JP3448971B2 - Method for producing liquid polyester resin and composition containing the resin - Google Patents

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester which can be synthesized and used as a resin for a film-forming material such as paints and inks, or as an adhesive resin, without using a solvent. Further, since it has a long-chain aliphatic hydrocarbon group, it can be used as a compatibilizer, an interfacial modifier, a pigment dispersant and the like.

[0001]

2. Description of the Related Art Conventionally, a resin system containing an organic solvent has been used for a film forming material such as a paint, an adhesive and an ink. It is known that these conventional resin systems scatter a large amount of organic solvent in coating, film forming processes such as printing processes, and curing and drying processes. With increasing interest in the global environment and the working environment, restrictions on the use of organic solvents have come to be imposed. For this reason, various countermeasures have been taken regarding the solvent-free use of the resin for the film-forming material.

The resin system used for solvent-free can be roughly classified into a precursor system and a polymer system. Since the precursor system uses a low molecular weight monomer or prepolymer, it is a liquid having a low viscosity, and the conventional film forming method can be used as it is. However, in the precursor system containing a low molecular weight substance in the composition, further improvement in safety and hygiene such as scattering of low molecular weight substance is desired. In terms of physical properties, it is known that it is difficult to control the properties of cured products in the case of coatings composed of resins in the oligomer domain (Soichi Muroi, "1992 Adhesion and Painting Study Group Lectures") , P4, 1993), and an increase in molecular weight while maintaining low viscosity is desired. On the other hand, in the polymer system, it is necessary to liquefy the solid polymer by some method or change the film forming method. As a typical conventional method of liquefying without using an organic solvent, it has been pointed out that a plastisol system which is liquefied by a non-volatile plasticizer makes it difficult to obtain a hard cured product and that the plasticizer migrates. Further, in latex systems such as emulsions and hydrosols, problems such as non-uniformity of cured products and slow drying speed have been pointed out. Even the water-soluble resin system, which is considered to be the most effective at the present time, has problems such as slow drying speed, water resistance, and wastewater treatment method. Most water-soluble resin systems contain 10% or more of an organic solvent in order to improve pigment dispersibility and film-forming property. Further, in the case of powder or hot melt resin system, since it is greatly different from the equipment by the conventional film forming method, it is necessary to introduce new equipment.

[0003]

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have found that a natural fatty acid ester moiety in a polyester synthesis obtained by ring-opening polymerization of epoxy and cyclic acid anhydride. It was found that a polyester having an oxidative curing site at the end can be obtained by using a saponified product. Further, while having a high molecular weight by using a specific cyclic acid anhydride, it has a low viscosity, the film-forming method conventionally used (the film-forming in the present invention, by a method such as printing and coating,
It means forming a resin film having a thickness of 0.1 to 100 μm on a substrate made of paper, metal, plastic, ceramics or the like. ) Is available, and after film formation, heat, light,
Further, they have found that a solventless polyester that can suppress the influence of curing inhibition by oxygen even when it is cured with an electron beam or the like and that gives a cured product in a short time can be obtained.

[0004]

The present invention provides a partially saponified oil (C) obtained by saponifying a cyclic acid anhydride (A), an epoxy compound (B) and a dry or semi-dry oil and fat at a saponification rate of 5 to 90%. It is a method for producing a liquid polyester resin by reacting with. Furthermore, the present invention is the method for producing the above liquid polyester resin, wherein 5 mol% or more of the epoxy compound (B) is an epoxy compound having an unsaturated double bond. Furthermore, the present invention is the method for producing the above liquid polyester resin having a number average molecular weight of 1,000 to 30,000. Furthermore, in the present invention, the cyclic acid anhydride (A) and the epoxy compound (B) are mixed and reacted at a ratio of (A) :( B) = 1: 0.8 to 1.2 (molar ratio). It is a method for producing the liquid polyester resin. Furthermore, the present invention is a liquid polyester resin produced by the above method. Furthermore, the present invention is a substantially solvent-free film-forming material obtained by blending the above-mentioned liquid polyester resin with a radical reaction initiator or a metal salt dryer.

