JPH0762086A - Polyether polyol, method for producing the same, and resin composition for coating - Google Patents

Abstract

PURPOSE:To obtain the subject bisphenol ether type low-viscosity polymer, good in compatibility and excellent in corrosion resistance, etc., by reacting a bisphenol A type epoxidized substance with a long-chain aliphatic carboxylic acid and a beta-keto ester of a tertiary alcohol. CONSTITUTION:This polymer is obtained by reacting (A) a bisphenol type epoxidized substance with (B) a long-chain aliphatic carboxylic acid (preferably ricinoleic acid, etc.), then reacting the resultant reactional product with (C) a beta-keto ester of a tertiary alcohol (e.g. tert-butyl acetoacetate) or reacting the component (A) with the component (C) and subsequently reacting the component (B) therewith. The polymer has the beta-keto ester in the side chain, a long- chain alkyl ester at both terminals, >=300g/equiv. hydroxyl group equiv. and 800-2000 weight-average formula {R1 and R1' are each an 8-22C alkyl; R2 and R2' are each a 2-4C alkylene; R3 is H or a 1-10C alkyl; A is C, S, etc.; X is OH or the beta-keto ester; [(n)+(p)] is 2-10; [(m)+(o)] is 1-45} is preferred as the polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to β-ketoesterification of hydroxyl groups in a polyether polyol resin obtained by modifying an epoxy resin with a fatty acid to improve compatibility with a low viscosity, and further has excellent adhesion to a metal surface. The present invention relates to a useful epoxy resin as a coating resin composition.

[0002]

2. Description of the Related Art A resin composition using a polyether polyol resin obtained by modifying an epoxy resin with fatty acids and polyisocyanates as a curing agent component has excellent adhesion to a metal surface and is therefore widely used as a coating material. However, for example, under more severe conditions such as adhesion and corrosion resistance with a steel sheet, sufficient properties cannot be obtained yet, and if the content of hydroxyl groups in the resin is increased to further improve adhesion,
The viscosity of the resin was significantly increased, resulting in a resin having extremely poor compatibility with the solvent.

Conventionally, in order to reduce the viscosity of the coating resin, for example, a method of esterifying the hydroxyl groups in the epoxy resin by heating a bisphenol type epoxy resin and diketene in the presence of an ester exchange catalyst is known. Has been.

[0004]

However, a resin obtained by esterifying a bisphenol type epoxy resin with diketene is
Although the effect of reducing the viscosity can be seen, the corrosion resistance and the adhesiveness are still not sufficient, and there is a problem that the anticorrosion property or the corrosion resistance is poor especially when applied to a rust surface.

The problem to be solved by the present invention is to provide a polyether polyol made of an epoxy resin as a raw material, which has low viscosity, good compatibility, and excellent corrosion resistance and adhesiveness, and a composition containing the same. .

[0006]

Means for Solving the Problems As a result of intensive investigations by the present inventors, it has been found that both ends of a bisphenol type polyether polyol are modified with fatty acids, and a hydroxyl group in a side chain is β-ketoesterified. The inventors have found that the above problems can be solved by the above and have completed the present invention.

That is, the present invention has a β-ketoester group on the side chain of the molecule and a long-chain alkyl ester group on both ends of the molecule, has a hydroxyl equivalent of 300 g / eq or more, and has a weight average molecular weight. Of bisphenol type polyether polyol and bisphenol type epoxidized product (A) having a ratio of 800 to 2,000 is reacted with a long-chain aliphatic carboxylic acid (B), and then with a β-ketoester (C) of a tertiary alcohol. Or a bisphenol type epoxidized product (A) is reacted with a β-ketoester (C) of a tertiary alcohol, and then a long-chain aliphatic carboxylic acid (B) is reacted. And a β-ketoester group on the side chain of the molecule, and a long-chain alkyl ester group on both ends of the molecule, and the hydroxyl equivalent A is 200 g / eq or more, and a bisphenol type polyether polyol weight average molecular weight of 800 to 2,000, relates coating resin composition characterized by containing a curing agent.

