WO2021234816A1 - Thermosetting resin composition and cured film - Google Patents

Abstract

The present invention addresses the problem of providing a thermosetting resin composition which contains a polyester resin as the base resin and is capable of using ester-exchange reaction as the curing reaction. This thermosetting resin composition is characterized by containing: a polyester resin (A) having a hydroxyl group (a) and an alkyl ester group (b); and an ester-exchange catalyst (B).

Description

Thermosetting resin composition and cured film

The present invention relates to a thermosetting resin composition and a cured film.

The present inventors are studying thermosetting resin compositions having a transesterification reaction as a curing reaction (Patent Documents 1 to 4). Recent studies have revealed that by making the transesterification reaction a curing reaction, it is possible to secure the same curing performance as the curing using a generally known melamine resin or polyisocyanate compound. ..

The above-mentioned Patent Documents 1 to 4 mainly disclose thermosetting resin compositions using an acrylic polymer as a substrate resin. On the other hand, thermosetting resin compositions are used in many fields. Therefore, the required physical properties of the cured resin may differ depending on the application and purpose. In some fields, when an acrylic polymer is used, a cured product having the desired physical characteristics may not be obtained.

In the conventional thermosetting resin composition, in addition to the acrylic polyol, a polyester polyol is also widely used. Since the chemical structure of the polyester polyol is different from that of the acrylic polyol, its physical properties are also different from those of the acrylic polyol. Therefore, if a thermosetting resin composition using a polyester polyol as a substrate resin and having a transesterification reaction as a curing reaction can be obtained, it is expected that it can be used in many new applications.

Japanese Patent No. 6398026 International release 2019/069783 International release 2019/139069 Japanese Unexamined Patent Publication No. 2003-119401

An object of the present invention is to provide a thermosetting resin composition in which a polyester resin is used as a base resin and a transesterification reaction can be a curing reaction.

The present invention is a thermosetting resin composition comprising a polyester resin (A) having a hydroxyl group (a) and an alkyl ester group (b), and a transesterification catalyst (B).
The present invention is a thermosetting resin composition comprising a polyester resin (C) and a polyol compound (D) having an alkyl ester group (b), and a transesterification catalyst (B).
The present invention is characterized by containing a polyester resin (E) having a hydroxyl group (a), a compound (F) having an alkyl ester group (b), and a transesterification catalyst (B). It is a thing.

The alkyl ester group (b) preferably has a structure represented by the following general formula (1) or (2).

(In both the general formula (1) and the general formula (2), R ₁ is an alkyl group having 50 or less carbon atoms.
R ₂ is, in part, an oxygen atom, a nitrogen atom and containing carbon atoms which may have 50 or less alkylene group)

The polyester resin preferably has a structural unit represented by the general formula (3) in the resin chain.

(In the formula, X is an alkylene group having 50 or less carbon atoms which may contain an oxygen atom and a nitrogen atom as a part).
R _b is an alkyl group having 50 or less carbon atoms.

The present invention has a structure represented by the following general formula (1).

(In the formula, Ra represents a tertiary alkyl group)
And the structure represented by the following general formula (2)

(In the formula, Rb represents a primary alkyl group)
It is also an alkyl ester compound characterized by having at least one of both in the molecule.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a resin composition containing a polyester resin as a substrate resin and having a transesterification reaction as a curing reaction. As such a thermosetting resin composition, by using a polyester resin, a cured product having excellent flexibility, glossiness, and adhesion can be obtained.

It is a figure which shows the result of the rigid pendulum test of the comparative example 1. FIG. It is a figure which shows the result of the rigid pendulum test of the comparative example 2. It is a figure which shows the result of the rigid pendulum test of Example 1. FIG. It is a figure which shows the result of the rigid pendulum test of Example 2. It is a figure which shows the result of the rigid pendulum test of the comparative example 3. FIG. It is a figure which shows the result of the rigid pendulum test of Example 3.

Hereinafter, the present invention will be described in detail.
The present invention relates to a thermosetting resin composition in which a polyester resin is used as a substrate resin and a transesterification reaction is used as a curing reaction. Conventionally, a thermosetting resin using a polyester resin as a base resin has generally been cured by using a polyester polyol having a hydroxyl group and using it in combination with a curing agent such as a melamine resin or an isocyanate compound.

The present inventors have disclosed thermosetting resin compositions having a transesterification reaction as a curing reaction in the above-mentioned Patent Documents 1 to 4 and the like. However, in these inventions, the study on the use of the polyacrylic resin as the substrate resin was mainly carried out, and the specific study on the thermosetting resin composition mainly composed of the polyester resin was not carried out. ..

In a polyester resin, many ester bonds are present, but even if the ester bonds in the resin chain cause transesterification, the molecular weight does not increase, and therefore a curing reaction does not occur. On the other hand, the presence of an alkyl ester causes transesterification to increase the molecular weight, which can cure the resin.

From the above viewpoint, it is essential in the present invention to use a resin composition having an alkyl ester group.
As the resin composition having the alkyl ester group, mainly
(I) A thermosetting resin composition (II) alkyl ester group containing a polyester resin (A) having a hydroxyl group (a) and an alkyl ester group (b) and an ester exchange catalyst (B). A thermosetting resin composition (III) containing a polyester resin (C) and a polyol compound (D) having (b), and an ester exchange catalyst (B), and a polyester resin having a hydroxyl group (a). Examples thereof include a thermosetting resin composition comprising (E) and a compound (F) having an alkyl ester group (b), and an ester exchange catalyst (B).
Further, a resin composition in which two or more of the polyester resins (A), (C) and (E) are used in combination can also be used.

That is, it has at least one polyester resin having a hydroxyl group and / or an alkyl ester group, and further, a polyol compound and a compound having an alkyl ester group are used in combination, if necessary. With such a composition, the resin as a whole has a hydroxyl group and an alkyl ester group.

The alkyl ester group is a functional group represented by the general formula of -COOR. Here, R is an alkyl group. In the polyester resin, the structure is a terminal structure such as a main chain end or a side chain end, and the ester bond in the main chain of the polyester resin does not correspond to this.

The alkyl group is not particularly limited, and known alkyl groups such as a methyl group, an ethyl group, a benzyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group are used. Those having a group can be used. The alkyl group preferably has 50 or less carbon atoms. Since the alkyl group is preferably produced as an alcohol during the transesterification reaction and volatilizes, the alkyl group preferably has 20 or less carbon atoms, and more preferably 10 or less. Further, the boiling point of the alcohol volatilized in the curing reaction is preferably 300 ° C. or lower, more preferably 200 ° C. or lower. R may be any of 1st grade, 2nd grade and 3rd grade, but it is most preferably 1st grade from the viewpoint of reactivity and cost.

In the present invention, the molar ratio of the alkyl ester group to the hydroxyl group is not particularly limited in the entire resin composition, but it is preferably in the range of 99/1 to 1/99. The lower limit is more preferably 90/10 and most preferably 80/20. The upper limit is more preferably 90/10 and most preferably 20/80.

The polyester resins (A) and (E) used in the compositions (I) and (III) above preferably have a hydroxyl value of 10 to 500. The lower limit is more preferably 30 and most preferably 50. The upper limit is more preferably 400, and most preferably 300.
Further, as described in detail below, when the alkyl ester group has a structure represented by the following general formula (1), it may be a hydroxyl group existing in the structure.

It is preferable that the hydroxyl group in the polyester resin is mainly introduced as a hydroxyl group at the end of the resin. Therefore, it can be introduced by adjusting the mixing ratio, molecular weight, etc. of the raw materials of the polyester resin. Polyester resins having a hydroxyl group are well known and can be produced by a general method. Further, a commercially available product can be used.

The polyester resins (A) and (C) used in the compositions of (I) and (II) above have an alkyl ester group.

The method for introducing the alkyl ester group into the resin is not particularly limited. For example, a method by esterifying a terminal carboxyl group with respect to a polyester resin having a carboxyl group terminal (method 1), during polymerization of the polyester resin. , A method of producing a polyester having a terminal alkyl ester by using a compound in which a part of polycarboxylic acid or hydroxycarboxylic acid is alkyl-esterified as a raw material (method 2), which has a predetermined structure during polyester resin polymerization. A method of producing a polyester resin having an alkyl ester group as a side chain by using a raw material (method 3), and a method of reacting a polyester polyol having a terminal hydroxyl group with a compound having both a carboxyl group and an alkyl ester group. (Method 4) and the like can be mentioned.

Hereinafter, these methods will be described in detail. The polyester resin in the present invention is not limited to the one produced by the method described in detail below.

Method (1) A method for subjecting a polyester resin having a carboxyl group terminal to an esterification reaction of a terminal carboxyl group- a method for substituting a polyester resin having a COOH group with an alkyl ester group will be described in detail below. do.
Although various reactions can be considered as such a reaction, the ester group represented by the following general formula is particularly preferable in that the reactivity of the transesterification reaction is excellent and the cost is low.

