JPH05247193A - Epoxidized polyester and its production - Google Patents

Abstract

PURPOSE:To obtain a new epoxidized polyester excellent in curability, flexibility, etc., and an industrial method for its production. CONSTITUTION:(1) The objective epoxidized polyester comprises >=3 epoxycyclohexene groups in the molecule and has 1,000-10,000 number-average molecular weight. (2) A method for producing the epoxidized polyester is to dissolve a polyester, comprising >=3 cyclohexene groups in the molecule and having 1,000-10,000 number-average molecular weight in a hydrocarbon-based solvent and/or an ester-based solvent and epoxidize the polyester with hydrogen peroxide in the presence of a weakly basic compound or (3) a method for producing the epoxidized polyester is to epoxidize the polyester with peracetic acid.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a cationically polymerizable resin,
The present invention relates to an epoxidized polyester suitable for constituent components such as an ultraviolet curable resin and an epoxy resin, and a stabilizer for a vinyl chloride resin, and a method for producing the same.

[0002]

2. Description of the Related Art A compound having an alicyclic epoxy group has higher cationic polymerizability than an olefinic epoxy group or a glycidyl type epoxy group, and is suitable for a cationically polymerizable resin or a cationically polymerizable ultraviolet curable resin. Is. or,
Since it has reactivity with acid anhydride type curing agents and amine type curing agents, it is widely used as an epoxy resin diluent. It is also used as a stabilizer for vinyl chloride resins.

Examples of such compounds having an alicyclic epoxy group include butadiene, cyclohexenecarbinol, cyclohexene dicarbinol, cyclohexenyl aldehyde, cyclohexenecarboxylic acid, tetrahydrophthalic anhydride, dicyclopentadiene and cyclopentadiene. Although various compounds have been devised as raw materials, most compounds have two or less alicyclic epoxy groups in one molecule, and their molecular weight is less than 1,000.

The alicyclic epoxy compound as described above has a low viscosity because of its low molecular weight and exhibits a good diluting performance when used as a diluent for an epoxy resin.
The resulting cured product is brittle. When used as a cationically polymerizable resin raw material or a cationically polymerizable ultraviolet curable resin raw material, the cured product is brittle and flexible because the molecular weight is low and the number of alicyclic epoxy groups in one molecule is small. It has the drawback that an excellent cured product cannot be obtained, and the water resistance of the cured product is insufficient. Further, when used as a stabilizer for vinyl chloride resin, there is a problem that solvent extractability and migration are high because of its low molecular weight. Further, when such a compound is used for the above-mentioned application, it is often used outdoors, and in this case, weather resistance is required for the alicyclic epoxy compound as a material. However, an alicyclic epoxy compound which can solve these problems has not been known so far, and its appearance has been strongly demanded.

On the other hand, the present inventors have made extensive studies on a method for producing such an epoxidized polyester. Although hydrogen peroxide is known as an epoxidizing agent, the industrial epoxidation technology of high molecular weight polyester with hydrogen peroxide is not known. This is because (1) the reaction with hydrogen peroxide is a heterogeneous reaction, and the contact between the aqueous hydrogen peroxide solution layer and the raw material oil layer is rate-determining, so the reaction is slow with high-viscosity high-molecular-weight polyester, and (2) Normal,
Since the hydrogen peroxide applied is an aqueous solution with a maximum concentration of 60% in terms of handling safety, if the epoxidation rate is slow, side reactions such as addition of water, catalyst, co-catalyst to the generated epoxy groups As the selectivity increases, the selectivity decreases, resulting in thickening and gelation of the reaction system, and (3) degrading water partitioning, which causes problems such as difficulty in post-treatment operations such as washing. it is conceivable that. These tendencies are stronger in polyesters having hydroxyl groups, and epoxidation of hydroxyl group-containing polyesters has been more difficult.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the above problems and provides a novel and useful epoxidized polyester as a constituent component of a cationically polymerizable resin, an ultraviolet curable resin, an epoxy resin, a vinyl chloride resin and the like. The purpose is to establish an industrial manufacturing method.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that an epoxidized polyester having a specific structure can achieve the intended object. .. Further, the present inventors have found that such an epoxidized polyester (1) epoxidizes a polyester having a specific structure in the presence of a specific solvent (2) a specific solvent, or (3) ) It was found that it can be industrially produced by epoxidation with peracetic acid in a non-aqueous system. The present invention has been completed based on such findings.

The epoxidized polyester according to the present invention is
It contains at least three bifunctional groups represented by the general formula (1) (hereinafter referred to as "epoxycyclohexane groups") in the molecule, and has a number average molecular weight of about 1,000 to about 10,000.
Is characterized in that

[Chemical 3] [In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an endomethylene group. ]

The number of epoxycyclohexane groups contained in the epoxidized polyester according to the present invention is 3 or more in one molecule, preferably 3 to 50, more preferably 3 to 30. If it is less than 3, the curability of the resin component will be unsatisfactory when applied as a component constituting various resin components, specifically, cationically polymerizable resin composition, cationically polymerizable photocurable resin, epoxy resin composition and the like. It is sufficient, and a sufficient stabilizing effect cannot be obtained for vinyl chloride resin.

The molecular weight of the epoxidized polyester is
About 1,000 to about 10,000, preferably about 1,000
Is about 5,000. Light curing at less than 1,000
Although various curability such as acid anhydride curing is good, the obtained cured product is brittle and is not sufficiently flexible. Further, when used as a component of a vinyl chloride resin composition, bleeding, solvent extraction and migration are high, which is not preferable. on the other hand,
When it exceeds 10,000, the viscosity of the resin composition prepared is high, the solubility in a solvent is lowered, and the workability is lowered.

Further, the iodine value of the epoxidized polyester is recommended to be 4 or less, more preferably 2.5 or less. When a cationically polymerizable resin, an ultraviolet curable resin, an epoxy resin, or a stabilizer for vinyl chloride resin, which is made by applying an epoxidized polyester having an iodine value of more than 4, is used outdoors, the material tends to turn yellow and the weather resistance tends to decrease. There is.

The oxirane oxygen concentration of the present epoxidized polyester is preferably about 0.5 to 10% by weight.