In the present invention, the cyclic acid anhydride (A) is a constituent component of the polyester, and examples thereof include succinic anhydride, itaconic anhydride, maleic anhydride, glutaric anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride and the like. Group cyclic acid anhydrides, aromatic cyclic acid anhydrides such as phthalic anhydride, isatoic acid anhydride, diphenic acid anhydride, etc., or saturated or unsaturated aliphatic hydrocarbon groups, aryl groups, halogen groups, hetero groups A derivative having a ring group bonded thereto can be used.

The use of cyclic acid anhydrides (A) represented by the following general formulas a to e in the present invention is effective in reducing the viscosity of the liquid polyester. It is also effective for high solidification when a solvent is used.

[Chemical 1] In the formula, R ¹ is a saturated or unsaturated aliphatic hydrocarbon group having 4 to 25 carbon atoms, preferably 5 to 22 carbon atoms, but when the carbon number is 22 or more, particularly 25, the degree of polymerization is difficult to increase, and Since the melting point is high, a dedicated heating system is required during film formation, which is not preferable, and conversely, the number of carbon atoms is less than 4, or the desired liquid polyester cannot be obtained if there is no substituent. Alternatively, it is not preferable because the viscosity increases. Further, as the aliphatic hydrocarbon group, both a linear type and a branched type can be used, but the linear type is preferable in terms of viscosity reduction.

Examples of the cyclic acid anhydride (A) having such an aliphatic hydrocarbon group include butylsuccinic anhydride, hexylsuccinic anhydride, octylsuccinic anhydride, dodecylsuccinic anhydride, tetradecylsuccinic anhydride. Thing, hexadecyl succinic anhydride, octadecyl succinic anhydride,
Nonenyl succinic anhydride, icosyl succinic anhydride, henicosyl succinic anhydride, docosyl succinic anhydride,
Decenyl succinic anhydride, tetradecenyl succinic anhydride, hexadecenyl succinic anhydride, heptadecenyl succinic anhydride, octadecenyl succinic anhydride, icocenyl succinic anhydride, henicosenyl Succinic anhydride,
An alkylsuccinic anhydride represented by the above general formula a, such as docosenylsuccinic anhydride, butyl maleic anhydride,
Pentyl maleic anhydride, hexyl maleic anhydride, octyl maleic anhydride, decyl maleic anhydride, dodecyl maleic anhydride, tetradecyl maleic anhydride, hexadecyl maleic anhydride, octadecyl maleic anhydride, Icosyl maleic anhydride, henicosyl maleic anhydride, docosyl maleic anhydride, decenyl maleic anhydride, tetradecenyl maleic anhydride, hexadecenyl maleic anhydride, octadecenyl maleic acid An alkyl maleic anhydride represented by the above general formula b, such as an acid anhydride, icosenyl maleic anhydride, henicocenyl maleic anhydride or docosenyl maleic anhydride,

Butyl glutaric anhydride, hexyl glutaric anhydride, heptyl glutaric anhydride, octyl glutaric anhydride, decyl glutaric anhydride, dodecyl glutaric anhydride, tetradecyl glutaric anhydride, hexadecyl glutaric acid Anhydride, octadecyl glutaric anhydride, icosyl glutaric anhydride, docosyl glutaric anhydride, decenyl glutaric anhydride, tetradecenyl glutaric anhydride, hexadecenyl glutaric anhydride, octadecenyl glutaric acid An alkyl glutaric anhydride represented by the above general formula c, such as anhydride, nonadecenyl glutaric anhydride, icosenyl glutaric anhydride, henicosenyl glutaric anhydride, docosenyl glutaric anhydride ,

4-n-butylcyclohexanedicarboxylic acid anhydride, 4-n-dodecylcyclohexanedicarboxylic acid anhydride, 4-n-tetradecylcyclohexanedicarboxylic acid anhydride, hexadecylcyclohexanedicarboxylic acid anhydride, octadecylhexahydroanhydride phthalate Acid, docosylcyclohexanedicarboxylic acid anhydride, dodecylcyclohexanedicarboxylic acid anhydride, tetradecylcyclohexanedicarboxylic acid anhydride, hexadecylcyclohexanecarboxylic acid anhydride, octadecylcyclohexanedicarboxylic acid anhydride, icosylcyclohexanedicarboxylic acid anhydride, docosyl Cyclohexanedicarboxylic acid anhydride, decenylcyclohexanedicarboxylic acid anhydride, hexadecenylcyclohexanedicarboxylic acid anhydride, octadecenylcyclohexyl Njikarubon anhydrides where cell sulfonyl cyclohexanedicarboxylic anhydride, alkyl cyclohexanedicarboxylic anhydride represented by the above general formula, such as Torii cosecant sulfonyl cyclohexanedicarboxylic anhydride,

