JPS6023416A - Synthetic resin and its preparation - Google Patents

Abstract

PURPOSE:To obtain a synthetic resin useful as a coating compound similar to URUSHI (japanese lacquer), etc., providing a cured material having improved adhesiveness to a material, by subjecting an addition product of a specific hydroxyaryl compound with an alpha,beta-unsaturated dibasic acid (anhydride) to polycondensation. CONSTITUTION:A hydroxyaryl compound (preferably cardanol) having 1-3 unsaturate double bonds, containing 15-20C hydrocarbon group and an alpha,beta-unsaturated dibasic acid (anhydride) (preferably maleic acid) are subjected to addition reaction to a compound shown by the formula I [R1 and R2 are H, OH, or 1-5C saturated hydrocarbon; R3 is 15-20C hydrocarbon containing 1-3 unsaturated double bonds; A is group shown by the formula II or formula III(R4 is H, or 1-5C saturated hydrocarbon); m is 0-2; n is 2-10], which is subjected to polycondensation, and, if necessary, the remaining acid anhydride group is subjected to half esterification with a monohydric alcohol (e.g., methyl alcohol), to give the desired synthetic resin shown by the formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION In detail, 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; Regarding the manufacturing method.

Conventionally, synthetic resins used for paints, adhesives, etc. for wood, metal, and plastics have good adhesion to materials and have properties such as chemical resistance, moisture resistance, water resistance, antibacterial property, hardness, and gloss. It is required that the physical and chemical properties of the coating film can be maintained over a long period of time. Such synthetic resin and l-
So, unsaturated polyester resin, amino alkyd resin,
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 and aesthetic appearance. , is widely used as a lacquer-like coating. However, when forming a cured coating film using the above-mentioned resins, the curing reaction depends on the oxidative polymerization reaction of the hydrocarbon groups, so it takes a long time. There is a problem that odor is generated by
I'm here. 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 novel 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 fibers, and a method for producing the same. The goal is to provide the following.

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 The present inventors have discovered that a polymer compound obtained by condensation polymerization of an addition product with an acid or its anhydride and, if necessary, halfesterization with a monohydric alcohol can achieve the above object, and has completed the present invention. .

That is, the synthetic resin of the present invention has the following formula [1]: (wherein R1
and R2 may be the same or different, and 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,
R3 has 1 to 3 unsaturated double bonds and has 15 or more carbon atoms
Represents 20 hydrocarbon groups, A is 1CH CH2 or -CH ” CH2 C OR
'1 1 1 11 (in the formula, R 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 It is an integer between ~10. However, the plural A's may be the same or different. ).

The synthetic resin represented by formula [I] 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, R1 and R2 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. Further, R3 is, for example, (CH2)7C,E(=CI-CH
-(CR2) 3 CR3, (C112)7CH= C
H-CI (-CH= represents a di- to tetravalent unsaturated hydrocarbon group having 15 to 20 carbon atoms, such as CH-CHCH2CH, 3, and has 1 to 3 unsaturated double bonds) Furthermore, A is added to R3 (-J), and multiple A's may be the same or different, R drop methyl group, ethyl group, propyl group, butyl, pentyl group, etc. It is a linear or branched hydrocarbon group.

Even when m is 0, that is, when A is substituted with a hydrogen atom, a hard material with appropriate flexibility can be obtained, but in order to obtain a hard material with sufficient crosslink density, is m
If it is 1 to 2, power ≦ childish.

Further, the number n of repeating units needs to 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.

l] exceeds 10, the viscosity becomes high and workability such as fluidity deteriorates, resulting in poor adhesion.

When using the above resin, for example, an epoxy resin is used as the bridge 4 and 11, and both are mixed in appropriate amounts.

It is possible to obtain a cured product. The curing reaction can be carried out under thermothermal conditions of 100 DEG C. for 30 minutes using, for example, tridimethylaminomethylphenol of IPHR as a catalyst.

Examples of epoxy resins used as crosslinking agents include EVA, bisphenol A, and bisphenol F.

Or polyfunctional grindyl ether type epoxy resin such as glycerin, polyoxyethylene glycol, polyoxypropylene glycol; grindyl ester copolymer of acrylic acid or methacrylic acid ￥s7) ylinodyl ester type epoxy/resin, resin Examples include J-type epoxy resin, epoxy resin, and epoxidized polybutadiene.