The epoxidized polyester according to the present invention is
A polyester having 3 or more difunctional groups (hereinafter referred to as "cyclohexene groups") represented by the general formula (2) in the molecule and having a number average molecular weight of about 1,000 to about 10,000. It can be industrially produced by epoxidizing (hereinafter referred to as "present polyester").

[Chemical 4] [In the formula, R ¹ and R ² are the same as in the general formula (1). ]

The present polyester is obtained by polyesterification of a dibasic acid having a cyclohexene group or its acid anhydride (hereinafter referred to as "main acid component") and a polyhydric alcohol.

Examples of the main acid component include alicyclic dibasic acids represented by the general formula (3) and acid anhydrides thereof, specifically, Δ ⁴ -tetrahydrophthalic acid and 3-methyl-Δ. ^Four
Examples thereof include tetrahydrophthalic acid, 4-methyl-Δ ⁴ -tetrahydrophthalic acid, Δ ⁴ -nadic acid, methyl-Δ ⁴ -nadic acid and acid anhydrides thereof.

[Chemical 5] [In the formula, R ¹ and R ² are the same as in the general formula (1). ]

The polyhydric alcohol has 2 to 55 carbon atoms.
And dihydric alcohols having 3 to 24 carbon atoms or more.

Examples of such dihydric alcohols are ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, and 1-butanediol. , 6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, bisphenol A, hydrogenated bisphenol A, bisphenol A
Ethylene glycol adduct, hydrogenated bisphenol A
Ethylene glycol adduct, bisphenol F, and the like.

Examples of trihydric or higher alcohols include glycerin, trimethylolpropane, trimethylolethane,
Examples include pentaerythritol, dipentaerythritol, sorbit, low condensation products of phenol and formalin, low condensation products of cresol and formalin, and the like.

In order to improve the physical properties of the cured product, other dibasic acids, tribasic or higher polybasic acids and their acid anhydrides (hereinafter referred to as "auxiliary acid components") are used together for polyesterification. Further, it is also possible to use a monovalent organic acid or a monohydric alcohol together for polyesterification in order to seal the hydroxyl group or carboxylic acid group at the terminal of the molecule.

Examples of the sub-acid component include the following aromatic polyvalent carboxylic acids and their acid anhydrides, as well as aliphatic polyvalent carboxylic acids and alicyclic polyvalent carboxylic acids and their acid anhydrides. Saturated aliphatic polycarboxylic acids, alicyclic polycarboxylic acids and their acid anhydrides are preferred for applications where importance is attached to weather resistance.

Such aromatic polycarboxylic acid is, for example,
It is represented by the general formula (4) or (5).

[Chemical 6] [In formula, m is an integer of 2-4. ]

[Chemical 7] [In the formula, l and p are the same or different and each is an integer of 1 to 2, and X is a direct bond or -O-, -S-, -SO.
_{-, - SO 2 -, -CH} 2 -, - C (CH 3) 2 -, - CO
A group represented by-is shown. ]

Specific compounds include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, benzophenonedicarboxylic acid, diphenylsulfonetetracarboxylic acid, diphenylsulfonedicarboxylic acid and biphenyltetracarboxylic acid. Acid, biphenyl dicarboxylic acid, diphenyl ether tetracarboxylic acid, diphenyl ether dicarboxylic acid, bis (3,4-dicarboxyphenyl) sulfoxide, 2,2-bis (3,4-dicarboxyphenyl)
Examples thereof include propane and acid anhydrides thereof.

The aliphatic and alicyclic polycarboxylic acid is represented by, for example, the general formula (6).

[Chemical 8] [In the formula, n is an integer of 2 to 4, R ³ may have an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, or a halogen atom,
It represents a saturated or unsaturated aliphatic hydrocarbon residue having 1 to 36 carbon atoms or a saturated alicyclic hydrocarbon residue having 4 to 30 carbon atoms. Specific examples of the compound include maleic acid, fumaric acid, malonic acid, succinic acid, dodecenylsuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, dodecanedioic acid, citric acid. , Isocitric acid, aconitic acid, tartaric acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetetracarboxylic acid, tricarboxycyclopentylacetic acid, cyclopentanetetracarboxylic acid, cyclobutanetetracarboxylic acid, 3,5,6-tricarboxynorbornane Examples include 2-acetic anhydride, het acid, tetrabromophthalic acid, tricarballylic acid, butanetetracarboxylic acid, and acid anhydrides thereof.

The monohydric alcohol has 1 to 2 carbon atoms.
Examples of the alcohol of 4 are butanol, hexanol, 2-ethylhexanol, octanol, decanol, isodecanol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol and oleyl alcohol.

Examples of the monovalent organic acid include carboxylic acids having 1 to 24 carbon atoms, and specific examples thereof include caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, myristic acid, palmitic acid and stearin. Acid, oleic acid, linoleic acid and the like can be mentioned.

A main acid component (a) and a polyhydric alcohol (d) which are essential constituents, and a sub-acid component (b) which is optionally used in combination, a monovalent organic acid (c) or a monovalent alcohol. Typical blending ratios (molar basis) of alcohol (e) are as follows. By using the components (b), (c), and (e) together, side reactions such as addition of water, catalyst, and cocatalyst to the produced epoxy group are suppressed, and water in the washing step of the post-treatment is further suppressed. It is possible to avoid problems such as deterioration of the layer separation property. This is particularly important in epoxidized polyesters having hydroxyl groups. (A) :( b) = 100: 0-40: 60 [(a) + (b)] :( c) = 100: 0-30: 70
(Preferably 100: 0 to 50:50) (d) :( e) = 100: 0 to 20:80 (preferably 100: 0 to 40:60) (a) :( b) is lower than 40:60. As a result, the number of epoxycyclohexane groups in the molecule is reduced, which causes a problem in that the performance when applied to a cationically polymerizable resin, an ultraviolet curable resin, an epoxy resin, a stabilizer for vinyl chloride resin, etc. is reduced. On the other hand, the hydroxyl groups contained in the components (b), (d) and (e) with respect to the carboxyl groups contained in the components (a), (b) and (c) are 0.8 to 1.5 times equivalent, preferably It is 0.9 to 1.4 times equivalent.