(In both the general formula (1) and the general formula (2), R ₁ is an alkyl group having 50 or less carbon atoms.
R ₂ is, in part, an oxygen atom, a nitrogen atom and containing carbon atoms which may have 50 or less alkylene group)

The structure represented by the general formula (1) is a structure that can be obtained by performing a reaction as shown in the following general formula (11) on the epoxy compound.

In the above reaction, the compound having an alkyl ester group and a carboxyl group to be used can be produced, for example, by a reaction between an acid anhydride and an alcohol as in the following reaction.

The acid anhydride used as a raw material in the reaction represented by the general formula (12) is not particularly limited, and for example, succinic anhydride, maleic anhydride, phthalic anhydride, and hexahydrophthalic acid having a cyclic structure are not particularly limited. Anhydrates of various dibasic acids such as anhydrides, methylhexahydrophthalic anhydrides, benzoic acid anhydrides, and itaconic acid anhydrides can be used. The reaction represented by the above general formula (12) is a well-known general reaction, and the reaction conditions and the like can be carried out under general conditions.

The compound having an alkyl ester group and a carboxyl group used in the synthesis method represented by the general formula (11) is not limited to the compound obtained by the method of the general formula (12), and other compounds are used. It does not matter if it is obtained by the method.

In the synthesis method represented by the general formula (11), a polyester resin having an epoxy group is used as an essential component.

The method for producing such a polyester resin is not particularly limited, and examples thereof include a method of reacting a compound having two or more epoxy groups with a carboxyl group-containing polyester resin. The compound having two or more epoxy groups is not particularly limited, and for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether. , Polypropylene glycol diglycidyl ether, Neopentyl glycol diglycidyl ether, 1.6-hexanediol diglycidyl ether, glycerin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol A alkylene glycol adduct diglycidyl ether, hydrogenated bisphenol A diglycidyl ether , Resolcinol diglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol polyglycidyl ether and the like.

Further, for example, by reacting epichlorohydrin with a polyester resin having a carboxylic acid terminal, an epoxy group can be introduced at the end of the polyester resin. By carrying out the above-mentioned reaction with such a polyester resin having a terminal epoxy group, a polyester resin compound having a functional group represented by the above-mentioned general formula (1) can be obtained. The general formula of such a reaction is shown below.

By carrying out the above-mentioned reaction with the polyester resin having a carboxyl group at the terminal, various epoxy group-containing polyester resins can be obtained. The polyester resin used as a raw material here will be described in detail below.

Further, the epoxy compound described above may be a cyclic epoxy compound.
That is, when a polyester resin having a cyclic epoxy group at the terminal is used, a compound having a structure represented by the general formula (2) can be obtained by the following reaction.

The polyester resin having a cyclic epoxy group at the terminal can be obtained, for example, by reacting a polyester resin having an acid terminal with a compound having two or more cyclic epoxy groups.

In carrying out the above-mentioned reaction, a polyester resin having an acid terminal can be used as a raw material.
The polyester resin having an acid terminal can usually be produced by an esterification reaction or a transesterification reaction between an acid component and an alcohol component.
Examples of the acid component include compounds usually used as an acid component in the production of polyester resin. Examples of the acid component include aliphatic polybasic acids, alicyclic polybasic acids, aromatic polybasic acids, and their anhydrides and esterified products.
The polyester resin having an acid terminal can also be obtained by a method of reacting an acid anhydride with a polyester polyol having a terminal hydroxyl group. The acid anhydride is not particularly limited, and the above-mentioned ones can be used.

As the aliphatic polybasic acid and their anhydrides and esterified products, generally, an aliphatic compound having two or more carboxyl groups in one molecule, an acid anhydride of the aliphatic compound, and an ester of the aliphatic compound are used. Fats such as succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, undecanoic acid, dodecane acid, brush acid, octadecane acid, citric acid, butanetetracarboxylic acid. Examples thereof include a group polyvalent carboxylic acid; an anhydride of the above aliphatic polyvalent carboxylic acid; an esterified product of a lower alkyl having about 1 to about 4 carbon atoms of the above aliphatic polyvalent carboxylic acid, and any combination thereof.
The aliphatic polybasic acid is preferably adipic acid and / or adipic acid anhydride from the viewpoint of smoothness of the obtained coating film.

The alicyclic polybasic acid, and their anhydrides and esterified products are generally compounds having one or more alicyclic structures and two or more carboxyl groups in one molecule, and acid anhydrides of the above compounds. And esterified compounds of the above compounds. The alicyclic structure is mainly a 4- to 6-membered ring structure. Examples of the alicyclic polybasic acid and its anhydrides and esterified products include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and 4-cyclohexene-1. , 2-dicarboxylic acid, 3-methyl-1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, etc. Alicyclic polyvalent carboxylic acid; an anhydride of the alicyclic polyvalent carboxylic acid; an esterified product of a lower alkyl having about 1 to about 4 carbon atoms of the alicyclic polyvalent carboxylic acid, and any of them. Combinations can be mentioned.

As the alicyclic polybasic acid and their anhydrides and esterified products, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid anhydride, 1, 3-Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid anhydride are preferred, and 1,2-cyclohexanedicarboxylic acid and / Alternatively, 1,2-cyclohexanedicarboxylic acid anhydride is more preferable.

The aromatic polybasic acids, and their anhydrides and esters, are generally aromatic compounds having two or more carboxyl groups in one molecule, acid anhydrides of the aromatic compounds, and esters of the aromatic compounds. Aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, trimellitic acid, pyromellitic acid; Acid anhydrides; lower alkyl esters of the above aromatic polyvalent carboxylic acids having about 1 to about 4 carbon atoms, and any combination thereof.
As the aromatic polybasic acid and its anhydrides and esterified products, phthalic acid, phthalic anhydride, isophthalic acid, trimellitic acid, and trimellitic anhydride are preferable.

Further, as the acid component, an acid component other than the aliphatic polybasic acid, the alicyclic polybasic acid and the aromatic polybasic acid, for example, coconut oil fatty acid, cottonseed oil fatty acid, hemp oil fatty acid, rice bran oil fatty acid, fish oil fatty acid. , Thor oil fatty acid, soybean oil fatty acid, flaxseed oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid and other fatty acids; Monocarboxylic acids such as acids, linoleic acid, linolenic acid, benzoic acid, p-tert-butyl benzoic acid, cyclohexanic acid, 10-phenyloctadecanoic acid; lactic acid, 3-hydroxybutanoic acid, 3-hydroxy-4-ethoxybenzoic acid Such as hydroxycarboxylic acids, etc., as well as any combination thereof.

The alcohol component includes polyhydric alcohols having two or more hydroxyl groups in one molecule, for example, ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4. -Butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,2-butanediol, 1,1 , 1-Trimethylol propane, 2-butyl-2-ethyl-1,3-propanediol, 1,2-pentanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,3-Dimethyltrimethylethylene glycol, tetramethylene glycol, 3-methyl-4,3-pentanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-Hexanediol, 1,5-hexanediol, 1,4-hexanediol, 2,5-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, neohydroxypivalate Dihydric alcohols such as pentylglycol ester, hydrogenated bisphenol A, hydrogenated bisphenol F, dimethylolpropionic acid; polylactone diol obtained by adding a lactone compound such as ε-caprolactone to the above dihydric alcohol; bis (hydroxyethyl) terephthalate and the like. Esteldiol compounds; polyetherdiol compounds such as alkylene oxide adducts of bisphenol A, polyethylene glycol, polypropylene glycol, polybutylene glycol; glycerin, trimethylolethane, trimethylolpropane, diglycerin, triglycerin, 1, 2, 6 -Trivalent or higher alcohols such as hexanetriol, pentaerythritol, dipentaerythritol, tris (2-hydroxyethyl) isocyanuric acid, sorbitol, mannit, etc .; lactone compounds such as ε-caprolactone are added to the above trivalent or higher alcohols. Polylactone polyol compound; fatty acid esterified product of glycerin and the like.

Further, as the alcohol component, an alcohol component other than the polyhydric alcohol, for example, monoalcohol such as methanol, ethanol, propyl alcohol, butyl alcohol, stearyl alcohol, 2-phenoxyethanol; propylene oxide, butylene oxide, "Cadura E10" ( Examples thereof include alcohol compounds obtained by reacting a monoepoxy compound such as a trade name, glycidyl ester of a synthetic highly branched saturated fatty acid manufactured by HEXION Specialty Chemicals) with an acid.

