JPWO2020218372A1 - Thermosetting resin composition, cured film and non-aqueous dispersion resin particles - Google Patents

Abstract

An object of the present invention is to provide a thermosetting resin composition which has good curability, can be used in various applications, has a transesterification reaction, and has good physical characteristics. .. A resin component containing a resin component (A) containing at least one film property modifier (A-1) selected from the group consisting of non-aqueous dispersion resin particles, block copolymers and polyester resin as an essential component. (A) is a thermosetting resin composition having an alkyl ester group and a hydroxyl group, and further containing an ester exchange catalyst (B).

Description

The present invention relates to thermosetting resin compositions, cured films and non-aqueous dispersion resin particles.

It is widely known to use a film property modifier typified by NAD (non-aqueous dispersion) in applications such as paints and adhesives. This is because paints and adhesives have a wide variety of physical characteristics required depending on the application and purpose, and it may be difficult to obtain sufficient performance with only a single component.

Examples of such a film property modifier include NAD (non-aqueous dispersion), block copolymer and the like. Further, it is widely practiced to add a polyester resin to a paint or an adhesive using an acrylic resin as a base resin. Such addition of the polyester resin is also performed to modify the physical characteristics of the film, and can be considered as one of the modifiers for the physical characteristics of the film.

Of these, NAD has a shell having a function as a dispersion stabilizer on the surface of a core made of insoluble resin particles. In such NAD, an ultra-high molecular weight one or a three-dimensional crosslinked one can be introduced into the core portion. In general, the physical properties of a film are such that a hard film reduces the elongation rate, and a soft film reduces the breaking strength. Therefore, by coexisting three-dimensionally crosslinked resin particles such as NAD in the coating film, the physical characteristics of the film can be improved without lowering the breaking strength and the elongation rate. Such non-aqueous dispersion resin particles are resins in a dispersed state rather than being dissolved in an organic solvent. Such a resin has excellent performance in that it can be used as a paint using a weak solvent and that it can be made into a high solid because the viscosity can be easily controlled. It is widely manufactured and used in the field of.

The non-aqueous dispersion generally has a reactive functional group on the surface of the non-aqueous dispersion particles, and is often used by mixing the non-aqueous dispersion with a resin solution, a curing agent solution, or the like and curing the non-aqueous dispersion. Patent Documents 1 to 4 and the like are known as such examples.

When such non-aqueous dispersion particles are used in a curable resin composition such as a paint, many attempts have been made to obtain a composition in combination with a matrix resin or a curing agent. As a result, good properties can be obtained in many physical properties such as strength and durability that are generally required for the thermosetting resin.

However, in the thermosetting resin composition using such non-aqueous dispersion particles, the thermosetting reaction used is generally a melamine cross-linking, an isocyanate cross-linking or the like, or a reaction between a carboxylic acid and an epoxy group. These curing agents are widely and generally used because they have good thermal reactivity and excellent properties of the obtained cured resin. However, since melamine resin generates formaldehyde during the curing reaction and is considered to be a cause of sick building syndrome, its use may be limited in recent years. Further, since the melamine resin does not have sufficient acid resistance, improvement in acid resistance is also required.
Further, although the polyisocyanate compound has a high curing reaction, it is not easy to handle due to its toxicity and is expensive. Furthermore, carboxylic acids and epoxy groups have problems in terms of storage stability.

It is known to use a non-aqueous resin dispersion having various alkyl ester groups in a curable composition using a non-aqueous resin dispersion (for example, Patent Documents 1 and 2 and the like). However, the introduction of this alkyl ester group was introduced in order to adjust the physical characteristics of the dispersion particles, and the curing reaction by the alkyl ester group was not expected. Therefore, in these prior documents, a curing reaction with a hydroxyl group is caused by using a melamine resin, an isocyanate compound, or the like in combination.

Furthermore, even when a block copolymer or polyester resin is used as the film property modifier, these are generally used in combination with a melamine resin or an isocyanate compound, and cross-linking is performed by a transesterification reaction. Has not been considered.