The polyether polyol of the present invention has β-ketoester groups on the side chains of the molecule and long-chain alkyl ester groups on both ends of the molecule, and has a hydroxyl equivalent of 300 g / e.
q or more and a weight average molecular weight of 800 to 2,
Bisphenol type polyether polyol having a molecular weight of 000, and its structure is not particularly limited, and more specifically, a polyether polyol having a bisphenol skeleton as a repeating unit, that is, a phenol of bisphenol via 2-hydroxypropylene. The main chain is a skeleton bonded to an oxygen atom, which is a hydrogen atom desorbed from a volatile hydroxyl group,
Examples thereof include those having a structure having a long-chain alkyl ester group at its terminal and a β-ketoester group capable of substituting a hydroxyl group existing in the side chain of the main skeleton.

When the hydroxyl equivalent of the polyether polyol is less than 300 g / eq, the resin viscosity is still high, and the coating resin composition has a metal surface or a rust surface due to the introduction of β-ketoester groups. The effect of improving the adhesiveness is not sufficiently exhibited.
Among them, the hydroxyl equivalent is 300 to 300 because it is excellent in low viscosity, excellent in reactivity with a curing agent and improved in coating strength.
It is preferably 1,000 g / eq.

When the weight average molecular weight is less than 800, a polyether polyol having bisphenol as a main skeleton cannot be introduced into the skeleton sufficiently as a polyether polyol, resulting in poor coating strength. Become a thing,
On the other hand, when it exceeds 2,000, the resin viscosity becomes high and the solubility becomes poor. Therefore, it is preferable that the weight average molecular weight is 1,000 to 1,500, from the viewpoint of excellent balance between the coating film strength and the low viscosity or solubility of the resin.

In the polyether polyol of the present invention, the terminal long-chain alkyl ester group may be directly bonded to the terminal aromatic nucleus forming the main chain, but is a group having an alkylene oxide polyaddition structure. Those that are bonded to aromatic nuclei via are preferable because the effect of reducing the resin viscosity is excellent. Specifically, an alkyl ester group having 8 to 22 carbon atoms has a structure linked to an aromatic nucleus through a group having a polyaddition structure of alkylene oxide having 2 to 4 carbon atoms, and In a group having a polyaddition structure of alkylene oxide, the one having 2 to 10 alkylene oxides having 2 to 4 carbon atoms in total in the molecule is added, while maintaining the excellent coating film strength, and a viscosity reducing effect. Is preferable because it is remarkable.

Further, the polyether polyol of the present invention can adjust the resin viscosity even within the same molecular weight by arbitrarily changing the ratio of the hydroxyl group and the β-ketoester group in the resin. The ratio of the hydroxyl group and the β-ketoester group in the epoxy resin is not particularly limited, and the total of the hydroxyl group and the β-ketoester group from the viewpoint of excellent balance between viscosity reduction effect, compatibility, and corrosion resistance and adhesion. On the other hand, the β-ketoester group is preferably 20% or more, and more preferably 20 to 80% from the viewpoint of further improving the adhesiveness.

Such bisphenol type polyether polyols are more preferably those represented by the following structural formula (1). Structural formula (1)

[0014]

[Chemical 2]

(In the structural formula (1), R1 and R'1 each independently represent an alkyl group having 8 to 22 carbon atoms as R2 and R '.
2 are each independently an alkylene group having 2 to 4 carbon atoms, R3
Is an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, R
4 represents an alkyl group having 1 to 10 carbon atoms, A represents an alkylidene group having 1 to 6 carbon atoms, a carbon atom or a sulfur atom, and X represents a hydroxyl group or a β-ketoester group composed of R3 and R4. N and p are n + p = 2 to 10
And m and o are m + o = 1 to 45,
It is an integer that satisfies the condition that o / (m + o) is 20% or more. )

Next, the production method of the present invention for producing the above-mentioned bisphenol type polyether polyol will be described in detail. In the production method of the present invention, the bisphenol type epoxidized product (A) may be reacted with a long-chain aliphatic carboxylic acid (B) and then with a β-ketoester (C) of a tertiary alcohol, or The bisphenol type epoxidized product (A) may be reacted with a β-ketoester (C) of a tertiary alcohol, and then with a long-chain aliphatic carboxylic acid (B). Among them, the former epoxidized product (A) contains a long-chain aliphatic carboxylic acid (B) because it can suppress the production of by-products and can introduce more β-ketoester groups into the molecular skeleton. React, then β-keto ester of tertiary alcohol (C)
Is preferred.