The method for producing the polyester resin having an acid terminal is not particularly limited, and the polyester resin can be produced according to a usual method. For example, the acid component and the alcohol component are heated in a nitrogen stream at about 150 to about 250 ° C. for about 5 to about 10 hours to carry out an esterification reaction or a transesterification reaction between the acid component and the alcohol component. Thereby, a polyester resin having an acid terminal can be produced.

Method (2) A method of producing a polyester resin having an alkyl ester group at the terminal by using a compound in which a part of polycarboxylic acid or hydroxycarboxylic acid is alkyl esterified as a raw material at the time of polyester resin polymerization. > In the production of the polyester resin, a compound in which a part of the polycarboxylic acid is alkyl-esterified can be used as a part of the raw material.
The compound in which a part of the polycarboxylic acid is alkyl-esterified is a compound having both an alkyl ester group (-COOR group) and a carboxyl group (-COOH group). Therefore, in the step of the esterification reaction for producing polyester, the carboxyl group reacts with the hydroxyl group and is incorporated into the polyester resin. Since the alkyl ester group is unreacted at the time of polyester polymerization, a polyester resin having an alkyl ester group can be obtained.

The compound in which a part of the polycarboxylic acid that can be used in the method for producing a polyester resin by such a method is alkyl esterified is not particularly limited, and an alkyl ester group (-COOR group) and a carboxyl group (-) are not particularly limited. Those having both COOH groups) can be used.
More specifically, among the various polycarboxylic acids described above, a partially alkylated compound can be mentioned.
More preferably, a compound obtained by reacting various acid anhydrides with an alcohol can be mentioned.
Examples of the acid anhydride include succinic anhydride, maleic anhydride, and phthalic anhydride. Examples of the compound exemplified as the acid anhydride that can be used in the reaction of the above general formula (12) can be mentioned. By reacting these acid anhydrides with a monohydric alcohol, a compound having both an alkyl ester group (-COOR group) and a carboxyl group (-COOH group) can be obtained.

The method for producing the polyester resin using this is not particularly limited, and the method can be performed according to a general method for producing a polyester resin for paint.

The polyester resin obtained by such a method has a terminal,

_RX is an alkyl group having 50 or less carbon atoms.
_RY is an alkylene group having 50 or less carbon atoms which may contain an oxygen atom and a nitrogen atom in a part thereof).
It is a polyester resin having at least one structure represented by.

Method (3) A method of producing a polyester resin having an alkyl ester group as a side chain by using a raw material having a predetermined structure at the time of polymerizing the polyester resin. In the production of the polyester resin, the following general formula (21) ) And a method for introducing an alkyl ester group as a side chain by using a compound having a structure represented by the general formula (22).

(In the formula, Ra represents a tertiary alkyl group)

(In the formula, Rb represents a primary alkyl group)

Among the above structures, the structure represented by the general formula (21) is a structure having two tertiary alkyl esters, and the structure represented by the general formula (22) is a structure having a primary alkyl ester. ..
The tertiary alkyl ester group is not particularly limited, and examples thereof include a t-butyl group.

The compound having the structure represented by the general formula (21) and the structure represented by the general formula (22) can be represented by the following general formula (23).

In the above general formula, X represents an alkylene group having 50 or less carbon atoms which may contain an oxygen atom and a nitrogen atom as a part. The number of carbon atoms is more preferably 30 or less, and even more preferably 20 or less.

When such a compound is heated, only the portion of COORa, which is a tertiary alkyl ester, is hydrolyzed to form a carboxylic acid group, but COORb, which is a primary alkyl ester group, is not hydrolyzed. Therefore, the following reactions occur.

In the system of polyester polymerization reaction, the carboxyl group generated by the above reaction reacts with the hydroxyl group in the system to form a part of the polyester chain.
Therefore, in the end, in the chain

It is possible to obtain a polyester resin having a structure represented by.
The alkyl ester group of -COORb having the structure represented by the above general formula causes a transesterification reaction with a hydroxyl group, whereby a curing reaction can be caused.

The above compound is also one of the present inventions. Such a compound can be obtained by a Michael addition reaction using a malonic acid tertiary ester compound and a compound having a primary ester group and an unsaturated bond as raw materials.
More specifically, the compound of the following general formula (24) obtained by reacting a malonic acid tertiary ester compound with a primary alkyl ester of (meth) acrylic acid can be mentioned.

The reaction between the malonic acid tertiary ester compound and the primary alkyl ester of (meth) acrylic acid is expressed by a general formula as follows.

When a polyester resin having the above-mentioned structure is obtained, it can be obtained by synthesizing a polyester resin in combination with various polycarboxylic acids and polyols.
Examples of other raw materials for the polyester resin that can be used here include those described above. The method for producing the polyester resin is not particularly limited, and the polyester resin can be produced by a general method.

Method (4) Method of reacting a polyester polyol having a terminal hydroxyl group with a compound having both a carboxyl group and an alkyl ester group. Is a well-known resin on the market. A polyester polyol having a hydroxyl group substituted with an alkyl ester group terminal can also be used.

That is, the terminal hydroxyl group can be converted into an alkyl ester group by the following reaction.

The raw material polyester resin used for such a reaction is not particularly limited, and for example, any polyester resin using the above-mentioned various polycarboxylic acids and polyols as raw materials can be used. A commercially available polyester resin can also be used. The commercially available polyester resin is not particularly limited, and for example, Claret polyol F-510, Claret polyol F-1010, Claret polyol F-1010, Claret polyol F-3010 (manufactured by Claret Co., Ltd.), Beckolite 46-118, Becko. Light 46-119, Becko Light 54-707, Becko Light M-6205-50, Becko Light M-6401-52, Becko Light M-6402-50 (manufactured by DIC Co., Ltd.), Adeka New Ace NS-2400, Adeka New Ace YT-101, Adeka New Ace F7-67, Adeka New Ace # 50, Adeka New Ace F1212-29, Adeka New Ace YG-108, Adeka New Ace V14-90, Adeka New Ace Y65-55 (manufactured by ADEKA Corporation) ), Tesslac 2455, Tessrack 2459, Tessrack 2460, Tessrack 2461, Tessrack 2462, Tessrack 2464, Tessrack 2469, Tessrack 2471 (manufactured by Hitachi Chemical Co., Ltd.) and the like.

The compound having both a carboxyl group and an alkyl ester group used in the above reaction is not particularly limited, but a compound represented by the general formula (12) detailed in the above method (1) is used. be able to.

The polyester resin obtained by the above method (4) has the same terminal as the polyester resin obtained by the above method (2).

_RX is an alkyl group having 50 or less carbon atoms.
_RY is an alkylene group having 50 or less carbon atoms which may contain an oxygen atom and a nitrogen atom in a part thereof).
It is a polyester resin having at least one structure represented by.

In the thermosetting resin composition of the present invention, in addition to the polyester resin described above, the compound (F) having an alkyl ester and / or the polyol compound (D) can be used in combination. The resin composition as a whole needs to have an alkyl ester group and a hydroxyl group. A compound having both an alkyl ester group and a hydroxyl group can also be used in combination.
The compounds that can be used as the compound (F) having such an alkyl group are exemplified below.

(F-1) Compound obtained as a derivative of a compound having an active methylene group The compound having an active methylene group represented by the following general formula (31) can be subjected to various compounds (for example, a vinyl group) by the reaction of the active methylene group. A compound having an alkyl ester group can be obtained by reacting with a compound having a compound, a compound having a halogen group, or the like). The compound obtained by such a reaction can also be used as the compound (F) of the present invention.

(In the formula, R ₁ represents a primary or secondary alkyl group. Y represents an OR ₁ group or a hydrocarbon group having 5 or less carbon atoms. When 2 R ₁ is present in one molecule, it represents. these R ₁ may be one which differs even in the same.)

The _{structure of R 1} is not particularly limited, but known components such as a methyl group, an ethyl group, a benzyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a sec-butyl group are known. Those having an alkyl group can be used.

Specific examples of the compound having such an active methylene group include malonic acid ester and acetoacetic ester. A compound obtained by reacting these compounds with a vinyl compound or a halogen group-containing compound can be used. Each of these will be described below.

(F-1-1) Compound obtained by reacting a compound having an active methylene group with a vinyl group-containing compound A compound having an active methylene group can be added to a double bond by a Michael addition reaction. A general Michael addition reaction with such a compound having an active methylene group is represented by the following formula (32).

In the above reaction, a compound represented by the following general formula (32-1) can also be obtained by causing a Michael reaction in both of the two hydrogens of the active methylene group.

The compound obtained by such a reaction has a structure represented by the general formula (32) and / or a structure represented by the general formula (32-1), which has two or more alkyl ester groups. Since it is a compound having, it can be particularly preferably used for the purpose of the present invention.