In addition, 4-n-butylphthalic anhydride, hexylphthalic anhydride, octylphthalic anhydride, decylphthalic anhydride, dodecylphthalic anhydride, tetradecylphthalic anhydride, pentadecylphthalic anhydride, hexadecylphthalic anhydride, octadecyl Phthalic anhydride, nonadecyl phthalic anhydride, icosyl phthalic anhydride, henicosyl phthalic anhydride, docosyl phthalic anhydride, decenyl phthalic anhydride, hexadecenyl phthalic anhydride, heptadecenyl phthalic anhydride, etc. Alkyl phthalic anhydride represented by the above general formula e And so on.

In the present invention, the epoxy compound (B) is a constituent component of the polyester and is not particularly limited as long as it is a compound having one epoxy group in the molecule, but has 1 to 25 carbon atoms, preferably 4 to 22 carbon atoms. By using the epoxy compound (B) having a saturated or unsaturated aliphatic hydrocarbon group, the copolymer can be effectively liquefied or reduced in viscosity. Examples of such epoxy compound (B) include methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, Undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, heptadecyl glycidyl ether,
Octadecyl glycidyl ether, nonadecyl glycidyl ether, icosyl glycidyl ether, hen icosyl glycidyl ether, docosyl glycidyl ether,
Triicosyl glycidyl ether, tetricosyl glycidyl ether, pentaycosyl glycidyl ether,
Decenyl glycidyl ether, undecenyl glycidyl ether, tetradecenyl glycidyl ether, hexadecenyl glycidyl ether, heptadecenyl glycidyl ether, octadecenyl glycidyl ether, nonadecenyl glycidyl ether, icosenyl Examples thereof include glycidyl ether and henicosenyl glycidyl ether, and both linear and branched types can be used, but the linear type is preferable in terms of viscosity reduction. In the present invention, the epoxy compound (B) may be an aromatic compound such as phenyl glycidyl ether, butyl phenyl glycidyl ether, phenyl nitro glycidyl ether, etc. in order to adjust solvent resistance and mechanical properties, in addition to the above compounds. Can be used.

When the liquid polyester is cured in the present invention, an epoxy compound (B) having an unsaturated double bond can be used. Examples of the epoxy compound (B) include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, and glycidyl cinnamate. The blending amount of the epoxy compound having an unsaturated double bond is preferably 5 to 100 mol% of the entire blending amount of the epoxy compound (B) used,
It is 30 to 90 mol%, and when it is less than 30 mol%, especially 5 mol%, it is difficult to obtain a hard film, and conversely, when 90 mol% or more is mixed, the film tends to become brittle, which is not preferable.

The cyclic acid anhydride (A) and the epoxy compound (B) are each selected from the above-mentioned one or two.
Used in combination of two or more species. The amount of components of the cyclic acid anhydride (A) and the epoxy compound (B) may be (A) :( B) =, depending on the impurity ratio of the raw material and the target molecular weight.
Although it is 1: 0.8 to 1.2 (molar ratio), basically equimolar combination is preferable.

In the present invention, the partially saponified oil and fat (C) is
It is a partially saponified fat or oil containing a hydroxyl group, which is obtained by partially saponifying a dry or semi-dry fat or oil having an iodine value of 100 or more. In the present invention, the partially saponified oil and fat (C)
Acts as an initiator, and the cyclic acid anhydride (A)
And to form the end of the polyester composed of the epoxy compound (B). Furthermore, partially saponified oil and fat (C)
Is a site that acts as an oxidative hardening site due to oxygen in the air. Examples of the dry or semi-dry oil and fat having an iodine value of 100 or more that can be used to obtain the partially saponified oil and fat (C) include
Eno oil, linseed oil, mustard oil, safflower oil, sunflower oil, soybean oil, tung oil, illipe oil, ochika oil, poppy oil, corn oil, carnauba wax, candelilla wax,
Rice oil, cottonseed oil, sesame oil, rapeseed oil and the like can be mentioned. Among them, eno oil, linseed oil, castor oil, safflower oil, sunflower oil, soybean oil, tung oil, iodine value 1
It is preferable to use 30 or more drying oils.