The bisphenol type epoxide (A) used in the present invention may be an epoxide having a molecular skeleton obtained by reacting bisphenol with a bisphenol type epoxy resin, or may be a bisphenol and bisphenol type epoxide. A bisphenol type polyether polyol obtained by reacting with an epoxy resin may be polyadded with an alkylene oxide, and further reacted with epihalohydrin. Examples of the bisphenol include bisphenol A, bisphenol F, bisphenol AD and bisphenol S. Examples of the bisphenol type epoxy resin include the above-mentioned diglycidyl ether of bisphenol.
Examples of epihalohydrin include epichlorohydrin and epibromohydrin.

In this case, the reaction ratio of the bisphenol and the bisphenol type epoxy resin is not particularly limited, and can be arbitrarily adjusted according to the target molecular weight or the presence or absence of polyaddition of alkylene oxide. That is, when the reaction is carried out so that the molar ratio of the bisphenol type epoxy resin is increased, the reaction product can be used as the bisphenol type epoxidized product (A), while the bisphenol is reacted so that the molar ratio is excessive. When it is allowed to do so, it becomes a bisphenol type polyether polyol for polyadding alkylene oxide. Also,
The higher the reaction ratio of the two, the higher the molecular weight.

When a polyaddition structure of alkylene oxide is further introduced into the main skeleton, it is carried out by polyadding an amount of 2 to 10 mol of alkylene oxide to 1 mol of the bisphenol in an autoclave. it can.

The alkylene oxide is not particularly limited, and examples thereof include ethylene oxide, propylene oxide, tetramethylene oxide, and the like. Among them, ethylene oxide is preferable because of its excellent effect of reducing the resin viscosity. . In this case, the epoxidized product (A) used in the present invention can be obtained by further reacting the above-mentioned epihalohydrin.

Then, the epoxidized product (A) thus obtained is reacted with an aliphatic carboxylic acid (B) or a β-ketoester (C) of a tertiary alcohol.
In the case of the former, the reaction ratio is not particularly limited, and usually, the carboxyl group in the aliphatic carboxylic acid (B) is equivalent to the terminal epoxy group of the epoxidized product (A),
Alternatively, it can be obtained by using in a range where the carboxyl group is slightly in excess, and by heating the reaction at 100 to 230 ° C. in the presence of a catalyst or in the absence of a catalyst.

The catalyst used here is not particularly limited, but examples thereof include alkali metal hydroxides such as sodium hydroxide and lithium hydroxide, triethylamine,
Tertiary amines such as tributylamine, pyridine and dimethylbenzylamine, imidazoles such as 2-ethyl-4-methylimidazole, quaternary ammonium salts such as triethylbenzylammonium chloride and tetramethylammonium chloride, tetrabutylphosphonium. Examples thereof include phosphonium salts such as chloride and ethyltriphenylphosphonium iodide, and phosphines such as triphenylphosphine.

The long-chain aliphatic carboxylic acid used in the present invention is not particularly limited, but higher fatty acids having 8 to 22 carbon atoms are preferable from the viewpoints of the effect of reducing viscosity and the strength or water resistance of the coating film. .

Among them, it is preferable to use a monobasic acid from the viewpoint of the effect of reducing the viscosity, and as the fatty acid, either a saturated carboxylic acid or an unsaturated carboxylic acid can be used, and the hydrocarbon chain has a hydroxyl group. It may be one. Specific examples thereof include stearic acid, oleic acid, palmitic acid, ricinooleic acid, dioxystearic acid, soybean oil fatty acid, castor oil fatty acid, sunflower oil fatty acid and the like. Among them, unsaturated carboxylic acids having a hydroxyl group in the hydrocarbon chain are preferable from the viewpoint of more excellent coating film strength, and specific examples thereof include ricinooleic acid, dioxystearic acid, castor oil fatty acid and the like.

