an esterification catalyst. Examples of the esterification catalyst used in the present invention include known catalysts such as alkali metal compounds such as sodium methoxide, sodium oleate, and anhydrous potassium carbonate; amine compounds such as pyridine, triethylamine, and diethylbenzylammonium chloride; Can be mentioned. Formula used in the manufacturing method of the present invention []
The compound represented by can be obtained, for example, by an addition reaction between a hydroxyaryl compound having an unsaturated hydrocarbon group containing 1 to 3 double bonds and an α,β unsaturated dibasic acid and/or its anhydride. and, if necessary, the acid anhydride group has 1 to 5 carbon atoms.
The desired product can be easily obtained by partially half-esterifying it with a saturated monohydric alcohol. Alternatively, a part of the hydroxyaryl compound having an unsaturated hydrocarbon group may be replaced with a compound having no hydroxyaryl group but having an unsaturated double bond and a hydroxyaryl compound having no unsaturated hydrocarbon group. You may do so. The above reaction is preferably carried out at a temperature of, for example, 80 to 240°C, and more preferably carried out in the presence of a known catalyst such as a peroxide or an iodine compound to accelerate the reaction. Furthermore, prior to the start of the above reaction, the unsaturated hydrocarbon compound containing an unsaturated double bond is used after being subjected to an isomerization treatment using an isomerization catalyst such as activated clay, an iodine compound, an alkali metal compound, etc. is preferable because the addition reaction can be carried out more advantageously. In the production method of the present invention, after obtaining the compound represented by the formula [], it is subjected to polycondensation polymerization, and then, if necessary, the acid anhydride group is monomerized with a monohydric saturated alcohol having 1 to 5 carbon atoms. The condensation polymerization is partially or completely half-esterified, but the condensation polymerization is carried out following the addition reaction between the above-mentioned hydroxyaryl compound having an unsaturated hydrocarbon group and an α,β unsaturated dibasic acid, or in combination with the addition reaction. At the same time, a polycondensation reaction may be carried out, and if necessary, the acid anhydride group may be half-esterified with a monohydric alcohol. Examples of the hydroxyaryl compound having an unsaturated hydrocarbon group used in the above reaction include monovalent hydroxyaryl compounds such as cardanol and gingol; divalent hydroxyaryl compounds such as urushiol, bilawanol, latcol, thithiol, and lenggol; phenol , polycondensation products of hydroxyaryl compounds such as cresol, xylenol, and catechol and higher alcohol compounds having unsaturated double bonds such as oleyl alcohol and linseed oil alcohol. High cardanol is preferred. Examples of the α,β unsaturated dibasic acid or its anhydride include maleic anhydride, maleic acid, fumaric acid, and derivatives thereof. These may be used alone or in combination, but maleic anhydride is preferred because of its high reactivity in addition and polycondensation. In the above addition reaction, α, β to the hydroxyaryl compound having an unsaturated hydrocarbon group
It is preferable that the amount of the unsaturated diacid base acid and/or its anhydride used is in a molar ratio of 1.0 to 3.0. When the molar ratio is less than 1.0, unreacted substances tend to remain,
A cured product with sufficient performance cannot be obtained. on the other hand,
If it exceeds 3.0, it tends to have a branched structure, which makes it difficult to control the molecular weight, increases viscosity, and reduces fluidity, resulting in poor workability. In addition, examples of unsaturated hydrocarbon compounds having an unsaturated double bond that can be used as substitutes for the hydroxyaryl compound having an unsaturated hydrocarbon group having an unsaturated double bond include terpenes, rosins, and low molecular weight polybutadienes. and unsaturated fatty acids. Furthermore, hydroxyaryl compounds include, for example, monovalent hydroxyaryl compounds such as phenol, cresol, and xylenol; divalent hydroxyaryl compounds such as catechol, resorcinol, and hydroquinone; and P-oxybenzoic acid,
Examples include salicylic acid, bisphenol A, bisphenol F, and alkylphenol resins. The total amount of the unsaturated hydrocarbon compound and hydroxyaryl compound used in the addition condensation reaction is preferably in a molar ratio of not exceeding 0.5 to the hydroxyaryl compound having an unsaturated hydrocarbon group. If it exceeds 0.5, unreacted substances may remain or the molecular weight may decrease, resulting in insufficient performance of the cured product. Monohydric alcohols for half-esterifying the acid anhydride groups remaining after addition and condensation polymerization include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, t-butyl alcohol, and pentyl alcohol. lower alcohols such as; glycol ethers such as ethylene glycol monoethyl ether and ethylene glycol monoallyl ether; and amino alcohols such as dimethylethanolamine and diethylethanolamine. The amount of these monohydric alcohols used is preferably 0 to 1.5 mol based on the acid anhydride group, and they may be used alone or in combination. The present invention will be explained in more detail below with reference to Examples and Experimental Examples. Example 1 In a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser, 600 g of cashew shell oil and activated clay (Galeon Earth H, trade name: Mizusawa) dried at 110°C for 3 hours were added. (manufactured by Kagaku Co., Ltd.) 12
After stirring at 220° C. for 1 hour, the mixture was cooled to 120° C. and sifted while hot to obtain 550 g of clay-treated cashew shell oil. 300g of the above white clay treated cashew shell oil and 196g of maleic anhydride were placed in the above container, and heated at 200℃ under stirring.
After reacting for 16 hours, it was cooled to 125°C. When 148 g of isobutyl alcohol was added to this reaction solution and the reaction was continued for another hour at the same temperature with stirring, a resin solution with a nonvolatile content of 90% and a viscosity of 100 poise (number average molecular weight Mn: approximately 1600) at 50°C was obtained. Obtained. Example 2 Using the same apparatus as in Example 1, 300 g of distilled cashew shell oil obtained by previously distilling cashew shell oil under reduced pressure,
75 g of rosin and 220 g of maleic anhydride were added under stirring.
The reaction was carried out at 200°C for 16 hours. After cooling the reaction solution to 125°C, 167g of isobutyl alcohol was added.
When the reaction was continued for an additional hour at the same temperature with stirring,
A resin solution with a non-volatile content of 80% and a viscosity at 50° C. of 120 poise (Mn: about 1800) was obtained. Example 3 Using the same apparatus as in Example 1, 300 g of distilled cashew shell oil obtained by distilling cashew shell oil under reduced pressure, 57 g of bisphenol A, and 196 g of maleic anhydride,
The reaction was carried out at 200° C. for 16 hours while stirring. 125% reaction solution
After cooling to ℃, 148g of isobutyl alcohol was added and the reaction was continued at the same temperature for 1 hour with stirring, resulting in a non-volatile content of 87% and a viscosity at 50℃.
A resin solution having a poise of 110 (Mn: approximately 1650) was obtained. Example 4 Using the same apparatus as in Example 1, 300 g of distilled cashew shell oil obtained by distilling cashew shell oil under reduced pressure and 172 g of maleic anhydride were reacted at 200° C. for 14 hours with stirring. Next, phenolic resin (nicanol)
110 g of HP210 (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added to the reaction mixture, and the reaction was further carried out at 200° C. for 2 hours with stirring. The reaction mixture was cooled to 80°C, 105g of isopropyl alcohol was added, and the reaction was continued at the same temperature for another 3 hours with stirring, resulting in a non-volatile content of 90% and a viscosity of 120 poise (Mn: approx. 1700) at 50°C. A resin solution containing the following properties was obtained. Experimental Example 1 Using each of the resins obtained in Examples 1 to 4, epoxy resin (Epiyute #828, trade name; epoxy equivalent 175 to 210, bisphenol) was added to the resins in the amounts listed in Table 1 below. A type epoxy resin (manufactured by Ciel Chemical Co., Ltd.) was added to obtain a resin composition. These resin compositions were cured, and the resulting cured coatings were tested for pencil hardness, impact resistance using a Teipon impact tester, Erichsen value, interlock adhesion, solvent resistance, and the like. The results are also listed in Table 1. At the same time, as a comparative example, an aromatic acid type oil-free polyester having a carboxyl group at the end was used instead of the synthetic resin of the present invention, and glycerin diglycidyl ether was used as a crosslinking agent. The same tests as above were conducted on the composition prepared in the above manner. The results are also listed in Table 1.