The partially saponified oil and fat (C) in the present invention
Can be quantitatively obtained by changing the amount of potassium hydroxide used in the conventional fat and oil saponification method. The partial saponification rate is 5 to 90.
%, Preferably 10 to 70%. Partial saponification rate is 10
%, Especially when it is lower than 5%, the content of the fat and oil bound to the polyester becomes low, the compatibility between the fat and oil and the polyester becomes poor, and separation and white turbidity easily occur, and the stability tends to be low. Further, yellowing after curing may cause a problem, which is not preferable. The partial saponification rate is 70
%, Especially when it is higher than 90%, the proportion of fatty acids resulting from saponification in the composition becomes high, which may cause bleaching after curing, distortion, odor, etc. Since the content of fats and oils is low, the compatibility of fatty acids and fats and oils with polyester is poor, and separation and turbidity occur, which is not preferable. The unsaturated carboxylic acid generated as a result of partial saponification may be removed by a method such as distillation, if necessary.

In the present invention, the cyclic acid anhydride (A)
As an initiator when the epoxy compound (B) reacts with
Alternatively, in order to control the molecular weight and viscosity of the liquid polyester, a hydroxyl group-containing compound having at least one hydroxyl group in the molecule may be used in combination with the partially saponified fat and oil (C). Examples of such a hydroxyl group-containing compound include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol,
Heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, icosyl alcohol, Aliphatic alcohols such as henicosyl alcohol, docosyl alcohol, triicosyl alcohol, tetricosyl alcohol, pentaicosyl alcohol, decenyl alcohol, methoxyethylene glycol, methoxydiethylene glycol, methoxytriethylene glycol, methoxytetraethylene glycol Kind,

Or ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polypropylene-polyethylene glycol, 1,4-butylene glycol,
Aliphatic diols such as 1,3-butylene glycol, polybutylene glycol, hexanediol and cyclohexanediol, bisphenols, bis (hydroxyphenyl) methane, bisphenols such as 2,2′-bis (hydroxyphenyl) propane, polyether diols , Polyester diol and the like, and compounds having three or more hydroxyl groups such as hexamethylol melamine, cyclodextrin, glycerin, trimethylol propane and 1,2,6-hexanetriol. Of these, aliphatic alcohols and aliphatic diols can be said to be preferable in order to liquefy or lower the viscosity of the polyester.

In the present invention, the compounding amounts of the partially saponified oil / fat (C) and the hydroxyl group-containing compound affect the molecular weight of the liquid polymer. Therefore, (number average molecular weight; Mn) = 1000
The compounding amount of the compound to obtain a liquid polyester of ˜30,000 is 0.001 to 0.2 equivalent, and more preferably 0.0 to 1 mol based on 1 mol of the cyclic acid anhydride (A).
It is 05 to 0.1 equivalent. Further, the compounding amount of the partially saponified oil / fat (C) is 5 of the total compounding amount of the hydroxyl group-containing compound used.
Is preferably 100 to 100 equivalent%, more preferably 10 to 9
It is 0 equivalent%. When it is 10 equivalent%, particularly 5 equivalent% or less, it is not preferable because the oxidative curability is difficult to be effectively exhibited, and when yellowing is a problem, it is preferably 90 equivalent% or less.

In the present invention, when an epoxy compound having an unsaturated double bond is used, a radical polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, p-t-to prevent gelation during the synthesis of liquid polyester. Phenols such as butylcatechol, 2,5-di-t-butylhydroquinone, t-butylhydroquinone, 2,5-diamylhydroquinone and di-t-butylparacresol, p-benzoquinone, naphthoquinone,
Quinones such as 2,5-diphenyl-p-benzoquinone,
It is also possible to use oximes such as quinonedioxime and cyclohexanooxime, amidines such as acetamidine acetate, quaternary ammonium salts, hydrazine salts and amine hydrochlorides. The radical polymerization inhibitor is 0.1 to 0.1 with respect to the epoxy compound having an unsaturated double bond.
It is preferable to add 4% by weight, preferably 0.1 to 1.0% by weight. If the content of the radical polymerization inhibitor is less than 0.1% by weight, the unsaturated double bond reacts during the synthesis of the liquid polyester and gels during the synthesis, making it difficult to continue the stable reaction. Become. vice versa,
Addition amount of radical polymerization inhibitor is 1% by weight, especially 4% by weight
If the amount is larger than the above range, the reactivity at the time of curing reaction of the liquid polyester is deteriorated, which is not preferable. Also,
Gelation can also be prevented by increasing the oxygen concentration in the reaction atmosphere.