In particular, when (meth) acrylic acid or a derivative thereof is used as the vinyl compound of the above general formula,

Will cause a reaction with. In the above general formula, R ₁ represents a primary or secondary alkyl group having 50 or less carbon atoms. R ₂ represents a hydrogen or methyl group. R ₁₆ is not particularly limited and may be any functional group depending on the purpose.

In the above reaction, a compound represented by the following general formula (34) can also be obtained by causing a Michael reaction in both of the two hydrogens of the active methylene group.

The compound represented by the general formula (34) can be obtained by adjusting the molar ratio of the (meth) acrylic acid ester to the active methylene compound in the formulation of the raw materials. Further, by preparing these molar ratios, it can also be obtained as a mixture of the compound represented by the general formula (33) and the compound represented by the general formula (34). The ester compound obtained by such a reaction is

The molecule has a structural unit represented by the structure of.

In the above-mentioned reaction, by using an acrylic acid derivative having two or more unsaturated bonds as a raw material, the structure represented by the above-mentioned general formula (35) and / or the structure represented by (36) can be molecularly formed. It can also be an ester compound having two or more in it. That is, it has the functional group.

A compound having a structure represented by the general formula of can be preferably used in the present invention. Such a compound is preferable in that it has high transesterification reactivity and has many COOR groups in the molecule, so that good curability can be obtained. _{Most preferably, n 3} and n ₄ in the above general formula are 2 to 12. Further, L, M, and C are not particularly limited as long as they have a structure such that the molecular weight of the compound is 3000 or less, and may have any functional group such as a hydroxyl group, an ester group, an ether group, and the like. Represents a hydrocarbon group.

Further, the above-mentioned "compound obtained by the reaction of a compound having a (F-1-1) active methylene group and a compound containing a vinyl group" is made from a compound having two or more unsaturated bonds in one molecule. A compound may be used and may have two or more structures represented by the above general formula (10) and / or a structure represented by the general formula (11) in one molecule.

Many compounds having a structure derived from a compound ester having an active methylene group are known, but the compound having the above structure is liable to undergo an addition reaction between a malonic acid ester or an acetoacetic ester and a vinyl group, and can be synthesized. It is easy, and the number of ester groups can be adjusted by selecting the starting material, which is particularly preferable in that the curing performance and the performance of the cured resin can be easily adjusted. Specifically, dimethyl malonate, diethyl malonate, din-butyl malonate, methyl acetoacetate, ethyl acetoacetate and the like can be preferably used.

Such a compound is obtained by carrying out a Michael addition reaction with a compound having an active methylene group using various (meth) acrylic acid derivatives having one or more unsaturated bonds as raw materials. The above-mentioned "(meth) acrylic acid derivative having one or more unsaturated bonds" is not particularly limited, and examples thereof include the following.

Examples of (meth) acrylates with 1 functional group are methyl (meth) acrylates, ethyl (meth) acrylates, isopropyl (meth) acrylates, n-butyl (meth) acrylates, iso-butyl (meth) acrylates, sec-butyl ( Examples thereof include meta) acrylate and t-butyl (meth) acrylate.

Examples of (meth) acrylates having 2 functional groups are 1,4-butanediol di (meth) acrylates, 1,3-butanediol di (meth) acrylates, 1,6-hexanediol di (meth) acrylates, and ethylene glycols. Di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate , 1,10-decanediol di (meth) acrylate, glycerin di (meth) acrylate, dimethylol-tricyclodecanedi (meth) acrylate (DCP-A), EO adduct diacrylate of bisphenol A (manufactured by Kyoeisha Chemical Co., Ltd.) Light acrylate BP-4EA, BP-10EA) Includes PO adduct diacrylate of bisphenol A (manufactured by Kyoeisha Chemical Co., Ltd .; BP-4PA, BP-10PA, etc.). Among them, PO adduct diacrylate of bisphenol A (manufactured by Kyoeisha Chemical Co., Ltd .; BP-4PA), dimethylol-tricyclodecandi (meth) acrylate (DCP-A) and the like can be preferably used.

Examples of (meth) acrylates having 3 functional groups include trimethylolmethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide-modified tri (meth) acrylate, and trimethylolpropane propylene oxide-modified tri (meth) acrylate. Includes meth) acrylate, pentaerythritol tri (meth) acrylate, glycerin propoxytri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate and the like. Among them, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate and the like can be preferably used.

Examples of (meth) acrylates having 4 functional groups are dipentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethylene oxide-modified tetra (meth) acrylate, and pentaerythritol propylene oxide-modified tetra (meth) acrylate. , Ditrimethylolpropane tetra (meth) acrylate and the like. Among them, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like can be preferably used.

Examples of (meth) acrylates having 5 or more functional groups are dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, propionic acid-modified dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth). Examples thereof include polyfunctional (meth) acrylates such as acrylates, ditrimethylolpropane hexa (meth) acrylates, and hexa (meth) acrylates of caprolactone modified products of dipentaerythritol.

(F-1-2) Compound obtained by reacting a compound having an active methylene group with a halogen-containing compound The compound obtained thereby can also be suitably used in the present invention. In particular, a compound in which the carbonyl carbon of the ester group is directly halogenated can be mentioned. The halogen is not particularly limited, and examples thereof include chlorine, bromine, and iodine. Examples of such a compound include compounds obtained by the reaction formula represented by the following general formula (39).

R ₁ and R ₂ are primary or secondary alkyl groups having 50 or less carbon atoms (R ₁ and R ₂ may be the same), W is a hydrocarbon group or -OR ₁ group having 5 or less carbon atoms, and Z is a halogen. n is 1 or 2

Specific examples of the compound corresponding to the compound (F-1) as described above are shown below.

In the formula, R represents the same or different primary or secondary alkyl group. n ₅ represents 1 to 10.

The compound (F-1) preferably contains 3 or more primary or secondary alkyl esters serving as cross-linking points in the molecule. That is, the larger the number of alkyl ester groups in the molecule, the higher the crosslink density of the cured resin, which is preferable in that the hardness of the cured product becomes good and the cured product having excellent physical properties can be obtained. It is more preferable that the primary or secondary alkyl ester is 5 or more in the molecule.

(F-2) Alkyl esterified product of polyfunctional carboxylic acid A compound obtained by reacting a polyfunctional carboxylic acid with an alcohol can also be used as a compound having an alkyl ester group of the present invention. Such a reaction can be expressed by the following general formula.

A compound having an alkyl ester group obtained by performing the same reaction on a carboxylic acid derivative can also be used for the purpose of the present invention.

Various polyfunctional carboxylic acids are general-purpose raw materials that are widely and inexpensively provided in many applications such as polyester raw materials, polyamide raw materials, neutralizers, synthetic raw materials and the like. A compound obtained by alkyl esterifying such a polyfunctional carboxylic acid by a known method can also be used in the present invention.

When such a compound is used as a compound having an alkyl ester group, it can be esterified at low cost by a known method, and a multivalent ester group can be introduced with a relatively low molecular weight. Further, esterification is preferable in that the compatibility with the organic solvent is improved and the product can be suitably used.

The polyfunctional carboxylic acid used here is not particularly limited, and for example, one having 50 or less carbon atoms can be used.
More specifically, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brushic acid, octadecanedioic acid, citric acid, butanetetra. An aliphatic polyvalent carboxylic acid such as a carboxylic acid;
1,2-Cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 3-methyl-1,2-cyclohexanedicarboxylic acid, 4-methyl An alicyclic polyvalent carboxylic acid such as -1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid;
Aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, trimellitic acid, pyromellitic acid;
Hydroxycarboxylic acids such as lactic acid, 3-hydroxybutanoic acid, 3-hydroxy-4-ethoxybenzoic acid;
And so on.

In the present invention, the above-mentioned method for alkyl esterifying a polyfunctional carboxylic acid is not particularly limited, and a known method such as dehydration condensation with an alcohol can be applied. Further, a method of alkyl esterifying a derivative of a polyfunctional carboxylic acid can also be mentioned.

The alkyl esterified product of the polyfunctional carboxylic acid preferably has a molecular weight of 10,000 or less. Such a setting is preferable in that the molecules are easy to move and the curing proceeds. The molecular weight may be lower, such as 6,000 or less, 4000 or less, and 2000 or less.

(F-3) A compound having an alkyl ester group having a structure represented by the following general formula (41).

n = 0 to 20
R ₁ is an alkyl group having 50 or less carbon atoms.
R ₃ is hydrogen or an alkyl group having 10 or less carbon atoms.
The above structure is described above.