[Table] As is clear from the above results, it was confirmed that the cured coating film of the synthetic resin of the present invention has excellent physical and chemical properties such as adhesion, solvent resistance, and hardness. . Further, the method for producing a synthetic resin of the present invention makes it possible to produce a synthetic resin with excellent performance through a simple process.

Claims (1)

[Claims] 1 Formula []: (In the formula, is an unsaturated aliphatic substituted phenol residue based on cashew shell oil, clay-treated cashew shell oil or distilled cashew shell oil, and R ¹ and R ² may be the same or different, respectively, and each unit may be the same or different and represent a hydrogen atom, a hydroxyl group, or a saturated hydrocarbon group having 1 to 5 carbon atoms, and R ³ is a group having 15 to 20 carbon atoms and having 1 to 3 unsaturated double bonds. represents a hydrocarbon group, A represents a group represented by [formula] or [formula] (in the formula, R ⁴ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 5 carbon atoms), and m represents a group represented by It is an integer of 0 to 2, and n is an integer of 2 to 10. However, multiple A
may be the same or different. ) A synthetic resin characterized by having a main chain represented by: 2 (a) to (b) maleic acid, maleic anhydride or fumaric acid added to cashew shell oil, clay-treated cashew shell oil or distilled cashew shell oil, and (c) the reaction product formed is the formula [] : (In the formula, R ¹ and R ² may be the same or different, and each has a hydrogen atom, a hydroxyl group, or a carbon number of 1
~5 saturated hydrocarbon groups, R ³ is 1~
A represents a hydrocarbon group having 15 to 20 carbon atoms and having ³ unsaturated double bonds; represents a hydrocarbon group), where m is an integer of 0 to 2. However, the plural A's may be the same or different. ) is formed by polycondensation of the compound represented by (d), and the remaining acid anhydride group is half-esterified with a monohydric saturated alcohol []: (In the formula, is an unsaturated aliphatic substituted phenol residue based on cashew shell oil, clay-treated cashew shell oil or distilled cashew shell oil, R ¹ , R ² , R ³ , A and m have the same meanings as above, and n is an integer between 2 and 10. ) A method for producing a synthetic resin having a main chain represented by: 3 The compound represented by formula [] is a hydroxyaryl compound having a hydrocarbon group having 15 to 20 carbon atoms and having 1 to 3 unsaturated double bonds, and α, β
-Produced by addition reaction with an unsaturated dibasic acid and/or its acid anhydride, or further half-esterifying the remaining acid anhydride group with a monohydric saturated alcohol having 1 to 5 carbon atoms. A method for producing a synthetic resin according to claim 2.