Further, during the alternating copolymerization reaction of the cyclic acid anhydride (A) and the epoxy compound (B), a known catalyst such as a Lewis base or a tertiary amine, such as sodium hydroxide, potassium hydroxide, Lithium chloride, diethyl zinc, tetra (n-butoxy) titanium, N, N-dimethylbenzylamine, etc. can be used. The amount of such a catalyst compounded is 0 to 0.5 mol with respect to the cyclic acid anhydride (A).
%, Preferably 0.1 to 0.3 mol%. The reaction proceeds even if these catalysts are not used, but it is effective in shortening the reaction time. However, if such a catalyst is blended in an amount of 0.3, particularly 0.5 mol% or more, the liquid polyester will be yellowed and a high molecular weight liquid polyester will not be obtained, which is not preferable.

The liquid resin of the present invention has a number average molecular weight (converted to polystyrene) of 1,000 to 3,000 measured by GPC method (gel permeation chromatograph) by adjusting the compounding amount of the hydroxyl group-containing compound or the catalyst.
It is synthesized so as to be 0, preferably 2000 to 20000. When the number average molecular weight is smaller than the above numerical value, the volume shrinkage rate during curing becomes large, which may lead to deterioration of mechanical properties such as strain and detachment from the substrate, and various physical properties such as solvent resistance and boiling water resistance. It is not preferable because it lowers, and liquid polyesters larger than the above values are not preferable because the low viscosity capable of forming a film cannot be maintained.

The liquid polyester of the present invention can be produced by heating in the temperature range of 60 to 100 ° C. by a known ring-opening copolymerization method without using a solvent. Further, in the present invention, a solvent may be used in order to lower the viscosity of the reaction solution or to stably proceed the copolymerization reaction. As the solvent used for such purpose, a solvent having a boiling point of 70 to 85 ° C. is preferable in order to facilitate temperature control during the reaction due to the boiling point, and for example, ethyl acetate, benzene, methyl ethyl ketone, etc. are generally used. Target. As the blending amount, when the amount of the solvent increases, the reactivity of the polymerization decreases and the production takes too much time, which is not suitable for practical use. Therefore, the cyclic acid anhydride (A), the epoxy compound (B), and the hydroxyl group-containing compound are not used. 0-60% by weight, preferably 15-3, of the total amount
It is 0% by weight. However, it is necessary to remove the solvent after the reaction is completed, and it can be said that it is preferable not to use it.

The viscosity of the obtained liquid polyester is 100 to 500,000 cp at 50 ° C. measured by a rotary vibration viscometer (VM-100, manufactured by Yamaichi Denki Co., Ltd.).
s, preferably 100 to 20000 cps.

The liquid polyester of the present invention can be used as a substantially solvent-free film forming material and an adhesive. However, a small amount of water or an organic solvent may be added to improve the film forming property. The amount that can be blended is up to 5% by weight based on the liquid polyester. When the liquid polyester of the present invention is cured, an organic peroxide such as benzoylperoxide, an azo compound such as azobisisobutyronitrile, ammonium persulfate, lauroyl peroxide may be added as necessary to enhance the curability. A general radical reaction initiator or a general photopolymerization initiator can be selected and used according to the type of unsaturated double bond introduced as a curing site. In order to promote the curability of the oxidative curing site, cobalt naphthenate, cobalt octoate, manganese naphthenate, copper naphthenate, zirconium naphthenate, vanadyl octoate, calcium naphthenate, barium naphthenate, zinc naphthenate, etc. Metal salts may be used as a dryer. The blending amount of these initiators and catalysts is preferably 0 to 3% by weight based on the blending amount of the liquid resin. Further, titanium white, colorants such as various pigments, lubricants and the like may be added.