Next, the epoxidized product (A) or the epoxidized product (A) reacted with an aliphatic carboxylic acid is reacted with a β-ketoester (C) of a tertiary alcohol.
The reaction conditions are not particularly limited, and the proportion of the β-ketoester (C) of the tertiary alcohol used is not particularly limited, and the hydroxyl group and β-ketoester in the finally obtained polyether polyol are not limited. Although it can be optionally used depending on the reaction ratio with the group, usually, the raw material epoxidized product (A) or the epoxidized product (A) is reacted with an equivalent amount of a long-chain aliphatic carboxylic acid or an excess amount of the long-chain aliphatic carboxylic acid. Can be used.

The β-ketoester of alcohol used in the present invention is not particularly limited, but specific examples include those represented by the following structural formula (2).

[0027]

[Chemical 3] R ¹ : a hydrocarbon group having 1 to 10 carbon atoms R ² : a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms R ³ : a hydrocarbon group having 1 to 15 carbon atoms

Further, specific examples of the β-ketoester represented by the structural formula (3) include, for example, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-iso-propyl, acetoacetate-. n-butyl, acetoacetic acid-iso-butyl, acetoacetic acid-ter
t-butyl, methyl α-acetopropionate, ethyl α-acetopropionate, α-acetopropionate-n-
Propyl, α-acetopropionate-iso-propyl, α-acetopropionate-n-butyl, α-acetopropionate-tert-butyl, α-methyl-β-ketovalerate ethyl, β-ketocaproate ethyl, benzoyl Examples include ethyl acetate. Among these, esters of tertiary alcohols are preferred because they have a faster reaction rate than esters of secondary or primary alcohols. This third
As an ester of a primary alcohol, acetoacetic acid-ter
Examples thereof include t-butyl and α-acetopropionate-tert-butyl.

In this transesterification reaction, an epoxy polyol resin and a β-ketoester of alcohol are mixed in an amount of 80 to 20.
It is preferable to proceed by heating to a temperature of 0 ° C. and removing alcohol as a by-product to the outside of the system.

If desired, a transesterification catalyst may be added.

Further, in the present invention, not only the above transesterification reaction as a method for introducing a β-ketoester group into a side chain but also a method for converting a hydroxyl group into a β-ketoester is performed in the presence of an acid or basic catalyst. Alternatively, a method of reacting diketene with acetoacetate may be used.

When a highly viscous resin or solid resin is used in the production method of the present invention, a solvent may be used. As the solvent that can be used, any non-alcoholic solvent can be used, and examples thereof include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Also, an alcohol solvent can be used as long as it is a tertiary alcohol, and examples thereof include tert-butanol.

When the epoxidized product (A) is first reacted with the β-keto ester of a tertiary alcohol,
Subsequently, the aliphatic carboxylic acid is reacted, and the specific method thereof can be performed under exactly the same conditions as those described above.

The coating resin composition of the present invention comprises the polyether polyol obtained by the above-mentioned production method, and further contains a curing agent as an essential component. The curing agent is not particularly limited as long as it is capable of reacting with a hydroxyl group, and examples thereof include an isocyanate compound, a blocked isocyanate compound, a melamine resin, and a resole-type phenol resin, but are particularly reactive. Isocyanate compounds are preferred because of their excellent properties and the formation of a stronger coating film.

Examples of the isocyanate compound include toluene diisocyanate, xylylene diisocyanate, cyclophenylmethane diisocyanate, hexamethylene diisocyanate, and a 3 mol adduct of trimethylolpropane with toluene diisocyanate, and a high molecular weight polyisocyanate obtained therefrom. To be

The mixing ratio of the isocyanate compound is not particularly limited, but the mixing ratio of the hydroxyl group equivalent and the isocyanate group equivalent in the polyether polyol resin is 0.4 to 1.2, preferably 0.6 to 1. A ratio of 0.0 is preferable.

In the coating resin composition of the present invention, the β-ketoester group in the polyether polyol has a carbonyl group in a keto-type and enol-type equilibrium state.
By this enolization phenomenon, it is possible to chelate with metals such as iron, zinc, copper, tin, and lead that compose the metal plate of the object to be coated. The chelation state is represented by the following structural formula (3). Structural formula (3)

[0038]

[Chemical 4]

This chelate structure can enhance the ionic adhesion to a metal.