[Production of Present Polyester: Polyesterification Step] The polyesterification can be carried out without a catalyst or in the presence of a generally used suitable esterification catalyst.

Examples of the esterification catalyst include protonic acids such as paratoluene sulfonic acid, phosphoric acid and sulfuric acid, solid acids such as zeolite, silica and alumina, stannous oxide such as stannous oxide and organic tin esters, titanate compounds, Examples include basic inorganic compounds such as aluminum alcoholate compounds, zinc oxide, magnesium oxide, calcium oxide, etc., and usually 0.01 to 3% by weight based on the total weight of raw materials.
Used to a degree.

The esterification conditions are not particularly limited as long as a predetermined effect can be obtained, but usually the reaction temperature is 100 to 300 ° C. and dehydration is carried out under normal pressure or reduced pressure. The dehydration can be performed by aeration with an inert gas such as nitrogen gas or carbon dioxide, or by promoting the dehydration under reflux of an azeotropic solvent such as xylene, toluene, hexane. The catalyst can be removed and used as a raw material for epoxidation, or the catalyst can be used as a raw material for epoxidation without being removed.

Although the reaction pressure depends on other conditions, it is preferable to carry out the reaction in the range of atmospheric pressure to 10 mmHg.

The reaction is usually continued for 2 to 20 hours to a predetermined molecular weight.

The acid value of the polyester is 50 or less, preferably 30 or less, and the iodine value is about 8 to 130.

Among the present polyesters, a cation-curable resin is obtained by applying an epoxidized polyester prepared from a polyester having a hydroxyl group in the molecule as a raw material.
When it is used as an ultraviolet curable resin or epoxy resin, the adhesion to metal or plastic is improved, and when a filler or pigment is used in these resins, its dispersibility is improved. Further, as a result of improving the adhesion between the pigment and the filler and the resin, the chalking is reduced and the weather resistance is improved. Further, when used as an epoxy resin, the curability is improved.

On the other hand, the epoxidized polyester prepared from a polyester having a hydroxyl group in the molecule is also effective when a curing agent that reacts with the hydroxyl group, such as a compound containing isocyanate or silanol, is used in combination.

The hydroxyl group-containing polyester used as a raw material for the epoxidized polyester can be easily produced by selecting the raw material composition so that the hydroxyl equivalent is more than the carboxyl equivalent, and esterifying in the same manner as above. You can The hydroxyl value of the hydroxyl-containing polyester is about 10 to 150, more preferably 40 to 12
It is about 0.

[Epoxidation Step 1: Epoxidation Step with Hydrogen Peroxide (Hydrogen Peroxide Method)] The polyester obtained in the above step is dissolved in a hydrocarbon solvent and / or an ester solvent to give a weak basicity. In the presence of the compound, epoxidation is performed with hydrogen peroxide using the epoxidation catalyst and the cocatalyst.

As the above solvent, those having poor compatibility with water are preferable, and specifically, the solubility of water in the solvent is preferably 20 g / 100 g or less, particularly 5 g / 100 g or less. If it exceeds 20 g / 100 g, side reactions such as addition of water to the produced epoxy group increase, which is not preferable.

Examples of the solvent having such solubility include aromatic hydrocarbons having 6 to 15 carbon atoms such as benzene, xylene, toluene, ethylbenzene and isopropylbenzene, cyclohexane, heptane, hexane, octane,
C4-30 aliphatic chain or cyclic hydrocarbons such as kerosene, ethyl acetate, butyl acetate, cellosolve acetate, carbitol acetate, methyl acetoacetate,
Examples thereof include ester solvents having 3 to 15 carbon atoms such as ethyl acetoacetate, methyl propionate, dimethyl phthalate and diethyl phthalate.

Although the amount of the solvent used depends on the viscosity of the polyester, it is usually preferably about 5 to 300% by weight based on the polyester. If it is less than 5% by weight, the reaction rate is not sufficient because of high viscosity, and if it exceeds 300% by weight, the reaction rate is lowered due to the decrease in the concentration of the raw material polyester, and the manufacturing cost is increased, which is not preferable.

As the weakly basic compound, carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate, metaphosphoric acid, orthophosphoric acid, pyrophosphoric acid, polyphosphoric acid and sodium or potassium salts of hypophosphorous acid. And the like, silicates such as sodium or potassium salts of orthosilicic acid and metasilicic acid, and acetates such as sodium acetate and potassium acetate.

The amount of the weakly basic compound added is recommended to be about 0.05 to 3% by weight based on the raw material polyester. If it is less than 0.05% by weight, the effect of suppressing side reactions due to addition of water to the epoxy group formed is low, and if it exceeds 3% by weight, the reaction rate is lowered, and the iodine value is not lowered sufficiently, which is not preferable.

Examples of the epoxidation catalyst include formic acid, alkali tungstate, alkali molybdate, Δ ¹ -tetrahydrophthalic anhydride, acetic acid, trifluoroacetic acid, monochloroacetic acid and the like. In particular, when formic acid, sodium tungstate, Δ ¹ -tetrahydrophthalic anhydride or the like is used, side reactions can be suppressed and the reaction rate can be increased.

The amount of catalyst is usually 5 to 100 mol%, particularly preferably 5 to 50 mol%, based on the total number of moles of cyclohexene groups in the polyester. When it is less than 5 mol%, the reaction rate is slow, and when it exceeds 100 mol%, side reactions such as addition of water and addition of a catalyst and a cocatalyst to the produced epoxy group increase, which is not preferable.

Examples of cocatalysts are phosphoric acid, phosphorous acid,
Mineral acids such as hypophosphorous acid, boric acid and sulfuric acid, organic proton acids such as paratoluene sulfonic acid and methane sulfonic acid, cation exchange type ion exchange resins, solid acids such as acidic zeolite and the like can be mentioned. In order to suppress side reactions and increase the reaction rate, phosphoric acid, boric acid, and cation exchange type ion exchange resins are preferable. It is also possible to use a salt obtained by previously reacting the co-catalyst with the weakly basic inorganic compound as a co-catalyst.