The method for producing a synthetic resin represented by formula [1] of the present invention is represented by formula [11] 1 R1' (wherein R', R2, R3, A and m have the same meanings as above) It is characterized by condensing and polycondensing the compound, and then, if necessary, converting the remaining acid anhydride group with a monovalent saturated alkyl having 1 to 5 carbon atoms. The condensation polymerization is preferably carried out at a temperature of 80°C to 2406°C, and more preferably in the presence of an esterification catalyst. Examples of the esterification catalyst used in the present invention include alkali metal compounds such as sodium methoxide, sodium oleate, and anhydrous potassium carbonate; amine compounds such as pyridine, ethylamine, and diethylbenzylammonium chloride; Examples include:

The compound represented by formula [11] used in the production method of the present invention is, for example, a hydroxyaryl compound having an unsaturated hydrocarbon group containing 1 to 3 double bonds, an α,β unsaturated dibasic acid and/or Or, it can be obtained by an addition reaction with its anhydride, and if necessary, the acid anhydride group can be added to an acid anhydride group having 1 to 5 carbon atoms. The desired product can be easily obtained by esterification. In addition, some of the hydroxyaryl compounds having an unsaturated hydrocarbon group are
The reaction may be carried out by replacing the compound with an unsaturated double bond and a hydroxyaryl compound without an unsaturated hydrocarbon group.

The above reaction is preferably carried out at a temperature of 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. Prior to the start of the reaction, an unsaturated hydrocarbon compound containing an unsaturated double bond is subjected to an isomerization treatment using an isomerization catalyst such as an active white compound, an iodine compound, an alkali metal compound, etc. It is preferable that 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 CII), it is subjected to polycondensation, and if necessary, the acid anhydride group is monomerized with a monohydric saturated alcohol having 1 to 5 carbon atoms. ZQ is partially or completely 7-phesterified, but the condensation polymerization reaction is carried out simultaneously with the above-mentioned unsaturation or i-addition reaction, and if necessary, the acid anhydride group is oxidized with a monohydric alcohol.・-It may be esterified.

The hydroxyaryl compounds having an unsaturated hydrocarbon group used in the above reaction include, for example, monovalent hydroxyaryl compounds such as cardanol and gingol; divalent hydroxyaryl compounds such as urunol, bilawanol, ratucol, thithiol, and cresol; phenol; Examples include condensation 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, but -valent hydroxyaryl compounds with high reactivity 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 can be used alone,
Although they may be used in combination, maleic anhydride is preferred because of its high reactivity in addition and polycondensation.

In the above addition reaction, it is preferable that the molar ratio of the α, β unsaturated dimer and/or anhydride thereof to the hydroxyaryl compound having an unsaturated hydrocarbon group is 10 to 30. If the molar ratio is less than 0, unreacted materials tend to remain and a cured product with sufficient performance cannot be obtained. On the other hand, if it exceeds 3.0, it tends to form a branched structure, making it difficult to control the molecular weight and increasing the viscosity.
Workability deteriorates due to the decrease in performance.

Further, examples of the unsaturated hydrocarbon compound having an unsaturated double bond that can be substituted with the hydroxyaryl compound having an unsaturated hydrocarbon group having an unsaturated double bond include terpene, rosin, and low molecular weight polybutadiene. and unsaturated fatty acids. Furthermore, examples of hydroxyaryl compounds include monohydric aryl compounds such as hafenol, cresol and xylenol; divalent hydroxyaryl compounds such as catechol, resolun and hydroquinone; and 1]-oxybenzoic acid, salicylic acid, bisphenol A, bisphenol. F.

Examples include alkylphenol resins.

The total amount of the unsaturated hydrocarbon compound and hydroxyaryl compound used in the addition condensation reaction is within a range of from 1 to 0.5 molar ratio to the hydroxyaryl compound having an unsaturated hydrocarbon group. preferable. 0
．． When it exceeds 5, the molecular weight of 9 remaining as unreacted substances decreases, resulting in insufficient performance of the cured product.

Addition and /II! 1. In the future, if necessary, add a monohydric alcohol and L4 to halfesterize the remaining acid anhydride group.
i1 Chyl alcohol, ethyl alcohol, flobyl alcohol, isopropyl alcohol, butyl alcohol,
Lower ethers such as isobutyl alcohol, t-butyl alcohol, and hyventyl alcohol; amino alcohols such as dimethylethanolamine and diethylethanolamine can be used. The amount of the equivalent alcohol used is preferably 0 to 1.5 mol based on the acid anhydride group, and 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 Removing the stirrer, thermometer, nitrogen inlet pipe, and reflux condenser
(=60 liters of cashew shell oil in 11 solo flasks)
Add 12 g of activated clay (Galleon Earth ■ (product name; manufactured by Mizusawa Kagaku ■) dried at 0 g and 110 °C for 3 hours,
After stirring at 220° C. for 1 hour, the mixture was cooled to 120° C. and heated for 1-1 hours to obtain 550 g of clay-treated cashew shell oil.