In the coating composition of the present invention, an organic solvent can be used, but when polyphenylene polymethylene polyisocyanate is used as the curing agent as described above, the composition is used without using a solvent. Can be

The coating resin composition of the present invention may further contain an extender such as a bituminous substance. Bituminous substances include coal tar, coal tar pitch, swollen carbonaceous material,
Examples include asphalt.

Further, a substitute for the above bituminous substance may be used as the extender. Examples of the substitutes include various ones. For example, aromatic oil resins, petroleum resins, and petroleum-based or coal-based high-boiling neutral oils generally used as diluents can be used.

The above-mentioned bituminous substances and their substitutes may be used alone or in combination, and the total amount of them is based on the polyether polyol resin (A). It is preferably 0.5 to 2.0 times the weight.

If necessary, various curing catalysts, fillers, diluents, dehydrating agents, resins and the like can be added to the composition of the present invention.

[0045]

The present invention will be further described below with reference to examples.
Various tests were evaluated according to the following methods. The samples for evaluation of hardness, flexibility, impact resistance and salt water resistance were metal plates obtained by drying each resin composition at room temperature for 7 days.

(Flexibility) JIS K-5400 (6.1)
According to 6). (Impact resistance) Based on JIS K-5400. (Load 500g) (Salt water resistance) Immersed in 5% salt water for 1 month and visually evaluated according to the following criteria.

◯: No discoloration, wrinkles or blisters. Δ: discolored, no wrinkles and no blisters ×: Discoloration, wrinkles, swelling.

(Rust-preventive property) As the object to be coated, "JIS G
After immersing a 3101 "sandblast plate in 3% saline solution, it was exposed outdoors for 3 days to cause rust, and the rust plate obtained by repeating this 10 times was coated with the coating resin composition obtained in each Example and Comparative Example. The product was applied, immersed in 5% salt water at 40 ° C. for 2 weeks, and the peel strength before and after immersion was measured with an adhesion tester manufactured by Elcometer.

Example 1 A bisphenol A type epoxy resin "EPIC" was used as an epoxy resin in a reactor having means for stirring and temperature indication.
LON 1055 "(manufactured by Dainippon Ink and Chemicals, Inc.,
Epoxy equivalent 475 g / eq) 475 parts by weight was supplied and dissolved in 110 parts by weight of xylene, then linoleic acid 278
1 part by weight of tributylamine was added as a catalyst, and the mixture was reacted at 150 ° C. for 8 hours. At this time, the acid value of the resin was 0.2. This resin solution was cooled to 130 ° C., 259 parts by weight of tert-butyl acetoacetate was added, and the reaction solution was heated to 130 ° C. while removing tert-butanol outside the reaction system. After stirring for an hour, an epoxy polyol resin was obtained. Then, xylene was added and the resin composition was adjusted so that the nonvolatile content was 90%. The resin solution thus obtained is ¹³ C-
From NMR measurement, it was confirmed that 57% of the hydroxyl groups in the equivalent ratio were β-ketoesterified. The structure is shown in Structural Formula (4). In addition, ¹³ C of this obtained epoxy resin
The NMR chart is shown in FIG. 1 (the attribution of each peak is shown in the structural formula (4)), and the infrared absorption spectrum chart is shown in FIG. The resin solution had a nonvolatile content of 90% and had a viscosity of 5,000 cps (25 ° C.). Then, a coating resin composition was obtained in accordance with the formulation shown in Table 2 and various tests were conducted. The results are shown in Table 2.

Structural formula (4)

[0051]

[Chemical 5]

Comparative Example 1 A bisphenol A type epoxy resin "EPIC" was used as an epoxy resin in a reactor having means for stirring and temperature indication.
LON 1055 "(manufactured by Dainippon Ink and Chemicals, Inc.,
Epoxy equivalent 475 g / eq) 475 parts by weight was supplied and dissolved in 110 parts by weight of xylene, then linoleic acid 278
1 part by weight of tributylamine was added as a catalyst, and the mixture was reacted at 150 ° C. for 8 hours. At this time, the acid value of the resin was 0.2. Xylene was added to this resin solution to obtain a resin composition having a nonvolatile content of 90%. Then, a coating resin composition was obtained in accordance with the formulation shown in Table 2 and various tests were conducted.
The results are shown in Table 2.