About the structure of the general formula (41) The structure of the general formula (41) is based on the α-substituted carboxylic acid ester skeleton.
In the general formula (41), n is 0 to 20.
The lower limit of n is more preferably 1. The upper limit of n is more preferably 5.
Further, it may be a mixture of a plurality of components having different values of n in the above general formula (41). In this case, the average value nav of n is preferably 0 to 5. The lower limit of nav is more preferably 1. The upper limit of nav is more preferably 3. The measurement of nav can be performed by NMR analysis. Furthermore, the value of n can also be measured by NMR analysis.

n may be 0, but a value exceeding 0 is preferable in that a thermosetting resin composition having higher reactivity can be obtained.
That is, when n is 1 or more, curing at a lower temperature can be achieved, and thereby the effect of the present invention can be more preferably exhibited.
More specifically, when n = 0, thermosetting at 120 ° C. can be performed, and when n = 1 or more, thermosetting at 100 ° C. can be performed.

In the above general formula (41), any alkyl group having 50 or less carbon atoms can be used as _{R 1, and it may be any of primary, secondary and tertiary.}

The alkyl group in the above alkyl ester group (that is, R ₁ in the above general formula) is an alkyl group having 50 or less carbon atoms, more preferably in the range of 1 to 20 carbon atoms, and further preferably 1 It is in the range of 10 to 10, and more preferably in the range of 1 to 6. Most preferably, it is in the range of 1 to 4. Within such a range, the curing reaction can be suitably proceeded, which is preferable.

Specific examples of the alkyl group include known examples such as a methyl group, an ethyl group, a benzyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a t-butyl group. Those having an alkyl group can be used.

_{R 3} in the above general formula (41) is hydrogen or an alkyl group having 10 or less carbon atoms. The alkyl group is not particularly limited, but is hydrogen, methyl group, ethyl group, benzyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group. It can be any alkyl group such as. Of these, hydrogen and methyl groups are particularly preferable.

The compound having the functional group (41) has the following general formula (42) corresponding to the structure represented by the general formula (41).

(V represents halogen and hydroxyl group)
It can be obtained by reacting an ester compound in which an active group V is introduced at the α-position of a carbonyl group having the above structure with a carboxylic acid or a carboxylic acid salt. This can be expressed by a general formula as follows.

In the above general formula, the compound that can be used as a raw material represented by the general formula (43) is not particularly limited as long as it is a carboxylic acid or a carboxylic acid derivative capable of causing the above-mentioned reaction. Examples of the carboxylic acid derivative include OM (carboxylate) for Y, OC = OR (acid anhydride), Cl (acid chloride) and the like. In the case of the above-mentioned Y = OM carboxylate, examples of the carboxylate include sodium salt, potassium salt, amine salt, zinc salt and the like.

The compound represented by the general formula (43) can be a compound having a skeleton corresponding to the target structure (a) represented by the general formula (41).

The production method of the compound represented by the general formula (42) is not particularly limited. Among the compounds represented by the above general formula (4), the compound of n = 0 is a compound having an active group represented by X ₂ in α-position, exemplified various α-hydroxy acids, the α halogenated carboxylic acid be able to. Specific examples thereof include methyl chloroacetate, ethyl chloroacetate, methyl bromoacetate, ethyl bromoacetate, t-butyl bromoacetate, methyl 2-chloropropionate, methyl glycolate, methyl lactate, ethyl lactate, butyl lactate and the like. Can be done.

Among the compounds represented by the general formula (42), for compounds having n = 1 or more, an example of the production method thereof is shown below.
The contents shown below are examples of the production method, and the present invention is not limited to the compounds obtained by the following production methods.

For example, it can be obtained by reacting a carboxylic acid having a halogen at the α-position, a salt thereof or a derivative thereof with a carboxylic acid alkyl ester having a halogen or a hydroxyl group at the α-position. This can be expressed by a general formula as follows.

Examples of the carboxylic acid having a halogen at the α-position, a salt thereof or a derivative thereof include alkali metal salts of carboxylic acids (potassium salt, sodium salt, etc.), acid anhydrides, acid chlorides and the like. Specifically, sodium chloroacetate or the like can be used as the compound represented by the general formula (44).

Examples of the carboxylic acid alkyl ester having a halogen or a hydroxyl group at the α-position include alkyl esters of α-substituted carboxylic acid compounds such as chloroacetic acid, bromoacetic acid and lactic acid. The alkyl group of the above alkyl ester is not particularly limited, and may be any alkyl group having 1 to 50 carbon atoms.
Such an alkyl group may be any of 1st to 3rd grade, and specifically, a methyl group, an ethyl group, a benzyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and sec-. Butyl group, t-butyl group and the like can be mentioned.

In the above reaction, _{it is preferable that X 2} and X ₃ are of different types. It is preferable to consider these as different types of functional groups and have different reactivity, and select a combination of functional groups so that _{X 2 remains unreacted.} Specifically, _{a combination of X 2} as a bromo group and X ₃ as a chloro group is particularly preferable.

Further, the value of n can be adjusted by adjusting the mixing ratio of the two raw materials in the above reaction. In the above reaction, it is generally obtained as a mixture of a plurality of kinds of compounds having different n. By purifying the compound represented by the above general formula (44), only a compound having a specific value of n may be used, or a mixture of a plurality of types of compounds having different values of n may be used. good.

The chemical structure represented by the general formula (42) can be formed by reacting the compound represented by the general formula (42) with various carboxylic acid compounds. Therefore, the compound represented by the above general formula (42) can be reacted with any "compound having a carboxylic acid group", and the compound having a chemical structure represented by the above general formula (41) is selected as a compound. There are numerous possible types of compounds.

In the present invention, it can be presumed that the thermosetting resin composition having remarkably excellent transesterification reaction is obtained from the structure represented by the above-mentioned general formula (41). The "compound having a carboxylic acid group" is not particularly limited, and any compound can be mentioned.

Further, the above-mentioned "compound having a carboxylic acid group" is preferably a compound having two or more functional groups. The "compound having two or more functional groups" means having two or more functional groups involved in the cross-linking reaction in the present invention, and specifically, a compound having two or more carboxylic acid groups may be used. Further, it may be a compound having a hydroxyl group or a compound having a polymerizable unsaturated bond.

When used as a resin composition, it is preferable to use a compound having two or more functional groups to cause a crosslinking reaction. Therefore, in order to obtain such a resin in the resin composition, it has two or more functional groups represented by the above-mentioned general formula (41), or a functional group other than the above-mentioned general formula (41). It is preferable to use a "compound having a carboxylic acid group" having.

The compound substituted with the structure represented by the general formula (41) preferably has a molecular weight of 10,000 or less. Such a setting is preferable in that the molecules are easy to move and the curing proceeds. The molecular weight may be lower, such as 6000 or less, 4000 or less, 2000 or less.

As an example of such a compound, the general structure of the compound when the above-mentioned reaction is carried out using citric acid as a polycarboxylic acid is shown below.

(F-4) A compound having two or more functional groups represented by the general formula (1) and / or functional groups represented by the general formula (2) Functional groups represented by the general formula (1) and / or general. The compound having a functional group represented by the formula (2) can be obtained by the production method as described above.
A compound having two or more such functional groups and a compound having such a functional group and a hydroxyl group can be suitably used as a component of a resin composition having a transesterification reaction as a curing reaction.

The compound having a functional group represented by the general formula (1) and / or a functional group represented by the general formula (2) is used as a curable functional group in the curable resin composition. Therefore, it is preferable that the compound has two or more functional groups. More specifically, it may have two or more functional groups represented by the above general formula (1) and / or a functional group represented by the general formula (2), or may have two or more functional groups represented by the above general formula (1). ) And / or a functional group represented by the general formula (2), and may further have a hydroxyl group or the like.

As described above, the functional group represented by the general formula (1) is subjected to the reaction represented by the general formula (11) or the reaction represented by the general formula (14) with respect to various epoxy compounds. And / or a functional group represented by the general formula (2) can be introduced.
Therefore, a compound obtained by carrying out a reaction represented by the above general formula (1) with a known epoxy compound can also be used in the present invention.
The epoxy compound that can be used for such a reaction is not particularly limited, and is, for example, an aliphatic polyfunctional liquid epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, or a biphenyl type epoxy. Examples thereof include resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol derivative epoxy resins, naphthalene skeleton or alicyclic skeleton-containing novolak epoxy resins, and epoxy resins having an oxylan ring of glycidyl ether. Can be done.
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule.

Further, as described above, an epoxy compound can be obtained by carrying out a reaction represented by the general formula (13) with a carboxylic acid or a derivative thereof.
Then, by carrying out the reaction represented by the above general formula (11) with the epoxy compound, the functional group represented by the general formula (1) and / or the functional group represented by the general formula (2) Can be obtained.
Therefore, by carrying out the above-mentioned reaction with various polycarboxylic acids and hydroxycarboxylic acids, a compound having two or more such functional groups and a compound having such a functional group and a hydroxyl group can be obtained.