Further, in the field of powder coating materials, Patent Document 5 describes that a transesterification reaction between a t-butyl ester group and a hydroxyl group is a curing reaction. However, this document does not disclose that a transesterification reaction occurs in the curing reaction between NAD and the resin.

The present inventors have disclosed in Patent Document 6 a thermosetting resin composition in which a transesterification reaction is a curing reaction. However, Patent Document 6 does not describe or suggest the use of NAD particles.

Japanese Unexamined Patent Publication No. 2001-40010 Japanese Unexamined Patent Publication No. 2001-261715 JP 2015-168693 Japanese Unexamined Patent Publication No. 10-298256 Japanese Unexamined Patent Publication No. 9-59543 Patent No. 6398026

In view of the above, the present invention provides a thermosetting resin composition which has good curability, can be used in various applications, has a transesterification reaction, and has good physical characteristics. Is the purpose.

The present invention contains a resin component (A) containing at least one film property modifier (A-1) selected from the group consisting of non-aqueous dispersion resin particles, block copolymers and polyester resin as an essential component. However, the resin component (A) is a thermosetting resin composition having an alkyl ester group and a hydroxyl group, and further containing an ester exchange catalyst (B).

The thermosetting resin composition may contain substantially no melamine resin, isocyanate compound or epoxy group.
It is preferable that at least a part of the non-aqueous dispersion resin particles has a skeleton derived from a monomer represented by the following general formula (1).

ｎ_１：１〜１０
（式中、Ｒ_１、Ｒ_２，Ｒ_３は、同一又は異なって、水素、アルキル基、カルボキシル基、アルキルエステル基又は下記Ｒ_４−［ＣＯＯＲ_５］ｎ_１で表される構造を表す。
Ｒ_４は、主鎖の原子数が５０以下であり、主鎖中にエステル基、エーテル基、アミド基、ウレタンからなる群より選択される１又は2以上の官能基を有していてもよく、側鎖を有していてもよい脂肪族、脂環族又は芳香族アルキレン基。
Ｒ_５は、炭素数５０以下のアルキル基。）

n ₁ : 1-10
_{(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 - represents a [COOR _5] structure represented by _{n 1.}
R ₄ has 50 or less atoms in the main chain, and may have one or more functional groups selected from the group consisting of an ester group, an ether group, an amide group, and urethane in the main chain. , An aliphatic, alicyclic or aromatic alkylene group which may have a side chain.
R ₅ is an alkyl group having 50 or less carbon atoms. )

The present invention is also a cured film, which is obtained by thermally curing the thermosetting resin composition.

The present invention is a non-aqueous dispersion resin particle having an alkyl ester group.
The alkyl ester group is also a non-aqueous dispersion resin particle characterized in that at least a part thereof is a skeleton derived from a monomer represented by the following general formula (1).

ｎ_１：１〜１０
（式中、Ｒ_１、Ｒ_２，Ｒ_３は、同一又は異なって、水素、アルキル基、カルボキシル基、アルキルエステル基又は下記Ｒ_４−［ＣＯＯＲ_５］ｎ_１で表される構造を表す。
Ｒ_４は、主鎖の原子数が５０以下であり、主鎖中にエステル基、エーテル基、アミド基、ウレタンからなる群より選択される１又は2以上の官能基を有していてもよく、側鎖を有していてもよい脂肪族、脂環族又は芳香族アルキレン基。
Ｒ_５は、炭素数５０以下のアルキル基。）

n ₁ : 1-10
_{(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 - represents a [COOR _5] structure represented by _{n 1.}
R ₄ has 50 or less atoms in the main chain, and may have one or more functional groups selected from the group consisting of an ester group, an ether group, an amide group, and urethane in the main chain. , An aliphatic, alicyclic or aromatic alkylene group which may have a side chain.
R ₅ is an alkyl group having 50 or less carbon atoms. )

The thermosetting resin composition of the present invention is cured by an ester exchange reaction between an alkyl ester group and a hydroxyl group, and further, by using a film property modifier, the physical properties are improved and excellent functions are obtained. A thermosetting resin composition having the above can be obtained. Further, it is also preferable that a resin composition having a high solid content (high solidification) and a low VOC can be obtained.