When the liquid polyester film of the present invention is formed on a substrate such as various steel plates, metal plates such as aluminum plates, plastic films and papers, roll coaters, knife coaters, curtain coaters can be used. , Coil coater, spray coater, lithographic printing, letterpress printing, stencil printing, intaglio printing, etc. During film formation, heating can facilitate film formation. Further, after the film formation, it can be cured by treating with heat, light, electron beam or the like. The heat source is not particularly limited, but in general, a heat circulation type oven or a heating roll is preferably used. As the light source, there are a mercury lamp, a xenon lamp, a fluorescent lamp, an incandescent lamp, various lasers and the like, but curing with UV light using a mercury lamp or the like is preferable because of its versatility.

[0026]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

(Synthesis Example-1) Synthesis of 20% saponified linseed oil Stirrer, temperature sensor, nitrogen inlet tube (flow rate: 20 ml)
/ Min) and a 500 ml four-necked round bottom flask equipped with a condenser, linseed oil (saponification value: 194 mg KOH / g), 250 g, ethanolic potassium hydroxide (0.5 N), 339 ml, were placed in a bath at 85 ° C. Reflux for 30 minutes with stirring. After allowing to cool to near room temperature, this is placed in a separating funnel, 350 ml of 0.5N hydrochloric acid is added, and the mixture is shaken sufficiently and neutralized. The mixture is allowed to stand for 30 minutes, and when completely separated into two layers, the lower layer (aqueous phase) is discarded and the supernatant is recovered. Put this in an eggplant-shaped flask (capacity: 500 ml), reduce the pressure to 5 mmHg with a vacuum pump equipped with a liquid nitrogen trap while heating in a water bath at 50 ° C, and remove volatile components such as water and ethanol. . The acid value of the obtained amber liquid was measured (hereinafter, the acid value in the present invention is JIS
The result measured according to K0070 is shown. ) By the way,
It was 37.1 ml KOH / g, and it was confirmed that the saponification rate was 19.1%. (Number of hydroxyl groups per 1g) = 0.677 × 10 ^-3

(Synthesis Example-2) Synthesis of 33% saponified linseed oil Stirrer, temperature sensor, nitrogen inlet pipe (flow rate: 20 ml)
/ Min) and a 1-liter four-necked round-bottomed flask equipped with a condenser, linseed oil (saponification value: 194 mg KOH / g), 250 g, ethanolic potassium hydroxide (0.5 N), 564.5 ml, were charged and heated at 85 ° C. Reflux for 30 minutes with stirring in the bath. After allowing to cool to near room temperature, this is placed in a separating funnel, 600 ml of 0.5N hydrochloric acid is added, and the mixture is shaken sufficiently and neutralized. The mixture is allowed to stand for 30 minutes, and when completely separated into two layers, the lower layer (aqueous phase) is discarded and the supernatant is recovered. Put this in an eggplant-shaped flask (capacity: 500 ml), depressurize to 51 mmHg with a vacuum pump equipped with a liquid nitrogen trap while heating in a water bath at 50 ° C., and remove volatile components such as water and ethanol. . When the acid value of the obtained amber liquid was measured, it was 60.3 ml KOH / g, and it was confirmed that the saponification rate was 31%. (Number of hydroxyl groups per gram) = 1.13 × 10 ⁻³

(Synthesis example-3) 50% saponified linseed oil synthesis stirrer, temperature sensor, nitrogen inlet tube (flow rate: 20 ml)
/ Min) and a 1-liter four-necked round bottom flask equipped with a condenser, linseed oil (saponification value: 194 mg KOH / g), 100 g, ethanolic potassium hydroxide (0.5 N), 339 ml, and placed in a water bath at 85 ° C. Reflux for 30 minutes with stirring. After allowing to cool to near room temperature, this is placed in a separating funnel, 350 ml of 0.5N hydrochloric acid is added, and the mixture is shaken sufficiently and neutralized. The mixture is allowed to stand for 30 minutes, and when completely separated into two layers, the lower layer (aqueous phase) is discarded and the supernatant is recovered. Put this in an eggplant-shaped flask (capacity: 300 ml), reduce the pressure to 5 mmHg with a vacuum pump equipped with a liquid nitrogen trap while heating in a 50 ° C water bath, and remove volatile components such as water and ethanol. . When the acid value of the obtained amber liquid was measured, it was confirmed to be 96 mlKOH / g, and the saponification rate was 49.5%. (Number of hydroxyl groups per 1g) = 1.69 × 10 ^-3