The polycarboxylic acid that can be used as a raw material for producing a compound having a functional group represented by the general formula (1) and / or a functional group represented by the general formula (2) by the above reaction is particularly limited. For example, those having 50 or less carbon atoms can be used.
More specifically, the above-mentioned polycarboxylic acids and hydroxycarboxylic acids can be mentioned. Further, since the functional group represented by the general formula (1) and / or the functional group represented by the general formula (2) has a hydroxyl group,
Palm oil fatty acid, cotton seed oil fatty acid, hemp seed oil fatty acid, rice bran oil fatty acid, fish oil fatty acid, tall oil fatty acid, soybean oil fatty acid, flaxseed oil fatty acid, tung oil fatty acid, rapeseed oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid Fatty acids such as: lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, p-tert-butyl benzoic acid, cyclohexanoic acid, 10-phenyloctadecanoic acid and other monocarboxylic acids. Can be used.

As a specific example of such a compound, for example, a compound having a structure as shown below can be mentioned.

The following compounds can be used as the polyol compound (D).
(D-1) Low molecular weight polyol A low molecular weight polyol (specifically, a molecular weight of 2,000 or less) can be used in the present invention as a compound having at least two hydroxyl groups in the molecule.
Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, diethylene glycol, trimethylene glycol, tetraethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, and 2,3. -Butandiol, 1,2-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,2-butanediol, 1,1,1-trimethylolpropane, 2-butyl-2-ethyl -1,3-Propanediol, 1,2-pentanediol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 2,3-dimethyltrimethylethylene glycol, tetramethylene glycol, 3 -Methyl-4,3-pentanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-Hexanediol, 2,5-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, hydroxypivalic acid neopentyl glycol ester, hydrogenated bisphenol A, hydrogenated bisphenol F, Dihydric alcohol such as dimethylol propionic acid; Polylactone diol obtained by adding a lactone compound such as ε-caprolactone to the above dihydric alcohol; Esteldiol compound such as bis (hydroxyethyl) terephthalate; alkylene oxide adduct of bisphenol A, polyethylene Polyetherdiol compounds such as glycols, polypropylene glycols and polybutylene glycols; glycerin, trimethylolethane, trimethylolpropane, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, tris (2). -Hydroxyethyl) Examples of trihydric or higher alcohols such as isocyanuric acid, sorbitol, and mannit.

Such low molecular weight polyols are known as general-purpose products and can be obtained at low cost. Further, the small molecule polyol has high water solubility and can be suitably used as a cross-linking agent for the purpose of curing in an aqueous system.

(D-2) Polyol Resin In the resin composition of the present invention, various polyols other than the polyester polyol can be used in combination. The polyol that can be used in combination is not particularly limited, and examples thereof include an acrylic polyol, a polycarbonate polyol, and a urethane polyol. Further, these polyol resins may have an alkyl ester group.

The acrylic polymer having an alkyl ester group preferably has at least a part of a structural unit as represented by the following general formula.

n ₁ : 1 to 10

Structure represented by [COOR _5] - _{(wherein, R 1, R 2, R} 3 are the same or different, hydrogen, an alkyl group, a carboxyl group, an alkyl ester group or the following _R 4.
R ₄ is the number of atoms of the main chain is 50 or less may have a main chain ester group in an ether group, an amide group, one or more functional groups selected from the group consisting of urethane , An aliphatic, alicyclic or aromatic alkylene group which may have a side chain.
R _5, the number 50 following an alkyl group having a carbon,
Examples of the compound represented by the above general formula include those disclosed in Patent Document 3.

Transesterification catalyst (B)
The thermosetting resin composition of the present invention contains a transesterification catalyst (B). That is, the transesterification catalyst (B) is blended in order to efficiently cause a transesterification reaction between the ester group and the hydroxyl group and obtain sufficient thermosetting property.

As the transesterification catalyst (B), any compound known as one capable of activating the transesterification reaction can be used.
Specifically, various acidic compounds such as, for example, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid or sulfonic acid; various basic compounds such as LiOH, KOH or NaOH, amines; sulfonic acid groups. Examples thereof include compounds having (dodecylbenzene sulfonic acid, phenol sulfonic acid, metasulfonic acid, paratoluene sulfonic acid) and compounds having a group consisting of an alkali metal salt or an amine salt of sulfonic acid. Further, a photoresponsive catalyst and a thermal latent catalyst that generate an acid by light or heat can also be used.
Among them, various substances such as PbO, zinc acetate, lead acetate, antimony trioxide, tetraisopropyl titanate, dibutyltin dilaurate, dibutyltin dioctate or monobutyltinic acid can be used to fully exert the effects of the present invention. It is desirable to use metal compounds and the like.

The ester exchange catalyst (B) in the present invention includes at least one compound (B-1) selected from the group consisting of an organic phosphorus compound, urea, dialkylurea, a sulfoxide compound, a pyridine and a pyridine derivative, and zinc and tin. Most preferably, it contains a compound (B-2) containing at least one metal element selected from the group consisting of titanium, aluminum and iron. ..
By using a specific compound (B-1) in combination with the above compound (B-2), the catalytic action can be improved and an excellent catalytic reaction can be produced.

Although the action of obtaining such an effect is not clear, it is presumed that the coordination of the compound (A) with the metal compound improves the catalytic activity. Therefore, as the compound (A), it is preferable to select a compound that can be coordinated to the metal compound.

The form of the thermosetting resin composition of the present invention is not particularly limited, but it is particularly preferable that the thermosetting resin composition has an organic solvent-based or water-based form. This is preferable in that thin film coating is possible and low temperature curing can be performed. The aqueous system may be either water-soluble or water-dispersible, and may be mixed with water such as ethanol, methanol, alcohol, glycol, ether, and ketone in an arbitrary ratio in addition to water. It may contain an aqueous solvent that can be produced.

The organic solvent-based thermosetting resin composition is a composition in which the above components are dissolved or dispersed in various organic solvents. The organic solvent that can be used is not particularly limited, and hydrocarbons such as 1-hexane, 1-octane, 1-decane, 1-tetradecane, cyclohexane, benzene and xylene, ethers such as dimethyl ether and diethyl ether, acetone and methyl ethyl ketone. , Etc., ketones such as trichloromethane, carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethylene and the like, ethanol, methanol, propanol, butanol, acetone, cyclohexanone and the like can be used.

Further, as the two-component resin composition, a solution containing an ester compound and a solution containing a hydroxyl group-containing compound may be combined and used immediately before use. This is preferable in that the storage stability is good. Further, a two-component type in which a catalyst solution containing a transesterification catalyst (B) is mixed with a solution containing a composition having an alkyl ester ester group and a hydroxyl group can also be used.

Further, in the case of a powder-shaped thermosetting resin composition such as a powder coating material, it can be produced by drying, mixing and pulverizing each of the above-mentioned components by a usual method.

The thermosetting resin composition of the present invention can be suitably used in the fields of thermosetting paints, thermosetting adhesives and the like.

When used as a thermosetting paint, in addition to the above-mentioned components, additives generally used in the paint field may be used in combination. For example, coloring pigments, extender pigments, brilliant pigments, etc., and any combinations thereof may be used in combination.

When a pigment is used, it is preferably contained in the range of 1 to 500% by weight in total, based on 100% by weight of the total solid content of the resin components. The lower limit is more preferably 3% by weight, still more preferably 5 parts by weight. The upper limit is more preferably 400% by weight, still more preferably 300% by weight.

Examples of the coloring pigment include titanium oxide, zinc flower, carbon black, molybdenum red, prusian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindolin pigment, slene pigment, and perylene pigment. , Dioxazine pigments, diketopyrrolopyrrole pigments and the like, and any combination thereof.

Examples of the extender pigment include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, alumina white and the like, with barium sulfate and / or talc being preferable, and barium sulfate being more preferable.

Examples of the bright pigment include aluminum (including vapor-deposited aluminum), copper, zinc, brass, nickel, aluminum oxide, mica, titanium oxide or iron oxide-coated aluminum oxide, titanium oxide or iron oxide. Aluminum oxide, glass flakes, hologram pigments, etc., and any combination thereof can be mentioned. The aluminum pigments include non-leaving type aluminum and leaving type aluminum.

If desired, the thermosetting paint may be added to paints such as thickeners, ultraviolet absorbers, light stabilizers, defoamers, plasticizers, organic solvents other than the hydrophobic solvents, surface conditioners, and antisettling agents. It may further contain an agent.