The present invention requires the resin component (A), the resin component (A) has an alkyl ester group and a hydroxyl group, and is a non-aqueous dispersion resin particle, a block copolymer and a polyester resin. It is characterized in that it contains at least one film property modifier selected from the group consisting of.

That is, in a thermosetting resin composition in which the ester exchange reaction is a resin curing reaction, heat is generated by blending at least one component selected from the group consisting of non-aqueous dispersion resin particles, block copolymers and polyester resins. It is characterized by modifying the physical properties of the curable resin composition. The film physical characteristic modifier preferably has an alkyl ester group and / or a hydroxyl group. By having these functional groups, it is incorporated into the crosslinked structure formed by the resin component (A), and a cured product having more excellent physical properties can be obtained.

The resin component (A) in the present invention is a part of the film physical characteristic modifier (A-1) and further contains another resin component (A-2). The resin component (A) has an alkyl ester group and a hydroxyl group as a whole, but the above-mentioned "other resin component (A-2)" has at least one functional group of an alkyl ester group and a hydroxyl group. It is preferable to have. When the above "other resin component (A-2)" does not have both an alkyl ester group and a hydroxyl group, the "other resin component (A-2)" does not participate in the curing reaction. This is because good physical properties cannot be obtained in the cured product.

In the thermosetting resin composition of the present invention, the addition of a transesterification catalyst is indispensable in order to cause a transesterification reaction. In the prior art, a thermosetting resin composition in which non-aqueous dispersion resin particles having an alkyl ester group are used in combination with a matrix resin has been known. However, in these compositions, since the transesterification catalyst was not used in combination, the cross-linking reaction between the alkyl ester and the hydroxyl group did not sufficiently occur. Therefore, it is presumed that the cross-linking reaction as in the present invention does not occur in each composition of the cited documents described above.

Hereinafter, each component used in the present invention will be described in detail.
In the following specification, "(meth) acrylate" means acrylate and / or methacrylate. "(Meta) acrylic acid" means acrylic acid and / or methacrylic acid. In addition, "(meth) acryloyl" means acryloyl and / or methacryloyl. In addition, "(meth) acrylamide" means acrylamide and / or methacrylamide.

(Non-aqueous dispersion resin particles)
First, the case where the film physical characteristic modifier (A-1) is a non-aqueous dispersion resin particle will be described in detail.
The non-aqueous dispersion resin particles used in the present invention preferably have an alkyl ester group. As a result, it is incorporated into the cross-linking reaction that occurs in the resin component (A) and becomes a part of the cured product.
Further, the non-aqueous dispersion resin particles may have a hydroxyl group. Those having a hydroxyl group are also incorporated into the cross-linking reaction that occurs in the resin component (A) to form a part of the cured product.
As a result, it exerts a function of modifying physical properties.

The non-aqueous dispersion resin particles mean a resin that is not dissolved in an organic solvent and is dispersed as particles. It is not particularly limited as long as it has such a form, but specifically, in a polymer obtained by using a polymerizable unsaturated monomer, a single amount of a dimer or more is partially used. By using a body, particles or the like having a crosslinked structure formed in a resin can be mentioned. Further, in order to form a crosslinked structure, a crosslinking agent such as a polyvalent isocyanate, a melamine-based crosslinking agent, or an acid / epoxy may be used. Further, an ultra-high molecular weight substance can be used.

The alkyl group in the above alkyl ester group is an alkyl group having 50 or less carbon atoms, more preferably in the range of 1 to 20 carbon atoms, still more preferably in the range of 1 to 10 carbon atoms, and further preferably in the range of 1 to 10 carbon atoms. Is 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 advanced, which is preferable.

The alkyl group is not particularly limited, and known ester groups such as methyl group, ethyl group, benzyl group, n-propyl, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group can be used. You can use what you have. The alkyl group preferably has 50 or less carbon atoms. Since the alkyl group is preferably produced as an alcohol and volatilized during the transesterification reaction, the alkyl group preferably has 20 or less carbon atoms, and more preferably 10 or less carbon atoms. Further, the boiling point of the alcohol volatilized in the curing reaction is preferably 300 ° C. or lower, and more preferably 200 ° C. or lower.