The amount of such a cocatalyst added is usually, based on the total number of moles of cyclohexene groups in the polyester.
0.3 to 10 mol% is preferable. If it is less than 0.3 mol%, the reaction rate is slow, and if it exceeds 10 mol%, side reactions such as addition of water and cocatalyst to the produced epoxy group increase, which is not preferable.

Any commercially available hydrogen peroxide may be used, but the higher the concentration, the better, and it is usually preferable to use a 60% aqueous solution.

The amount of hydrogen peroxide used is 100 to 300 based on the total number of moles of cyclohexene groups in the polyester.
About mol% is preferable. When the amount is 100 mol% or less, the iodine value does not easily decrease to 4 or less, and when the amount is 300 mol% or more, the production cost increases, which is disadvantageous.

The order of adding the weakly basic compound, the catalyst, the co-catalyst and the hydrogen peroxide is not particularly limited,
After adding the weakly basic compound, the catalyst and the co-catalyst, hydrogen peroxide may be added dropwise or charged at the same time.

The reaction temperature is preferably about 40 to 90 ° C. If the temperature is lower than 40 ° C, the reactivity is low, and if the temperature is higher than 90 ° C, side reactions such as addition of water, catalyst and cocatalyst to the generated epoxy group increase, and the decomposition rate of hydrogen peroxide also increases, which is not preferable. ..

The reaction is usually carried out at normal pressure, but if necessary, it may be carried out under reduced pressure or under pressure.

The reaction time is usually about 1 to 15 hours.

The post-treatment after completion of the reaction is not particularly limited. For example, after washing with water, neutralization to decompose residual hydrogen peroxide, and further washing with water, or repeated washing with water,
The solvent can be distilled off to produce an epoxidized polyester. When it is not necessary to remove the solvent, it is possible to obtain a product by azeotropic dehydration with a solvent. or,
You may perform filtration as needed.

The epoxidation of the present polyester containing a hydroxyl group is basically possible by the above method.

[Epoxidation Step 2: Epoxidation Step with Peracetic Acid (Peracetic Acid Method)] The epoxidized polyester according to the present invention can also be produced by epoxidizing the present polyester in a non-aqueous system with peracetic acid. Specifically, the polyester is dissolved in a solvent selected from a ketone solvent, a hydrocarbon solvent, an ester solvent and glacial acetic acid, and then epoxidized with peracetic acid.

The peracetic acid applied to the reaction may be produced by any production method, and specifically, AMP may be used.
Method, gas phase method, liquid phase method, and the like, peracetic acid by oxidation of acetaldehyde, peracetic acid by acetylation of hydrogen peroxide, and the like.

The amount of peracetic acid used is preferably 100 to 300 mol% based on the total number of moles of cyclohexene groups in the polyester. When the amount is 100 mol% or less, the iodine value does not easily decrease to 4 or less, and when the amount is 300 mol% or more, the production cost increases, which is disadvantageous.

Further, if necessary, the polyester of the present invention may be used in advance of acetone, methyl ethyl ketone, methyl isobutyl ketone, or another ketone solvent having 3 to 10 carbon atoms, the above-mentioned hydrocarbon solvent, the above-mentioned ester solvent, and glacial acetic acid alone or. Two or more kinds are appropriately combined, preferably 5 to 3
The epoxidation is carried out after dissolving in a solvent in an amount of about 00 wt%.

The reaction temperature is preferably 0 to 100 ° C. When the temperature is 0 ° C or lower, the reaction rate is slow, and it is difficult to reduce the iodine value of the epoxidized polyester to 4 or lower.
Above 0 ° C, side reactions such as addition of by-produced acetic acid to the epoxy group and decomposition of peracetic acid increase, which is not preferable.

The reaction is usually carried out at normal pressure, but if necessary, it may be carried out under reduced pressure or under pressure.

The reaction time is usually about 1 to 15 hours.

As the reaction system, a batch method or a multistage continuous method can be applied.

The post-treatment method is not particularly limited, and examples thereof include a method of removing low volatile components such as acetic acid and a solvent by-produced by vacuum distillation.

The epoxidized polyester of the present invention is an epoxy resin which can be cured with various curing agents such as acid anhydride compounds, amine compounds and phenol compounds, as well as cationic polymerizable resins and cationically polymerizable ultraviolet curable resins. , A material suitable for vinyl chloride resin stabilizers, etc.
Since it has good weather resistance, it becomes a material suitable for outdoor use.

[0064]

The present invention will be described in detail below with reference to examples. The number average molecular weight (Mn) of the target substance in each example
Is a value obtained by analyzing the measurement result obtained by GPC and converting the result into polystyrene. The number of cyclohexene groups (X) and the number of epoxycyclohexane groups (Z) contained in one molecule, the conversion rate of cyclohexene groups at the time of epoxidation, and the selectivity to epoxycyclohexane groups were calculated according to the following formulas.

[0065]

[Equation 1]

[Equation 2]

[Equation 3]

[Equation 4] The symbols in the above formulas are as follows. IV [PE]: Iodine value of polyester IV [EPE]: Iodine value of epoxidized polyester IV [THPA]: Iodine value of tetrahydrophthalic anhydride Mn [PE]: Number average molecular weight of polyester Mn [EPE]: Epoxidized polyester Number average molecular weight Mw [THPA]: Molecular weight of tetrahydrophthalic anhydrides OX-OX: Oxirane oxygen

Further, the properties of the epoxidized polyester were evaluated by the following methods. [Curing properties with acid anhydride] Curing conditions : 4-methylhexahydrophthalic anhydride equivalent to 0.9 equivalent to epoxy group of epoxidized polyester was added, and tin octylate was added to the epoxidized polyester as a curing promoter. After blending 1 part by weight and defoaming, 20 g of it was placed in the center of a JIS No. M16 spring washer 5
Place in a 0 cm ³ polypropylene beaker at 130 ° C
It was cured for 10 hours at 150 ° C. for 10 hours. Tg : Measured by DSC. Flexibility : The presence or absence of peeling or cracking after the cured product was placed in -20 ° C dry ice-methanol was visually observed.