Examples of the thickener include inorganic thickeners such as silicate, metallic silicate, montmorillonite, and colloidal alumina; a copolymer of (meth) acrylic acid and (meth) acrylic acid ester, and poly. Polyacrylic acid-based thickeners such as sodium acrylate; have a hydrophilic part and a hydrophobic part in one molecule, and the hydrophobic part is adsorbed on the surface of pigments and emulsion particles in the paint in an aqueous medium. , An associative thickener that exhibits a thickening effect by associating the hydrophobic portions with each other; a fibrous derivative-based thickener such as carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose; Protein-based thickeners; Arginic acid-based thickeners such as sodium alginate; Polyvinyl-based thickeners such as polyvinyl alcohol, polyvinylpyrrolidone, and polyvinylbenzyl ether copolymers; Pluronic polyethers, polyether dialkyl esters, polyether dialkyl ethers, Polyether-based thickeners such as polyether epoxy modified products; Anhydrous maleic acid copolymer-based thickeners such as partial esters of vinylmethyl ether-maleic anhydride copolymers; Polyamide thickeners such as polyamideamine salts Etc., as well as any combination thereof.

The polyacrylic acid-based thickeners are commercially available, and are, for example, "ACRYSOLASE-60", "ACRYSOLTT-615", "ACRYSOLRM-5" (hereinafter referred to as "trade names") manufactured by Roam and Hearth, and San Nopco. Examples thereof include "SN Thickener 613", "SN Thickener 618", "SN Thickener 630", "SN Thickener 634", and "SN Thickener 636" (hereinafter referred to as product names).

Further, the above-mentioned association type thickener is commercially available, for example, "UH-420", "UH-450", "UH-462", "UH-472", "UH-540" manufactured by ADEKA. "UH-752", "UH-756VF", "UH-814N" (hereinafter, trade name), "ACRYSOLRM-8W", "ACRYSOLRM-825", "ACRYSOLRM-2020NPR", "ACRYSOLRM" manufactured by Roam and Hearth. -12W "," ACRYSOLSCT-275 "(above, product name), San Nopco's" SN Thickener 612 "," SN Thickener 621N "," SN Thickener 625N "," SN Thickener 627N "," SN Thickener 660T "( As mentioned above, the product name) and the like can be mentioned.

The thermosetting resin composition of the present invention may contain at least one curing agent component selected from the group consisting of a polyisocyanate compound, a melamine resin and an alkoxysilane compound.
The curing agent component is not particularly limited, and polyisocyanate compounds, melamine resins, and alkoxysilane compounds, which are known as curing agents that cause a reaction with a hydroxyl group, can be used.

When the curing agent is a polyisocyanate compound and / or a melamine resin, the blending amount (that is, (curing agent amount) / (curing agent amount + resin component amount) with respect to the total amount of the resin component and the curing agent is 0.01. It is preferably in the range of about 50% by weight. It is preferable that the blending amount is in the range of this, because the curing reaction by the ester exchange reaction and the curing reaction by another curing agent occur at the same time.
The lower limit is more preferably 0.01% by weight, further preferably 1% by weight. The upper limit is more preferably 30% by weight, further preferably 20% by weight.

When the curing agent is an alkoxysilane compound, the (curing agent amount) / (curing agent amount + resin component amount) is preferably 0.001 to 10% by weight. The range of such a blending amount is preferable in that a curing reaction by a transesterification reaction and a curing reaction by another curing agent occur at the same time.

The object to be coated to which the heat-curable paint can be applied is not particularly limited, and is, for example, a paint for cans, a PCM paint; an outer panel of an automobile body such as a passenger car, a truck, a motorcycle, or a bus; an automobile part; Various examples can be given such as household electric products such as mobile phones and audio equipment, building materials, furniture, adhesives, coating agents for films and glass, and the like. When used as an automobile paint, it can be used for the effect of any layer such as an intermediate coating paint, a base paint, and a clear paint.

The object to be coated may be a metal surface such as the metal material and a vehicle body formed from the metal material, which may be subjected to surface treatment such as phosphate treatment, chromate treatment, composite oxide treatment, or the like. It may be an object to be coated having a coating film.
Examples of the object to be coated having the coating film include those obtained by subjecting a base material to a surface treatment as desired and forming an undercoat coating film on the substrate. In particular, a vehicle body on which an undercoat film is formed by an electrodeposition paint is preferable, and a car body on which an undercoat film is formed by a cationic electrodeposition paint is more preferable.

The object to be coated may be a plastic material, a plastic surface of an automobile part molded from the plastic material, or the like, if desired, surface-treated, primer-coated, or the like. Further, the plastic material and the metal material may be combined. Since the thermosetting resin composition of the present invention can be cured at a low temperature, it can be suitably used as a paint for plastics.

The coating method of the heat-curable paint is not particularly limited, and examples thereof include air spray coating, airless spray coating, rotary atomization coating, curtain coat coating, roll coat coating, and the like, and air spray coating and rotary atomization. Painting or the like is preferable. At the time of painting, electrostatic electricity may be applied if desired. By the above coating method, a wet coating film can be formed from the above water-based coating composition.

The wet coating film can be cured by heating. The curing can be carried out by a known heating means, for example, a drying oven such as a hot air furnace, an electric furnace, or an infrared induction heating furnace. The wet coating is preferably at a temperature in the range of 100-300 ° C., more preferably 120-270 ° C., and even more preferably 140-220 ° C., preferably in the range of about 10-about 60 minutes, and more preferably about 15 ° C. It can be cured by heating for about 40 minutes.

When the thermosetting resin composition of the present invention is used in the field of coating materials, it is required to have sufficient curing performance having performances such as smoothness, water resistance and acid resistance.
On the other hand, when used in the fields of adhesives and adhesives, the high curable ability required for paints is not required. The thermosetting resin composition of the present invention can be of a level that can be used as a paint, but even a composition that does not reach such a level is used in the fields of adhesives, pressure-sensitive adhesives, and the like. May be available.

The present invention is a cured film characterized by being formed by three-dimensionally cross-linking the above-mentioned thermosetting resin composition.
Such a cured film has sufficient performance so that it can be used as a paint / adhesive.

Hereinafter, the present invention will be described in more detail based on Examples. The present invention is not limited to the following examples. In the text, the part represents the weight.

Comparative Example Kuraray Polyester F-3010 (trade name: manufactured by Kuraray Co., Ltd.) 250 parts, propylene glycol monomethyl ether acetate 53.6 parts, aromatic hydrocarbon (T-SOL 100: trade name manufactured by JXTG Energy Co., Ltd.) 53 .6 parts were mixed to prepare polyester resin A.

Synthesis example 1
Kuraray polyol F-3010 (manufactured by Kuraray Co., Ltd.) 250 parts, Ricacid SA (succinic anhydride; trade name: manufactured by Shin Nihon Rika Co., Ltd.) 8.6 parts, propylene glycol monomethyl ether acetate 55.4 parts, aromatic hydrocarbons ( 55 parts of T-SOL 100) was added and reacted at 70 ° C. until the hydrocarbon SA was dissolved, and the disappearance of the hydrocarbon SA was confirmed by NMR. Next, 36 parts of Epolite 100MF (trimethylolpropane triglycidyl ether; manufactured by Kyoeisha Chemical Co., Ltd.), 8 parts of propylene glycol monomethyl ether acetate, and 8 parts of aromatic hydrocarbon (T-SOL 100) were added and reacted at 90 ° C. for 5 hours. I let you. The reaction was confirmed by acid value measurement. Further, 24 parts of monomethyl succinate, 5 parts of propylene glycol monomethyl ether acetate, and 5 parts of aromatic hydrocarbon (T-SOL 100) were added and reacted at 90 ° C. for 13 hours to synthesize polyester resin B.

Synthesis example 2
30 parts of Kuraray polyol F-3010 (manufactured by Kuraray Co., Ltd.), 2 parts of monomethyl succinate and 30 parts of toluene were mixed and reacted at 125 ° C. for 4 hours. The reaction was confirmed by acid value measurement and the polyester resin C was used.

Synthesis example 3
85 parts of isophthalic acid, 60 parts of adipic acid, 80 parts of neopentyl glycol and 35 parts of trimethylolpropane were mixed and reacted at 230 ° C. for 6 hours. After completion of the reaction, the polyester resin D was diluted with a mixed solvent of xylene, aromatic hydrocarbon (T-SOL 100) and propylene glycol monomethyl ether acetate to a solid content of 70%.

Synthesis example 4
75 parts of isophthalic acid, 51 parts of adipic acid, 26 parts of monomethyl succinate, 78 parts of neopentyl glycol and 34 parts of trimethylolpropane were mixed and reacted at 230 ° C. for 6 hours. After completion of the reaction, the polyester resin E was diluted with a mixed solvent of xylene, aromatic hydrocarbon (T-SOL 100) and propylene glycol monomethyl ether acetate to a solid content of 70%.

Synthesis example 5
130 parts of adipic acid, 104 parts of neopentyl glycol, 7 parts of paratoluenesulfonic acid, and 234 parts of toluene were charged into a flask equipped with a water diversion tube. A dehydration reaction was carried out while refluxing the mixture, and the reaction was carried out for 6 hours to obtain polyester resin F.