In the present invention, it is preferable to use an alkyl ester group in the non-aqueous dispersion resin particles that easily causes a transesterification reaction. Such a structure will be described in detail below as (E-1) and (E-2).

(E-1)
Examples of such a monomer include a compound having a structure represented by the following general formula (2).

（式中、Ｒ_６、Ｒ_７、Ｒ_８は、同一又は異なって、水素、アルキル基、カルボキシル基、アルキルエステル基を表す。
Ｒ_９は、炭素数５０以下のアルキル基を表す）

(In the formula, R ₆ , R ₇ , and R ₈ represent hydrogen, an alkyl group, a carboxyl group, and an alkyl ester group, which are the same or different.
R ₉ represents an alkyl group having 50 or less carbon atoms)

Examples of the compound represented by the general formula (2) include alkyl ester derivatives of known unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid.

The most typical monomer having an alkyl ester group represented by the general formula (2) and a polymerizable unsaturated bond is an ester of (meth) acrylic acid and an alcohol, for example, methyl (meth). ) Acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, benzyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate , T-butyl (meth) acrylate can be mentioned.
Among these, tertiary alkyl esters such as t-butyl (meth) acrylate are most preferable from the viewpoint of cross-linking reactivity.

Since t-butyl (meth) acrylate is an ester of a tertiary alkyl, the transesterification reaction rate is high, and therefore the curing reaction proceeds efficiently. Therefore, it is superior in cross-linking reactivity to primary alkyl esters and secondary alkyl esters, and is a highly preferable raw material for providing an ester group that achieves the object of the present invention.

(E-2)
The monomer having an alkyl ester group may be a compound in which a polymerizable unsaturated bond and an ester group are bonded via a linking group. Such monomers

ｎ_１：１〜１０
（式中、Ｒ_１、Ｒ_２、Ｒ_３は、同一又は異なって、水素、アルキル基、カルボキシル基、アルキルエステル基又は下記Ｒ_４−［ＣＯＯＲ_５］ｎ_１で表される構造を表す。
Ｒ_４は、主鎖の原子数が５０以下であり、主鎖中にエステル基、エーテル基、アミド基、ウレタンからなる群より選択される１又は2以上の官能基を有していてもよく、側鎖を有していてもよい脂肪族、脂環族又は芳香族アルキレン基。
Ｒ_５は、炭素数５０以下のアルキル基。）
の一般式で表されるものを使用することができる。
当該構造では、アクリル樹脂主鎖から連結基を介してアルキルエステル基が存在するものである。このような構造の好ましい点については、以下に詳述する。

n ₁ : 1-10
_{(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 - represents a [COOR _5] structure represented by _{n 1.}
R ₄ has 50 or less atoms in the main chain, and may have one or more functional groups selected from the group consisting of an ester group, an ether group, an amide group, and urethane in the main chain. , An aliphatic, alicyclic or aromatic alkylene group which may have a side chain.
R ₅ is an alkyl group having 50 or less carbon atoms. )
The one represented by the general formula of can be used.
In this structure, an alkyl ester group is present from the main chain of the acrylic resin via a linking group. The preferred points of such a structure will be described in detail below.

More specifically, as the structure represented by the above general formula (1), for example,

ｎ_２：１〜１０
（式中、Ｒ_１０は、Ｈ又はメチル基。
Ｒ_１１は、主鎖の原子数が４８以下であり、主鎖中にエステル基、エーテル基及び／又はアミド基を有していてもよく、側鎖を有していてもよいアルキレン基。
Ｒ_１２は、炭素数５０以下のアルキル基。）
で表されるものが例示できる。このような化合物は（メタ）アクリル酸の誘導体であり、（メタ）アクリル酸又はその誘導体を原料として使用する公知の合成方法によって得ることができる。

n ₂ : 1-10
(In the formula, R ₁₀ is an H or methyl group.
R ₁₁ is an alkylene group having a main chain having 48 or less atoms, which may have an ester group, an ether group and / or an amide group in the main chain, and may have a side chain.
R ₁₂ is an alkyl group having 50 or less carbon atoms. )
An example is represented by. Such a compound is a derivative of (meth) acrylic acid, and can be obtained by a known synthetic method using (meth) acrylic acid or a derivative thereof as a raw material.