300 g of the above-mentioned white clay processing power/knee grain oil and 196 g of maleic anhydride were placed in the container, reacted with stirring at 200°C for 16 hours, and then cooled to 125°C. When 148.9% of isobutyl alcohol was added to this reaction solution and the reaction was continued at the same temperature for an hour with stirring, the non-volatile content was 90% and the viscosity at 50°C was 100 poise (number average molecular weight M
A resin solution with n: about 1600) was obtained.

Example 2 Using the same apparatus as in Example 1, 300 g of distilled cashew shell oil obtained in advance from vacuum distillation 1 to 75 rosin.
g and 220 g of maleic anhydride were reacted at 200° C. for 16 hours with stirring. After cooling the reaction solution to 125°C,
When Inobutyl Alcohol 1671 was added and the reaction was further carried out at the same temperature for 1 hour with stirring, the non-volatile content was 80% and the viscosity at 50°C was 120 poise (Mn: about 180
0 ) was obtained.

Example 3 300 g of distilled cashew shell oil obtained by distilling cashew shell oil under reduced pressure using the same equipment as in Example 1, and bisphenol A.
57.9 and 196 g of anhydrous maleic e were reacted at 200° C. for 16 hours with stirring. The reaction solution was heated to 125°C.
After cooling to a temperature of
A resin solution having a n of about 1650 was obtained.

Example 4 Using the same apparatus as in Example 1, 300 g of distilled cashew shell oil obtained from vacuum distillation 1 to 1 and 172 g of maleic anhydride were reacted at 200° C. for 14 hours with stirring. Then, apply Kanol HP 210 to the phenolic resin.
(trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.) IIOg 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, 105.9 t of isopropyl alcohol was added, and an additional 3 t was added at the same temperature under stirring.
After reacting for a period of time, a resin solution having a non-volatile content of 90% and a viscosity of 120 poise (Mll: about 1700) at 50°C was obtained.

Experimental Example 1 Using each of the resins obtained in Examples 1 to 4, epoxy resin (Epinete+-828, trade name; epoxy resin M175-2
10, Bisphenol A type epoxy resin, / L Chemical ■
) was added to obtain a resin composition.

These resin compositions were cured, and the resulting cured coating film was tested for pencil hardness, impact resistance using a Tibon impact tester,
Erichsen value, interlock adhesion, solvent resistance, etc. were tested. 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 terminal carboxyl group was used instead of the synthetic resin of the present invention, and the crosslinking agent and (-) were all the same except that glycerin diglycidyl ether was used. The same test as above was conducted on a composition prepared using the same.

The results are also listed in Table 1.

As is clear from the following 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.

(50-

Claims (1)

[Scope of Claims] 1 Formula [I]: (In the formula, 171 and R2 may be the same or different, respectively, or may be the same or different for each unit, and may be a hydrogen atom, a hydroxyl group, or represents a saturated hydrocarbon group having 1 to 5 carbon atoms (~, R3 represents a hydrocarbon group having 15 to 20 carbon atoms having 1 to 3 unsaturated double bonds (~, A is - CHCHHz or -CM'CH2COIR'I1
．． l I+ (wherein R 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 an integer of 2 to 10. is an integer. However, the plural A's may be the same or different. ) A synthetic resin characterized by having the structure shown in the following. 2. Formula [■]: 1 R''' (wherein R1 and R2 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 (- 5R3 represents a hydrocarbon group having 15 to 20 carbon atoms and having 1 to 3 unsaturated double bonds;
A is CHCH2 or -CHCH2CO:R'+ l l
I+ °＼. . . 2/\. . 2°＼. 1□. (In the formula, R represents a hydrogen atom or a saturated hydrocarbon group having 1 to 5 carbon atoms.) [~, m is an integer of 0 to 2. However, a plurality of A's may be the same or different. ) Formula [l] characterized by condensation polymerization of the compound represented by: 3) The compound represented by formula [11] has a hydrocarbon group having 15 to 20 carbon atoms and having 1 to 3 unsaturated double bonds. A hydroxyaryl compound is reacted with an α.β-unsaturated dibasic acid and/or its acid anhydride, or an acid anhydride group is further reacted with a monohydric saturated alcohol having 1 to 5 carbon atoms. - The method for producing a synthetic resin according to claim 2, wherein the synthetic resin is produced by esterification.