[Characteristics of UV-cured product] Curing conditions : Triphenylsulfonium hexafluorophosphate as a photo-curing cationic polymerization catalyst was dissolved in a 50% by weight acetone solution of epoxidized polyester in an amount of 150 mol% based on the epoxy group. A 50 μm thick standard test plate (JIS G-3303 (SPTE)) of 50 × 0.3 mm is applied with a thickness of 50 μm, dried at 50 ° C. and 3 mmHg for 2 hours, and then irradiated with an ultraviolet ray curing device (UE011-227-01, Irradiation was performed with a high pressure mercury lamp (1 Kw / 12.5 cm) at a distance of 4 cm for 1 minute using Eye Graphics. Gelability : The above-mentioned curing test plate was immersed in 50 ml of chloroform for 24 hours, and evaluated by the degree of the cured product remaining. Weather resistance test : The degree of yellowing of the coating film was evaluated after the cured plate was tested with a weatherometer for 500 hours.

[Characteristics of PVC (soft PVC) additive] Polyvinyl chloride (Zeon 101EP, manufactured by Zeon Corporation) 100 parts by weight Dioctyl phthalate 50 parts by weight Calcium stearate 0.3 parts by weight Zinc stearate 0.2 parts by weight Epoxidized polyester 3 parts by weight Preparation of test piece : The above components were mixed and kneaded with a two-roll at 165 ° C. for 4 minutes, and then at the same temperature of 100 kg / cm ²
After pressing for 10 minutes, a colorless and transparent vinyl chloride soft sheet having a thickness of 1 mm was prepared. Thermal stability : The test piece was left to stand at 170 ° C. for 1 hour, and the degree of coloring was visually observed. Bleed resistance : The degree of whitening after the above test piece was immersed in running water was visually observed.

Production Example 1 Δ ⁴ -Tetrahydrophthalic anhydride (hereinafter “THPA”)
Is abbreviated. ) 608 g (4 mol), 1,4-butanediol 270 g (3 mol), 2-ethylhexanol 2
86 g (2.2 mol) of stannous oxide as a catalyst was added to the flask in an amount of 0.05% by weight and 3% by weight of xylene with respect to the total weight of the raw materials, and 760 to 210 ° C under azeotropic dehydration of xylene. React for 10 hours under the condition of 450 mmHg,
A polyester having an acid value of 0.5 was obtained. After distilling off xylene,
Neutralized with sodium hydroxide, washed with water, dehydrated and filtered, then acid value 0.1, hydroxyl value 10, iodine value 91.5, Mn
1,200 polyester was obtained. The number of X in this product was 4.4.

Example 1 100 g of the polyester obtained in Production Example 1 was mixed with 50 g of xylene.
Dissolved in water and heated to 65 ° C., 5 g of formic acid, 1.9 g of Amberlyst 15 (cation exchange type ion exchange resin; manufactured by Rohm and Haas Japan), 0.1 g of sodium acetate.
Was added with stirring, and 36.8 g of 60% hydrogen peroxide aqueous solution was added.
After adding dropwise mol% (hereinafter referred to as “A”) = 180 mol% based on the corresponding cyclohexene group,
Epoxidation was carried out by holding at 6 ° C for 6 hours. The reaction crude product was washed with water, neutralized to pH 8 with 5% by weight sodium carbonate, washed with water, and then xylene and water were distilled off to obtain a highly viscous liquid epoxidized polyester (oxirane oxygen: 4.7% by weight, iodine value). : 1.8, Mn: 1,300, Z: 3.9, reaction rate 98.0
%, Selectivity 87.8%). Furthermore, the ester group in 1730 cm ^-1 in infrared spectroscopic analysis, 860 cm ^-1 and 780 cm ^-1
The characteristic absorption of the epoxy group was detected. There was no gelation during the reaction, no gelation during the post-treatment step, and no decrease in the layer separation during washing with water, and the workability was good. The characteristics of this product were as follows. Acid anhydride curing properties: Good flexibility, Tg: 145 ° C UV curing properties: Good gelation properties, good weather resistance PVC additive properties: Good thermal stability, good bleed resistance

Example 2 50 g of xylene was added to 100 g of the polyester obtained in Production Example 1.
After being heated to 65 ° C., 5 g of formic acid, 1 g of phosphoric acid and 0.1 g of sodium carbonate were added with stirring, and 40.8 g (A = 200 mol%) of 60% hydrogen peroxide aqueous solution was added dropwise. ,
Epoxidation was carried out by holding at 65 ° C for 6 hours. Hereinafter, in the same manner as in Example 1, a highly viscous liquid epoxidized polyester (oxirane oxygen: 5.0% by weight, iodine value: 2.8,
Mn: 1,300, Z: 4.1, reaction rate 96.9%, selectivity 94.4%) were obtained. Furthermore, it is 1730 cm by infrared spectroscopic analysis.
^-1 of the ester group, characteristic absorption of epoxy group was detected in the 860 cm ^-1 and 780 cm ^-1. The workability was good without gelation during the reaction, gelation during the post-treatment step, and deterioration of the layer separation during washing with water. The characteristics of this product were as follows. Acid anhydride curing properties: good flexibility, Tg: 147 ° C UV curing properties: good gelation properties, good weather resistance PVC additive properties: good thermal stability, good bleed resistance

Example 3 50 g of xylene was added to 100 g of the polyester obtained in Production Example 1.
After heating to 65 ° C., 7 g of formic acid, 1 g of sodium monohydrogen phosphate and 0.05 g of sodium carbonate were added with stirring,
After dripping 40.8g (A = 200mol%) of 60% hydrogen peroxide aqueous solution, it hold | maintained at 65 degreeC for 6 hours, and epoxidized. Thereafter, in the same manner as in Example 1, a highly viscous liquid epoxidized polyester (oxirane oxygen: 4.6% by weight, iodine value: 2.8, Mn: 1,300, Z: 3.8, reaction rate 96.9%) , Selectivity 86.9%) was obtained. Furthermore, the ester group in 1730 cm ^-1 in infrared spectroscopic analysis, characteristic absorption of epoxy group was detected in the 860 cm ^-1 and 780 cm ^-1. The workability was good without gelation during the reaction, gelation during the post-treatment step, and deterioration of the layer separation during washing with water. The characteristics of this product were as follows. Acid anhydride curing characteristics: Good flexibility, Tg: 144 ° C UV curing characteristics: Good gelling property, good weather resistance PVC additive characteristics: Good thermal stability, good bleed resistance