The _{number of atoms in the main chain of R 11} is more preferably 40 or less, further preferably 30 or less, and further preferably 20 or less. The _{atom that may be contained in the main chain of R 11} is not particularly limited, and may have an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or the like in addition to the carbon atom. More specifically, _{the main chain of R 11} has an ether group, an ester group, an amino group, an amide group, a thioether group, a sulfonic acid ester group, a thioester group, a siloxane group and the like in addition to the alkyl group. There may be. The lower limit of the number of atoms is not particularly limited, but the number of atoms is more preferably 2 or more, further preferably 3 or more, and most preferably 4 or more.

Such a compound in which (meth) acrylic acid and an ester group are _{bonded via a linking group represented by R 11} is particularly preferable in that the reaction rate of transesterification tends to be high. The reaction rate is increased because the side chain structure is long and the ester group is present at the end of the chain, the ester group is easy to move and the degree of freedom is increased, so that it is easy to approach the hydroxyl group, thereby reacting. Is presumed to be promoted.

_{R 5, R 12} in the general formula (1), (3), a primary, may be any of the tertiary. That is, in _{the case of a structure having linking groups R 4} and R ₁₁ , even an alkyl ester group having originally low reactivity can cause a transesterification reaction satisfactorily. Therefore, any of the primary, secondary, and tertiary ester groups can satisfactorily proceed with the cross-linking reaction by the transesterification reaction.

More specifically, as the structure represented by the general formula (1), for example, a compound represented by the following general formula (4) and the like can be mentioned.

（式中、Ｒ_１３は、炭素数１〜５０のアルキル基。
Ｒ_１４は、主鎖の原子数が４４以下であり、主鎖中にエステル基、エーテル基及び／又はアミド基を有していてもよく、側鎖を有していてもよいアルキレン基。
Ｒ_１５は、Ｈ又はメチル基。
Ｒ_１６は、炭素数５０以下のアルキル基。
Ｒ_１７は、Ｈ又はメチル基。
ｎ_３は、０又は１。
ｎ_４は、１又は２。）

(In the formula, R ₁₃ is an alkyl group having 1 to 50 carbon atoms.
R ₁₄ is an alkylene group having a main chain having 44 or less atoms, which may have an ester group, an ether group and / or an amide group in the main chain, and may have a side chain.
R ₁₅ is an H or methyl group.
R ₁₆ is an alkyl group having 50 or less carbon atoms.
R ₁₇ is an H or methyl group.
n ₃ is 0 or 1.
n ₄ is 1 or 2. )

The compound represented by the above general formula (4) is synthesized by reacting a compound that produces an active anion such as a malonic acid ester or an acetacetic acid ester having an unsaturated bond in the molecule with an unsaturated compound having an alkyl ester group. It is an esterified compound.

That is, malonic acid ester and acetoacetic ester have a methylene group sandwiched between carboxycarbons, and it is widely known that this methylene group is easily anionized and easily causes an anion reaction. A compound having an unsaturated bond in the alkyl group of such a malonic acid ester or acetoacetic acid ester (for example, malonic acid or acetoacetic acid and an unsaturated simple monolith having a hydroxyl group, which will be described in detail below as a "hydroxyl-containing monomer". By reacting an ester compound with a metric) with an alkyl ester compound having an unsaturated group, a compound having both an unsaturated group and an alkyl ester group can be synthesized.

In a compound having such a structure, only the alkyl ester group can be easily changed by using a widely used raw material, and as a result, the curing reactivity can be easily adjusted. Further, it is particularly preferable in that the curing reactivity can be adjusted by changing the reaction rate to the active methylene group.