Example 2 300 parts by weight of an epoxy resin (epoxy equivalent 300) obtained by glycidyl etherification of ethylene oxide polyaddition of bisphenol A type polyether polyol and 172 parts by weight of decanoic acid were mixed, and 1 part by weight of triethylamine was added. After reacting at 150 ° C. for 10 hours, it is cooled to 60 ° C., 63 parts by weight of diketene are added, and 5 hours 60-
Stirring was continued while maintaining the temperature at 70 ° C. Thereafter, toluene was added to obtain a resin solution having a nonvolatile content of 90%. In the resin thus obtained, it was confirmed from the measurement of ¹³ C-NMR that 70% of hydroxyl groups in the equivalent ratio were β-ketoesterified. Then, a coating resin composition was obtained in accordance with the formulation shown in Table 2 and various tests were conducted. The results are shown in Table 2.

Comparative Example 2 Ethylene oxide polyaddition of bisphenol A type polyether polyol was added with 300 parts by weight of epoxy resin (epoxy equivalent of 300) under glycidyl etherification, 63 parts by weight of diketene, and maintained at 60 to 70 ° C. for 5 hours. While stirring was continued. After that, toluene is added and the nonvolatile content is 90%.
Resin solution. Then, a coating resin composition was obtained in accordance with the formulation shown in Table 2 and various tests were conducted. The results are shown in Table 2.

Example 3 300 parts by weight of castor oil fatty acid was mixed with 350 parts by weight of an epoxy resin (epoxy equivalent: 350) obtained by converting propylene oxide polyaddition of bisphenol A type polyether polyol into glycidyl ether, and 1 part by weight of triethylamine was added. After reacting at 150 ° C for 10 hours, 60
The mixture was cooled to 0 ° C, 113 parts by weight of ethyl acetoacetate was added, and stirring was continued while maintaining the temperature at 60 to 70 ° C for 5 hours.
Then, toluene was added to form a resin solution having a nonvolatile content of 90%. In the resin thus obtained, it was confirmed by ¹³ C-NMR measurement that 40% of the hydroxyl groups in equivalent ratio were β-ketoesterified. Then, a coating resin composition was obtained in accordance with the formulation shown in Table 2 and various tests were conducted. The results are shown in Table 2.

COMPARATIVE EXAMPLE 3 300 parts by weight of castor oil fatty acid was mixed with 350 parts by weight of an epoxy resin (epoxy equivalent of 350) obtained by converting propylene oxide polyaddition of bisphenol A type polyether polyol into glycidyl ether, and 1 part by weight of triethylamine was added. After reacting at 150 ° C for 10 hours, 60
After cooling to ℃, toluene was added to obtain a resin solution having a nonvolatile content of 90%. Then, a coating resin composition was obtained in accordance with the formulation shown in Table 2 and various tests were conducted. The results are shown in Table 2.

Incidentally, Examples 1, 2, 3 and Comparative Example 1,
The viscosities of the resin solutions obtained in 2 and 3 are shown in Table 1.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

[0061]

EFFECTS OF THE INVENTION According to the present invention, a polyether polyol having a low viscosity and good compatibility, and a coating resin composition having corrosion resistance and adhesion, particularly excellent rust prevention and corrosion resistance in coating on a rust surface. Can provide things.

Therefore, the coating resin composition of the present invention is extremely useful as a coating material.

[Brief description of drawings]

FIG. 1 is a ¹³ C-NMR chart of the epoxy resin of the present invention obtained in Example 1.

FIG. 2 is a chart diagram of an infrared absorption spectrum of the epoxy resin of the present invention obtained in Example 1.