Example 4 50 g of xylene was added to 100 g of the polyester obtained in Production Example 1.
Dissolved in water, heated to 65 ° C., formic acid 6 g, boric acid 0.63
g, 0.54 g of sodium metasilicate are added with stirring to 60%.
After dripping 40.8 g (A = 200 mol%) of hydrogen peroxide aqueous solution, it was held at 65 ° C. for 6 hours for epoxidation. Thereafter, in the same manner as in Example 1, a highly viscous liquid epoxidized polyester (oxirane oxygen: 4.9% by weight, iodine value: 1.9, Mn: 1,300, Z: 4.0, reaction rate of 97.
9%, selectivity 91.6%). Furthermore, the ester group in 1730 cm ^-1 in infrared spectroscopic analysis, 860 cm ^-1 and 780cm
The characteristic absorption of epoxy group was detected at ^-1 . The workability was good without gelation during the reaction, gelation during the post-treatment step, and deterioration of the layer separation during washing with water. The characteristics of this product were as follows. Acid anhydride curing properties: Good flexibility, Tg: 145 ° C UV curing properties: Good gelation properties, good weather resistance PVC additive properties: Good thermal stability, good bleed resistance

Example 5 100 g of the polyester obtained in Production Example 1 was mixed with 50 g of xylene.
After being heated to 65 ° C., 6.6 g of Δ ¹ -tetrahydrophthalic anhydride, ¹ g of phosphoric acid and 0.3 g of sodium carbonate were added with stirring, and 40.8 g of a 60% aqueous hydrogen peroxide solution (A = 2) was added.
(00 mol%) was added dropwise, and the mixture was held at 65 ° C. for 5 hours for epoxidation. Thereafter, in the same manner as in Example 1, a highly viscous liquid epoxidized polyester (oxirane oxygen: 4.
8% by weight, iodine value: 1.4, Mn: 1,300, Z: 3.9
, The reaction rate was 98.5%, and the selectivity was 89.3%). Furthermore, by infrared spectroscopic analysis, an ester group at 1730 cm ^-1
Characteristic absorption of epoxy group was detected in the 0 cm ^-1 and 780 cm ^-1. The workability was good without gelation during the reaction, gelation during the post-treatment step, and deterioration of the layer separation during washing with water. The characteristics of this product were as follows. Acid anhydride curing characteristics: Good flexibility, Tg: 144 ° C UV curing characteristics: Good gelling property, good weather resistance PVC additive characteristics: Good thermal stability, good bleed resistance

Production Example 2 THPA 532 g (3.5 mol), isophthalic acid 249
g (1.5 mol), trimethylolpropane 269.4 g
(2 mol), 450 g (5 mol) of 1,4-butanediol, 360 g (2.5 mol) of 2-ethylhexanoic acid, and 0.1% by weight of zinc oxide as a catalyst relative to the total weight of the raw material, xylene 3 Charge the weight% into a flask and heat it to 160 ° C.
From 220 to 220 ° C under azeotropic dehydration of xylene at normal pressure,
The reaction was carried out for 7 hours under a nitrogen gas atmosphere to obtain a polyester having an acid value of 1.2. After the esterification reaction, xylene was distilled off under reduced pressure with heating. The quality of the obtained polyester is as follows: acid value 1.2, hydroxyl value 60, iodine value 57.0, Mn 2.00
0 and X were 4.5.

Example 6 100 g of the polyester obtained in Production Example 2 was mixed with 50 parts of butyl acetate.
g, and after heating to 65 ° C., 5 g of formic acid, 1 g of phosphoric acid,
Sodium carbonate (0.2 g) was added with stirring, and 60% aqueous hydrogen peroxide solution (22.9 g, A = 180 mol%) was added dropwise.
Epoxidation was carried out by holding at 65 ° C for 7 hours. Hereinafter, in the same manner as in Example 1, a highly viscous liquid epoxidized polyester (oxirane oxygen: 2.1% by weight, iodine value: 1.7,
Mn: 2,400, Z: 3.1, reaction rate 97.0%, selectivity 62.3%) were obtained. Furthermore, infrared spectroscopic analysis shows 1730 cm
^-1 of the ester group, characteristic absorption of epoxy group was detected in the 860 cm ^-1 and 780 cm ^-1. The workability was good without gelation during the reaction, gelation during the post-treatment step, and deterioration of the layer separation during washing with water. The characteristics of this product were as follows. Acid anhydride curing properties: Good flexibility, Tg: 105 ° C UV curing properties: Good gelling property, good weather resistance

Example 7 A high-viscosity liquid epoxidized polyester (oxirane oxygen: 2.2% by weight, iodine value: 10.0, Mn: 2,300) was used in the same manner as in Example 6 except that 3.5 g of sodium carbonate was applied. ,
Z: 3.2, reaction rate 82.5%, selectivity 76.4%). Furthermore, the ester group in 1730 cm ^-1 in infrared spectroscopic analysis, characteristic absorption of epoxy group was detected in the 860 cm ^-1 and 780 cm ^-1. The workability was good without gelation during the reaction, gelation during the post-treatment step, and deterioration of the layer separation during washing with water. Although the curing characteristics of this product were equivalent to those of the polyester obtained in Example 6, the weather resistance of the photocured product was
It was a little inferior.

Production Example 3 608 g (4 mol) of THPA and 146 g (1
Mol), trimethylolpropane 269.4 g (2 mol), 1,6-hexanediol 118 g (1 mol),
Ethylene glycol 62 g (1 mol), 2-ethylhexanol 390 g (3 mol), zinc oxide as a catalyst 0.1 wt% to the total weight of the raw material, xylene 3 wt% was charged to the flask, 160 to 220 ℃. The reaction was carried out for 7 hours under azeotropic dehydration of xylene under atmospheric pressure and nitrogen gas aeration to obtain a polyester having an acid value of 0.6. After the esterification reaction, xylene was distilled off under heating and reduced pressure to obtain a raw material for epoxidation. The polyester obtained has an acid value of 0.
6, hydroxyl value 73.5, iodine value 68.5, Mn1,600,
The number of X was 4.3.