(Synthesis Example-4) Synthetic stirrer for 20% saponified tung oil, temperature sensor, nitrogen inlet pipe (flow rate: 20 ml)
/ Min) and a 1-liter four-necked round-bottomed flask equipped with a condenser, tung oil (saponification number: 192), 250 g, ethanolic potassium hydroxide (0.5 N), 339 ml, were charged and stirred in a water bath at 85 ° C. While refluxing for 30 minutes. After allowing to cool to near room temperature, this is placed in a separating funnel, 350 ml of 0.5N hydrochloric acid is added, and the mixture is shaken sufficiently and neutralized. The mixture is allowed to stand for 30 minutes, and when completely separated into two layers, the lower layer (aqueous phase) is discarded and the supernatant is recovered. Put this in an eggplant-shaped flask (capacity: 500 ml), reduce the pressure to 5 mmHg with a vacuum pump equipped with a liquid nitrogen trap while heating in a water bath at 50 ° C, and remove volatile components such as water and ethanol. . When the acid value of the obtained amber liquid was measured, it was 38.0 ml KOH / g, and it was confirmed that the saponification rate was 20%. (Number of hydroxyl groups per 1g) = 0.684 × 10 ^-3

[0031]

[Table 1]

(Example-1) Stirrer, temperature sensor,
A 500 ml four-neck round bottom flask equipped with a nitrogen inlet tube and a condenser was charged with 20% saponified linseed oil (Synthesis Example 1) 36.9 g MHPA 84.0 g BGE 65.0 g DMBA 1.35 g. , The temperature in the flask is 85 while stirring in a water bath.
Raise the temperature to ℃. The reaction solution became viscous in the polymerization tank as the polymerization reaction proceeded. After continuing the reaction for 10 hours,
When the acid value was measured, it was 18 mlKOH / g.
When heating was continued for another 10 hours, the acid value was 10 ml.
Since KOH / g was reached, the reaction was terminated by cooling. When the molecular weight of the obtained yellow viscous liquid was measured by the GPC method, the number average molecular weight was Mn = 2000, and the viscosity (50 ° C.) of the liquid polymer was 25,000 cps.

(Example-2) Stirrer, temperature sensor,
In a 500 ml four-neck round bottom flask equipped with a nitrogen inlet tube and a condenser, 20% saponified linseed oil (Synthesis Example 1) 36.9 g MHPA 84.0 g GMA 42.6 g DGE 42.8 g DMBA 1 .35 g of hydroquinone 0.213 g was charged, and the temperature inside the flask was adjusted to 85 while stirring in a water bath.
Raise the temperature to ℃. The reaction solution became viscous in the polymerization tank as the polymerization reaction proceeded. After continuing the reaction for 10 hours,
When the acid value was measured, it was 20 mlKOH / g.
When heating was continued for another 10 hours, the acid value was 12 ml.
Since KOH / g was reached, the reaction was terminated by cooling. When the molecular weight of the obtained viscous liquid was measured by the GPC method, the number average molecular weight was Mn = 2750, and the viscosity (50 ° C.) of the liquid polymer was 2500 cps.

(Examples 3 to 11) Raw materials having the compositions shown in Table 2 were charged in the same manner as in Examples 1 and 2, and an ester liquid polymer was synthesized under each reaction condition.
The reaction was terminated when the reaction time was 20 hours or when the acid value became 15 mlKOH / g or less, and the molecular weight and viscosity of the obtained viscous liquid polyester were measured (Table 2).