Synthesis example 6
28 parts of methyl acrylate, 36 parts of di-tbutyl malonate, 28 parts of potassium carbonate, 1.5 parts of 18-crown-6 ether and 64 parts of tetrahydrofuran were mixed and stirred at 50 ° C. for 1 hour. After completion of the reaction, cyclohexane and water were added and washed with water. The organic layer was neutralized with a saturated aqueous solution of ammonium chloride, washed twice with water, and the obtained organic layer was concentrated under reduced pressure to obtain ester compound A.

Synthesis example 7
117 parts of adipic acid, 40 parts of ester compound A, 104 parts of neopentyl glycol, 7 parts of paratoluenesulfonic acid, and 261 parts of toluene were charged into a flask equipped with a water diversion tube. A dehydration reaction was carried out while refluxing the mixture, and the reaction was carried out for 6 hours to obtain polyester resin G.

Synthesis example 8
118 parts of isophthalic acid, 50 parts of adipic acid, 47 parts of neopentyl glycol and 80 parts of trimethylolpropane were charged in a reaction apparatus equipped with a rectification column, the temperature was raised to 160 ° C, and the temperature was further increased to 160 to 230 ° C for 3 hours. The temperature was gradually increased.
Then, after continuing the reaction at 230 ° C. for 30 minutes, the rectification tower was replaced with a water diversion device, 13 parts of xylene was added to the content part, and xylene was also added to the water diversion device to co-boil water and xylene. After water was removed, the reaction was carried out until the acid value became 10 mgKOH / g or less, and the mixture was cooled to adjust the solid content with cyclohexanone to obtain a polyester polyol H which is a polyester resin solution having a resin solid content of 50%.

Synthesis example 9
40 parts of methyl acetoacetic acid, 60 parts of methyl acrylate, 48 parts of potassium carbonate, 1.5 parts of 18-crown-6 ether and 100 parts of tetrahydrofuran were mixed and stirred at 50 ° C. for 3 hours. After completion of the reaction, cyclohexane and water were added and washed with water. The organic layer was neutralized with a saturated aqueous solution of ammonium chloride, washed twice with water, and the obtained organic layer was concentrated under reduced pressure to obtain ester compound B.

Synthesis example 10
Ester compound C was obtained by adding triethylbenzylammonium chloride and a polymerization inhibitor to 190 parts of monomethyl succinate and 201.5 parts of trimethylolpropane triglycidyl ether (Kyoeisha Chemical Co., Ltd. Epolite 100MF) and reacting at 90 ° C. for 10 hours or more. ..

Synthesis example 11
16 parts of diethyl malonate, 14 parts of potassium carbonate and 60 parts of tetrahydrofuran were mixed and heated to 50 ° C. Twelve parts of ethyl chloroformate was added dropwise over 1 hour, and the mixture was stirred at 70 ° C. for 10 hours. After completion of the reaction, 140 parts of toluene and 100 parts of 10% saline solution were added. The organic layer was washed twice with 100 parts of water and then concentrated under reduced pressure to obtain an ester compound D.

Synthesis example 12
54 parts of ethylene glycol monoacetacetate monomethacrylate, 43 parts of methyl acrylate, 33 parts of potassium carbonate, 2 parts of 18-crown-6 ether and 97 parts of tetrahydrofuran were mixed and stirred at 50 ° C. for 3 hours. After completion of the reaction, cyclohexane and water were added and washed with water. The organic layer was neutralized with a saturated aqueous solution of ammonium chloride and washed twice with water, and the obtained organic layer was concentrated under reduced pressure to obtain Monomer A.

Synthesis example 13
90 parts of methyl chloroacetate, 130 parts of potassium carbonate and 250 parts of dimethylformamide were mixed, and 78 parts of methacrylic acid was added dropwise at 30 to 40 ° C. to the mixed solution. After completion of the dropping, 8 parts of triethylamine was added, and the mixture was stirred at 50 ° C. for 4 hours. After completion of the reaction, the mixture was washed with 500 parts of water. 300 parts of toluene was added to the organic layer, and the mixture was washed with 300 parts of water four times. The obtained organic layer was distilled under reduced pressure to obtain Monomer B.

Synthesis example 14
100 parts of 2-ethylhexyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester EH), 150 parts of monomer A, 125 parts of 2-hydroxyethyl acrylate, and 125 parts of styrene are used as a monomer mixture, and 2,2'-azobis (2'-azobis) as an initiator. 25 parts of 2,4-dimethylvaleronitrile) (Fujifilm Wako Pure Chemical Industries, Ltd. V-65) was dissolved in an aromatic hydrocarbon (T-SOL 100) to prepare an initiator solution. 500 parts of aromatic hydrocarbon (T-SOL 100) was placed in a stirable flask, and the monomer solution and the initiator solution were added dropwise while filling with nitrogen. The polymerization temperature at this time was set to 100 ° C. The dropping was carried out in 2 hours, and further aging at 100 ° C. for 4 hours to obtain a polymer solution A.

Synthesis example 15
175 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester NB), 150 parts of monomer B, 125 parts of 4-hydroxybutyl acrylate, and 50 parts of styrene are used as a monomer mixture, and 2,2'-azobis (2'-azobis) as an initiator. 25 parts of 2,4-dimethylvaleronitrile) (Fujifilm Wako Pure Chemical Industries, Ltd. V-65) was dissolved in an aromatic hydrocarbon (T-SOL 100) to prepare an initiator solution. 500 parts of aromatic hydrocarbon (T-SOL 100) was placed in a stirable flask, and the monomer solution and the initiator solution were added dropwise while filling with nitrogen. The polymerization temperature at this time was set to 100 ° C. The dropping was carried out in 2 hours, and further aging at 100 ° C. for 4 hours to obtain a polymer solution B.

(Preparation of paint composition)
Comparative Examples 1 to 8 and Examples 1 to 27
Each component shown in the table was mixed, a coating film of 400 μm was prepared by WET using an applicator, and cured at 150 ° C. for 30 minutes. Then, a rigid pendulum test was performed with a gel fraction and a adjusting solution. The results are shown in Tables 1-6.

(Evaluation method)
Paint compositions were prepared according to the compositions shown in Tables 1 to 6, and evaluated according to the following criteria.
Gel fraction The film obtained in the examples was dissolved in acetone reflux using Soxhlet for 30 minutes, and the residual weight% of the film was measured as the gel fraction.
The gel fraction was set to 0 to 40% as x as being unusable for practical use.
The gel fraction was set to Δ with a gel fraction of 40 to 60% assuming that a certain degree of curing was observed.
A gel fraction of 60 to 80% was marked as ◯ as it could withstand practical use.
A gel fraction of 80 to 100% was given as ◎ as having excellent performance.

Rigid pendulum tester Using A &D's rigid pendulum tester (model number RPT-3000W), the temperature was raised to 200 ° C at a heating rate of 5 ° C / min and kept at 200 ° C for 5 minutes, and the cycle and logarithm at that time. The change in the decay rate was calculated. In particular, it was used to confirm the cured state of the coating film.
Pendulum: FRB-100
Film thickness (WET): 100 μm

From the results in Tables 1 to 6, it is clear that the thermosetting resin composition of the present invention has good curing performance.

The thermosetting resin composition of the present invention can be used as a coating composition, an adhesive composition, or the like.

Claims (6)

1. A thermosetting resin composition comprising a polyester resin (A) having a hydroxyl group (a) and an alkyl ester group (b), and a transesterification catalyst (B).
2. A thermosetting resin composition comprising a polyester resin (C) and a polyol compound (D) having an alkyl ester group (b), and a transesterification catalyst (B).
3. A thermosetting resin composition comprising a polyester resin (E) having a hydroxyl group (a), a compound (F) having an alkyl ester group (b), and a transesterification catalyst (B).
4. The thermosetting resin composition according to claim 1, 2, or 3, wherein the alkyl ester group (b) has a structure represented by the following general formula (1) or (2).
   

   

   

   (In both the general formula (1) and the general formula (2), R ₁ is an alkyl group having 50 or less carbon atoms.
   R ₂ is, in part, an oxygen atom, a nitrogen atom and containing carbon atoms which may have 50 or less alkylene group)
5. The thermosetting resin composition according to claim 1, 2, 3 or 4, wherein the polyester resin has a structural unit represented by the general formula (25) in the resin chain.
   

   

   (In the formula, X represents an alkylene group having 50 or less carbon atoms which may contain an oxygen atom and a nitrogen atom as a part, and R _b is an alkyl group having 50 or less carbon atoms.
6. Structure represented by the following general formula (21)
   

   

   (In the formula, Ra represents a tertiary alkyl group)
   And the structure represented by the following general formula (22)
   

   

   (In the formula, Rb represents a primary alkyl group)
   An alkyl ester compound characterized by having at least one of both in the molecule.

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