Example 8 100 g of the raw material polyester obtained in Production Example 3 was dissolved in 50 g of butyl acetate and heated to 65 ° C., then 5 g of formic acid and 1 part of phosphoric acid
g and 0.3 g of sodium carbonate were added with stirring, and 30.6 g (A = 200 mol%) of 60% aqueous hydrogen peroxide solution was added dropwise, and then the mixture was kept at 65 ° C. for 7 hours for epoxidation. Thereafter, in the same manner as in Example 1, a highly viscous liquid epoxidized polyester (oxirane oxygen: 3.1% by weight, iodine value:
3.1, Mn: 1,800, Z: 3.4, reaction rate 95.5%,
The selectivity was 78.3%). Furthermore, 17
Of ester groups 30 cm ^-1, characteristic absorption of epoxy group was detected in the 860 cm ^-1 and 780 cm ^-1. The workability was good without gelation during the reaction, gelation during the post-treatment step, and deterioration of the layer separation during washing with water. The characteristics of this product were as follows. Acid anhydride curing properties: Good flexibility, Tg: 110 ° C UV curing properties: Good gelling property, good weather resistance

Example 9 100 g of the polyester obtained in Production Example 3 was mixed with 10 parts of butyl acetate.
After being dissolved in 0 g and heated to 65 ° C., 0.7 g of sodium tungstate, 1 g of phosphoric acid, 0.2 g of sodium carbonate and 0.2 g of cetylpyridinium chloride were added with stirring, and 30.6 g of 60% hydrogen peroxide aqueous solution was added. After (A = 200 mol%) was dropped, the mixture was kept at 65 ° C. for 7 hours for epoxidation. Hereinafter, in the same manner as in Example 1, a highly viscous liquid epoxidized polyester (oxirane oxygen: 3.3% by weight, iodine value:
2.2, Mn: 1,700, Z: 3.5, reaction rate 96.8%,
The selectivity was 82.3%). Furthermore, 17
Of ester groups 30 cm ^-1, characteristic absorption of epoxy group was detected in the 860 cm ^-1 and 780 cm ^-1. The workability was good without gelation during the reaction, gelation during the post-treatment step, or deterioration of the layer separation during washing with water. The characteristics of this product were as follows. Acid anhydride curing property: Good flexibility, Tg: 112 ° C UV curing property: Good gelation property, good weather resistance

Example 10 100 g of the polyester obtained in Production Example 3 was added to 30 g of acetone.
And then heated to 40 ° C., 103.7 g (A = 150 mol%) of 25% peracetic acid in acetone was added dropwise, and then 40
After holding at ℃ for 7 hours for epoxidation, the volatile components were distilled off to give a highly viscous liquid epoxidized polyester (oxirane oxygen: 3.4% by weight, iodine value: 1.1, Mn: 1,70
0, Z: 3.6, reaction rate 98.4%, selectivity 83.4%)
Got Furthermore, the ester group in 1730 cm ^-1 in infrared spectroscopic analysis, characteristic absorption of epoxy group was detected in the 860 cm ^-1 and 780 cm ^-1. There was no gelation during the reaction and the workability was good. The characteristics of this product were as follows. Acid anhydride curing properties: good flexibility, Tg: 108 ° C UV curing properties: good gelation properties, good weather resistance

Production Example 4 Reaction was carried out in the same manner as in Production Example 2 except that 581 g (3.5 mol) of 3-methyl-Δ ⁴ -tetrahydrophthalic anhydride was used in place of THPA, and an acid value of 5.3 and a hydroxyl value were obtained. A polyester having 64, iodine value of 49.5, Mn of 2,200 and X of 4.3 was obtained.

Example 11 100 g of the polyester obtained in Production Example 4 was mixed with 50 parts of butyl acetate.
g, and after heating to 65 ° C., 5 g of formic acid, 1 g of phosphoric acid,
Sodium carbonate (0.2 g) was added with stirring, and 60% hydrogen peroxide aqueous solution (22.1 g, A = 200 mol%) was added dropwise.
Epoxidation was carried out by holding at 65 ° C for 7 hours. Thereafter, in the same manner as in Example 1, a highly viscous liquid epoxidized polyester (oxirane oxygen: 2.2% by weight, iodine value: 1.9,
Mn: 2,600, Z: 3.6, reaction rate 96.2%, selectivity 75.5%) were obtained. Furthermore, infrared spectroscopic analysis shows 1730 cm
^-1 of the ester group, characteristic absorption of epoxy group was detected in the 860 cm ^-1 and 780 cm ^-1. The workability was good without gelation during the reaction, gelation during the post-treatment step, or deterioration of the layer separation during washing with water. The characteristics of this product were as follows. Acid anhydride curing properties: good flexibility, Tg: 106 ° C UV curing properties: good gelation properties, good weather resistance

Production Example 5 Reaction was carried out according to Production Example 2 except that 219 g (1.5 mol) of adipic acid was used instead of isophthalic acid, and the acid value was 1.
0, hydroxyl value 57.2, iodine value 58.0, Mn2,100,
A polyester having X of 4.8 was obtained.

Example 12 The high-viscosity liquid epoxidized polyester (oxirane oxygen: 2.0) which was epoxidized according to Example 6 except that the polyester obtained in Production Example 5 was used in place of the polyester obtained in Production Example 2. 4% by weight, iodine value: 1.4, Mn: 2,400,
Z: 3.6, reaction rate 97.6%, selectivity 69.7%). Furthermore, the ester group in 1730 cm ^-1 in infrared spectroscopic analysis, characteristic absorption of epoxy group was detected in the 860 cm ^-1 and 780 cm ^-1. The workability was good without gelation during the reaction, gelation during the post-treatment step, and deterioration of the layer separation during washing with water. The characteristics of this product were as follows. Acid anhydride curing characteristics: Good flexibility, Tg: 103 ° C UV curing characteristics: Good gelation, good weather resistance

Production Example 6 760 g (5.0 mol) of THPA, 202.1 g (1.5 mol) of trimethylolpropane, 236 g (2 mol) of 1,6-hexanediol, 2-ethylhexanol 39
The reaction was carried out in the same manner as in Production Example 2 except that 0 g (3.0 mol) was used, and the acid value was 1.8, the hydroxyl value was 45.9, and the iodine value was 88.0.
Mn of 1,300 and X were obtained as 4.5 polyester.