Claims (15)

[Claims] 1. A β-ketoester group on the side chain of the molecule and a long-chain alkyl ester group on both ends of the molecule, a hydroxyl group equivalent of 300 g / eq or more, and a weight average molecular weight of 800-2. Bisphenol type polyether polyol of 000. 2. The polyol according to claim 1, wherein the proportion of β-ketoester groups in the total number of hydroxyl groups and β-ketoester groups in the polyol is 20% or more. 3. A structure in which an alkyl ester group having 8 to 22 carbon atoms is linked to a terminal aromatic nucleus of the main chain through a group having a polyaddition structure of alkylene oxide having 2 to 4 carbon atoms. The polyol according to claim 2, wherein the alkylene oxide having a polyaddition structure of alkylene oxide has 2 to 10 alkylene oxides having 2 to 4 carbon atoms added in total in the molecule. 4. A polyether polyol represented by the following structural formula (1). [Chemical 1] (In the structural formula (1), R1 and R'1 are each independently an alkyl group having 8 to 22 carbon atoms, R2 and R'2 are each independently an alkylene group having 2 to 4 carbon atoms, and R3 is a carbon number. 1
An alkyl group having 10 to 10 or a hydrogen atom, R4 an alkyl group having 1 to 10 carbon atoms, A an alkylidene group having 1 to 6 carbon atoms, a carbon atom or a sulfur atom, X
Represents a hydroxyl group or a β-ketoester group composed of R3 and R4, n and p are integers such that n + p = 2 to 10, m and o are m + o = 1 to 45, and o / (m + o) is an integer that satisfies the condition of 20% or more. ) 5. A bisphenol type epoxide (A)
With a long-chain aliphatic carboxylic acid (B) and then with a β-ketoester (C) of a tertiary alcohol, or with the bisphenol type epoxidized product (A).
A method for producing a polyether polyol, which comprises reacting with a β-ketoester (C) of a tertiary alcohol, and then reacting with a long-chain aliphatic carboxylic acid (B). 6. A bisphenol type epoxide (A)
The method according to claim 5, wherein the long-chain aliphatic carboxylic acid (B) is reacted with the β-ketoester (C) of a tertiary alcohol. 7. A bisphenol-type epoxidized product (A) reacted with a long-chain aliphatic carboxylic acid (B) or a bisphenol-type epoxidized product (A) with β-ketoester (C) per 1 mol of hydroxyl groups. 0.1 mol to 1.0
The method according to claim 5 or 6, wherein the reaction is carried out in a molar manner. 8. A bisphenol type epoxidized product (A)
The method according to claim 5, 6 or 7, wherein is an epoxide obtained by reacting an alkylene oxide polyadduct of bisphenol with epihalohydrin. 9. The epoxidized product (A) has 2 to 2 carbon atoms.
Long-chain aliphatic carboxylic acid (B) which is obtained by polyadding 2 to 10 alkylene oxides of 4 in one molecule.
Is an alkyl group having 8 to 22 carbon atoms. 10. A bisphenol type epoxidized product (A)
A long-chain aliphatic carboxylic acid (B) or a bisphenol type epoxidized product (A) is reacted with a β-ketoester of a tertiary alcohol in the range of 80 to 200 ° C. The manufacturing method described in 1 above. 11. The method according to claim 10, wherein the β-ketoester of the tertiary alcohol is acetoacetic acid t-butyl ester. 12. A molecule having a β-ketoester group in its side chain and long-chain alkyl ester groups at both ends of the molecule, and having a hydroxyl group equivalent of 300 g / eq or more, and
A coating resin composition comprising a bisphenol type polyether polyol having a weight average molecular weight of 800 to 2,000 and a curing agent. 13. A polyether polyol having a structure in which an alkyl ester group having 8 to 22 carbon atoms is linked to a bisphenol skeleton via a group having a polyaddition structure of alkylene oxide having 2 to 8 carbon atoms. And
The composition according to claim 12, wherein in the group having a polyaddition structure of alkylene oxide, 2 to 10 alkyleneoxy groups are added in the total number in the molecule. 14. The composition according to claim 13, wherein the β-ketoester group in the polyether polyol is an acetoacetyl group. 15. The composition according to claim 11, 12, 13 or 14, wherein an isocyanate compound is used as a curing agent.