The compound that can be used as the "alkyl ester compound having an unsaturated group" used in the above reaction is not particularly limited, and is an (meth) acrylic acid alkyl ester, a methylenemalonic acid alkyl ester, or a lactone compound having an unsaturated group (for example, γ). -Crotonolactone, 5,6-dihydro-2H-pyran-2-one) and the like can be used.

The reaction can be carried out under basic conditions, for example, by a reaction of an alkali metal salt in the presence of crown ether in an organic solvent or the like.
An example of such a synthetic reaction is shown below.

It can also be obtained by esterification of a carboxylic acid corresponding to the alkyl ester compound represented by the above general formula (1).
That is, the compound represented by the following general formula (1-2) is a carboxylic acid corresponding to the alkyl ester compound represented by the above general formula (1).

ｎ_１：１〜１０
（式中、Ｒ_１、Ｒ_２、Ｒ_３は、同一又は異なって、水素、アルキル基、カルボキシル基、アルキルエステル基又は下記Ｒ_４−［ＣＯＯＨ］ｎ_１で表される構造。
を表す
Ｒ_４は、主鎖の原子数が５０以下であり、主鎖中にエステル基、エーテル基、アミド基、ウレタンからなる群より選択される１又は２以上の官能基を有していてもよく、側鎖を有していてもよい脂肪族、脂環族又は芳香族アルキレン基。）

n ₁ : 1-10
Structure represented by [COOH] _{n 1} - _{(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 has a main chain having 50 or less atoms, and has one or more functional groups selected from the group consisting of an ester group, an ether group, an amide group, and a urethane in the main chain. It may also have an aliphatic, alicyclic or aromatic alkylene group which may have a side chain. )

A known compound exists as a compound represented by the above general formula (1-2). An unsaturated group-containing ester compound can also be obtained by subjecting such a known compound to an ordinary esterification reaction (for example, a reaction with an alcohol corresponding to the alkyl group of the desired alkyl ester).

Examples of specific chemical structures of compounds that can be synthesized by the methods exemplified above are shown below. The present invention is not limited to the compounds exemplified below.

式中、Ｒはアルキル基を表す。

In the formula, R represents an alkyl group.

Also in the compound represented by the above general formula, R in the 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 to 10 carbon atoms. It is in the range of 1 to 6, 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 advanced, which is preferable.

(E-2-X)
The compound represented by the general formula (1) may be a compound having a functional group and an unsaturated group represented by the following general formula (31).

n = 0 to 20
R ₆₁ is an alkyl group having 50 or less carbon atoms.
R ₆₃ is hydrogen or an alkyl group having 10 or less carbon atoms.

That is, in the compound represented by the general formula (1), _five COOR groups may have a structure represented by the general formula (31).

The ester group represented by the general formula (31) has high reactivity in the transesterification reaction, although the reason is unknown. Therefore, by using the ester compound having the functional group as a part or all of the resin component, a thermosetting resin composition having more excellent curing performance than before can be obtained.

(About the structure of general formula (31))
The structure of the general formula (31) is based on an α-substituted carboxylic acid ester skeleton.
In the general formula (31), 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 (31). 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, whereby the effect of the present invention can be more preferably exhibited.

In the above general formula (31), any alkyl group having 50 or less carbon atoms can be used as _{R 61, and it may be any of primary, secondary and tertiary.}

The compound having the functional group (31) is a carboxylic acid or carboxylic acid salt compound corresponding to the structure of the target compound according to the following general formula (32).

(X represents halogen and hydroxyl group)
It can be obtained by reacting an ester compound in which an active group X is introduced at the α-position of a carbonyl group having the above structure. 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 (33) is a carboxylic acid or any carboxylic acid derivative that can cause the above-mentioned reaction. Can be done. Examples of the carboxylic acid derivative include OM (carboxylic acid salt) in Y, OC = OR (acid anhydride), Cl (acid chloride) and the like. In the case of the above-mentioned Y = OM carboxylic acid salt, examples of the carboxylic acid salt include sodium salt, potassium salt, amine salt, zinc salt and the like. When used as a monomer of a polymer, a compound having an unsaturated group can be used as a compound represented by the general formula (33).