[0035]

[Table 2]

(Comparative Example-1) Stirrer, temperature sensor,
In a 500 ml four-neck round bottom flask equipped with a nitrogen inlet tube and a condenser, linseed oil 25.0 g HHPA 77.0 g GMA 36.0 g BGE 32.0 g BOH 3.9 g DMBA 1.35 g. Hydroquinone (0.213 g) was charged, and the temperature inside the flask was adjusted to 85 while stirring in a water bath.
Raise the temperature to ℃. The reaction solution became viscous in the polymerization tank as the polymerization reaction proceeded. After continuing the reaction for 10 hours,
When the acid value was measured, it was 20 mlKOH / g.
When heating was continued for another 5 hours, the acid value was 15 mlK.
Since the amount became OH / g or less, the reaction was terminated by cooling. The obtained liquid was a slightly turbid and viscous liquid, and when the molecular weight of the polymer was measured by the GPC method, the number average molecular weight; Mn
= 2340, and the viscosity of the liquid polymer (50 ° C) is 17
It was 000 cps. This liquid polymer is 1
When left standing for a day, it separated into two phases.

(Comparative Example-2) Stirrer, temperature sensor,
A 500 ml four-neck round bottom flask equipped with a nitrogen inlet tube and a condenser was charged with MHPA 84.0 g GMA 42.6 g DGE 42.8 g DOH 7.9 g DMBA 1.35 g hydroquinone 0.213 g. , The temperature in the flask is 85 while stirring in a water bath.
Raise the temperature to ℃. The reaction solution became viscous in the polymerization tank as the polymerization reaction proceeded. After continuing the reaction for 10 hours,
When the acid value was measured, it was 20 mlKOH / g.
When heating was continued for another 5 hours, the acid value was 15 mlK.
Since the amount became OH / g or less, the reaction was terminated by cooling. When the molecular weight of the obtained viscous liquid was measured by the GPC method, the number average molecular weight was Mn = 2750, and the viscosity (50 ° C.) of the liquid polymer was 11500 cps.

3% by weight of benzoylperoxide and cobalt naphthenate were added to the liquid polyesters obtained in Examples 1 to 13 and Comparative Examples 1 and 2, and the mixture was sufficiently mixed to cure. Liquid resin composition was formed into a film on a tin plate with an applicator of 0.5 mil, and heated under various temperature conditions for a certain period of time. The characteristic values of the obtained cured film are shown in Table 3. The measurement of each physical property value follows the method described below. Pencil hardness; Adhesion according to JIS-K-5440: Residual rate (%) by cellotape peeling test (cross-cut method) Retort resistance: Whitening after 1 hour in 130 ° C autoclave (○: No whitening, Δ: Solvent resistance: Residual rate (%) after 50 MEK rubs Yellowing: Color difference meter (CR from Minolta Camera Sales Co., Ltd. CR
-200, Δ (Lab method) Δb value

[0039]

[Table 3]

[0040]

INDUSTRIAL APPLICABILITY According to the present invention, as a solvent-free coating material, a film-forming material such as ink, a curable liquid resin for adhesives, a compatibilizer, an interface modifier, a pigment dispersant, and a metal chelating agent. The low temperature curable liquid polyester used can be easily obtained. Further, since it contains an oxidatively curable unsaturated fatty acid ester as a terminal functional group, it is possible to improve the inhibition of curing by oxygen in the air during curing,
It can be cured in air even with a relatively small amount of catalyst. Furthermore, since an unsaturated fatty acid which is originally poorly compatible with polyester is bound to the polyester terminal, it can be used as a compatibilizing agent or a dispersant for alkyd resin and the like.

Front page continuation (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08G 63/00-63/91 C09D 167/06-167/08 WPI / L (QUESTEL)

Claims (6)

(57) [Claims] 1. A liquid polyester obtained by reacting a cyclic acid anhydride (A) with an epoxy compound (B) and a partially saponified oil or fat (C) obtained by saponifying a dry or semi-dry oil or fat at a saponification rate of 5 to 90%. Resin manufacturing method. 2. The method for producing a liquid polyester resin according to claim 1, wherein 5 mol% or more of the epoxy compound (B) is an epoxy compound having an unsaturated double bond. 3. The method for producing a liquid polyester resin according to claim 1, which has a number average molecular weight of 1,000 to 30,000. Wherein the cyclic acid anhydride (A) and the epoxy compound (B) (A) :( B ) = 1: 0.8~1.2 ( made by blending in a ratio of molar ratio) reaction according Item 1 to 3
The method for producing a liquid polyester resin according to item 1 . 5. The method according to any one of claims 1 to 4.
Liquid polyester resin produced by the method . 6. A substantially solvent-free film-forming material obtained by blending the liquid polyester resin according to claim 5 with a radical reaction initiator or a metal salt dryer.