Example 13 100 g of the polyester obtained in Production Example 6 was mixed with 100 parts of toluene.
g, dissolved in g, heated to 65 ° C., formic acid 10 g, phosphoric acid 0.1 g.
45 g and 0.45 g of sodium dihydrogen phosphate dihydrate were added with stirring, and 43.2 g of a 60% aqueous hydrogen peroxide solution (A
(= 220 mol%) was added dropwise, and the mixture was held at 65 ° C. for 7 hours for epoxidation. Hereinafter, in the same manner as in Example 1, a highly viscous liquid epoxidized polyester (oxirane oxygen:
4.8% by weight, iodine value: 1.3, Mn: 1,400, Z: 4.
Two of them were obtained, a reaction rate of 98.5% and a selectivity of 92.6%). Furthermore, by infrared spectroscopic analysis, an ester group at 1730 cm ^-1
Characteristic absorption of epoxy group was detected in the 0 cm ^-1 and 780 cm ^-1. The workability was good without gelation during the reaction, gelation during the post-treatment step, or deterioration of the layer separation during washing with water. The characteristics of this product were as follows. Acid anhydride curing characteristics: Good flexibility, Tg: 145 ° C. UV curing characteristics: Good gelation, good weather resistance

Comparative Example 1 Epoxidization was carried out under the same conditions as in Example 2 except that xylene was changed to acetone, and after-treatment was carried out without washing with water. After neutralization and filtration, volatile components were distilled off. Highly viscous liquid epoxidized polyester (oxirane oxygen: 0.5
% By weight, iodine value: 2.5, Mn: 1,600, Z: 0.5
, The reaction rate 97.3%, the selectivity 9.4%). Furthermore,
Infrared spectroscopy characteristic absorption of the ester groups to 1730 cm ^-1 in is detected, but the characteristic absorption of the epoxy groups of 860 cm ^-1 and 780 cm ^-1 was unclear. When the curing property of this product with an acid anhydride was evaluated, gelation was insufficient and Tg and flexibility could not be evaluated.

Comparative Example 2 Epoxidation was carried out under the same conditions as in Example 2 except that sodium carbonate was not added. However, the reaction liquid became a highly viscous gel at the 4th hour after the reaction and stirring became impossible.

Comparative Example 3 152 g (1 mol) of THPA and 584 g (4 mol of adipic acid)
Mol), 450 g (5 mol) of 1,4-butanediol, 0.1 wt% of zinc oxide as a catalyst, and 5 wt% of xylene were charged into a flask, and the amount of xylene was adjusted to 160 to 220 ° C. The temperature was raised under azeotropic dehydration, and the reaction was carried out for 20 hours under normal pressure and nitrogen gas aeration. Thereafter, the same treatment as in Production Example 2 was carried out to obtain polyester (acid value: 6.2, hydroxyl value: 3.2, iodine value: 28.1, Mn: 12,000, X:
13.3 pieces) were obtained.

100 g of the above polyester was mixed with butyl acetate 2
Epoxidation was carried out in accordance with Example 6 except that the compound was dissolved in 00 g. The reaction crude was reprecipitated in 1000 g of methanol for 2 times.
Repeatedly, dried under reduced pressure and solidified at room temperature with epoxidized polyester (oxirane oxygen: 0.8% by weight, iodine value: 3.
9, Mn16,000 and Z were 8.0, the reaction rate was 86.1%, and the selectivity was 53.2%). In addition, the infrared spectroscopic analysis shows 1730c
of ester groups m ^-1, 860 cm ^- characteristic absorption of epoxy group was detected in ¹ and 780 cm ^-1. This product was incompatible with 4-methylhexahydrophthalic anhydride and was insufficiently cured. Further, it was insoluble in acetone solvent, and the ultraviolet curing characteristics could not be evaluated.

Comparative Example 4 The characteristics of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, which is a representative compound having two epoxycyclohexane groups in place of the epoxidized polyester of the present invention, are shown. The evaluation was as follows. Acid anhydride curing characteristics: Poor flexibility, Tg: 148 ° C UV curing characteristics: Good gelling property, weather resistance: Slightly poor PVC additive characteristics: Good thermal stability, poor bleeding resistance

[0093]

The epoxidized polyester according to the present invention is excellent in workability, exhibits excellent curability and is excellent in flexibility when applied to a cationically polymerizable resin, an ultraviolet curable resin, an epoxy resin and the like. It gives a cured product and has excellent thermal stability, bleed resistance, migration resistance, and extraction resistance when used as a stabilizer for vinyl chloride resins.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shoji Tani 13 Shin-Nippon Rika Co., Ltd. 13 Yagura-cho, Yashimajima, Fushimi-ku, Kyoto-shi, Kyoto Prefecture

Claims (3)

[Claims] 1. A bifunctional group represented by the general formula (1):
Includes three or more species in the molecule and has a number average molecular weight of about 1,
An epoxidized polyester characterized in that it is from 000 to about 10,000. [Chemical 1] [In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an endomethylene group. ] 2. One of the bifunctional groups represented by the general formula (2).
Number average molecular weight of more than 3 species in the molecule is about 1.0
The epoxy according to claim 1, wherein from 0 to about 10,000 polyesters are dissolved in a hydrocarbon solvent and / or an ester solvent and epoxidized with hydrogen peroxide in the presence of a weakly basic compound. Method for producing modified polyester. [Chemical 2] [In the formula, R ¹ and R ² are the same as in the general formula (1). ] 3. The method for producing an epoxidized polyester according to claim 1, wherein the polyester according to claim 2 is epoxidized with peracetic acid in a non-aqueous system.