The compound represented by the general formula (32) can be a compound having a skeleton corresponding to the target structure represented by the general formula (31).

The production method of the compound represented by the general formula (32) is not particularly limited. Among the compounds represented by the general formula (32), the compound having n = 0 is a compound having an active group represented by X at the α-position, and various α-hydroxy acids and α-halogenated carboxylic acids can be mentioned. Can be done. 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 (32), for compounds having n = 1 or more, an example of a 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 above general formula (34).

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 any alkyl group having 1 to 50 carbon atoms may be used.
Such an alkyl group may be any of the 1st to 3rd grades, 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, a sec-. Butyl group, t-butyl group and the like can be mentioned.

In the above reaction, _{it is preferable that X 1} and X ₂ are of different types. It is preferable that these are different types of functional groups and have different reactivity, and the combination of functional groups is selected so that _{X 1 remains unreacted.} Specifically, _{a combination of X 1} as a bromo group and X ₂ 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 having the chemical structure represented by the above general formula (31), only those having a specific value of n may be used, or a mixture of a plurality of types of compounds having different values of n. It may be.

The chemical structure represented by the general formula (31) can be formed by reacting the compound represented by the general formula (32) with various carboxylic acid compounds. Therefore, if a carboxylic acid having an unsaturated group is used as the "compound having a carboxylic acid group", a compound having a functional group represented by the above general formula (31) and a polymerizable unsaturated group can be obtained. ..

（式中、Ｒ_６１は、炭素数５０以下のアルキル基。
Ｒ_６２は、水素又はメチル基。
ｎは、１〜２０）Specifically, for example, when the compound represented by the general formula (32) is reacted with (meth) acrylic acid, the compound represented by the following general formula (36) is obtained.

(In the formula, R ₆₁ is an alkyl group having 50 or less carbon atoms.
R ₆₂ is a hydrogen or methyl group.
n is 1 to 20)

_{R 61} in the compound represented by the general formula (36) may be any of primary, secondary and tertiary as long as it has 50 or less carbon atoms. However, it is more preferably the first grade or the second grade, and most preferably the first grade.

(E-2-Y)
The compound represented by the general formula (1) is a compound having a functional group represented by the following general formula (41) and / or a functional group represented by the following general formula (42) and an unsaturated group. There may be.

（上記一般式（４１）、一般式（４２）のいずれにおいても、Ｒ_６１は炭素数５０以下のアルキル基。
Ｒ_６４は、一部に、酸素原子、窒素原子を含んでいてもよい炭素数５０以下のアルキレン基）

(In both the general formula (41) and the general formula (42), R ₆₁ is an alkyl group having 50 or less carbon atoms.
R ₆₄ is an alkylene group having 50 or less carbon atoms which may contain an oxygen atom and a nitrogen atom in a part thereof).

That is, in the compound represented by the general formula (1), _five COOR groups have a structure represented by the general formula (41) and / or a structure represented by the general formula (42). There may be.

_{The R64} group in the above general formula (41) is an alkylene group having 50 or less carbon atoms which may contain an oxygen atom and a nitrogen atom as a part, and specifically, a methylene group, an ethylene group and an n- group. It may contain a cyclic structure such as a propylene group, an i-propylene group, an n-butylene group, or a benzene ring or a cyclohexyl ring (carbon chains 1 to 50). Of these, an ethylene group is particularly preferable because the raw material is inexpensive and has excellent reactivity.

Examples of the compound having the structure represented by the general formula (41) include the compound represented by the following general formula (43).

（式中、Ｒ_６１は炭素数５０以下のアルキル基。
Ｒ_６４は、一部に、酸素原子、窒素原子を含んでいてもよい炭素数５０以下のアルキレン基。
Ｒ_６５は、水素又はメチル基。）

(In the formula, R ₆₁ is an alkyl group having 50 or less carbon atoms.
R ₆₄ is an alkylene group having 50 or less carbon atoms which may contain an oxygen atom and a nitrogen atom as a part.
R ₆₅ is a hydrogen or methyl group. )

Of the ester compounds represented by the general formula (43), the ester compound represented by the following general formula (45) is more preferable.

The method for producing the ester compound having a functional group represented by the general formula (41) is not particularly limited, and examples thereof include a method of reacting an epoxy compound with a compound having an alkyl ester group and a carboxyl group. can. When this is expressed by a general formula, the reaction is as follows.

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 of 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 (52) is not particularly limited, and for example, succinic anhydride, maleic anhydride, phthalic anhydride, and hexahydrophthalic acid having a cyclic structure. 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 (51) 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 (51) is not limited to the compound obtained by the method of the general formula (52), and other compounds are used. It does not matter if it is obtained by the method.

In the synthetic method represented by the general formula (51), an epoxy compound is used as an essential component. The epoxy compound is not particularly limited as long as it has an unsaturated double bond and an epoxy group, and any epoxy compound can be used.

Examples of the epoxy compound that can be used in the above-mentioned reaction include any known epoxy compound, and examples thereof include glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, and trimethylolpropane triglycidyl ether. ..

For example, if epichlorohydrin is used, an epoxy group can be introduced into a compound having various skeletons by reacting it with a phenol compound, a carboxylic acid compound, a hydroxyl group-containing compound or the like. By carrying out the above-mentioned reaction with such an arbitrary epoxy compound, a compound having a functional group represented by the above-mentioned general formula (41) can be obtained. The general formula of such a reaction is shown below.

Examples of the hydroxycarboxylic acid having a carboxyl group and an unsaturated group include (meth) acrylic acid.

Further, the epoxy compound described above may be a cyclic epoxy compound.
That is, when the cyclic epoxy compound is used as the epoxy compound, a compound having a structure represented by the general formula (52) can be obtained by the following reaction.

Examples of the alicyclic epoxy compound that can be used in the above-mentioned general formula include 3,4-epoxycyclohexylmethylmethacrylate, 3', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate and the like. ..

Specific examples of the functional group represented by the following general formula (41) and / or the compound represented by the following general formula (42) and the compound having an unsaturated group are as follows. Examples thereof include the represented compounds.

An example of a specific chemical structure of the compound represented by the general formula (1) that can be synthesized by the method exemplified above is shown below. The present invention is not limited to the compounds exemplified below.

（上記一般式中、Ｒ_６１は、炭素数５０以下のアルキル基を表す）

(In the above general formula, R ₆₁ represents an alkyl group having 50 or less carbon atoms).

Also in the compound represented by the above general formula, R in the 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 to 10 carbon atoms. It is in the range of 1 to 6, 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 advanced, which is preferable.

By using one or more of such acrylic monomers having an alkyl ester group as a part of a resin raw material in any known method for producing non-aqueous dispersion resin particles, the present invention is used. It can be a particularly suitable non-aqueous dispersion resin particle.

The method for producing such non-aqueous dispersion resin particles is not particularly limited. For example, a (comb-shaped) macromonomer is produced, this is copolymerized with another monomer, and the crosslinked structure is obtained during the polymerization. A method of producing the above can be mentioned by using the monomer forming the above in combination.

The method for producing the macromonomer is not particularly limited, but a method of reacting a polymer containing a carboxyl group with a compound having an epoxy group and a polymerizable unsaturated group, or a method containing a hydroxyl group as shown in the following general formula. There is a method of reacting a polymer having a hydroxyl group at the terminal with a polymer or a chain transfer agent to react with a compound having an isocyanate group and a polymerizable unsaturated group. In addition, there is a method of using α-methylstyrene dimer as a chain transfer agent. (Step 1)

A polymerization reaction is carried out in which the macromonomer is used in combination with the unsaturated polymerizable monomer (step 2).
In step 2, NAD can be obtained by reacting in a poor solvent in which the product of step 2 is difficult to dissolve.
Further, a comb-shaped polymer can be obtained by adjusting the monomer composition and the like and reacting in a solvent in which the result of step 2 is soluble. Even in such a lost polymer, if a carboxyl group is introduced, a comb-type macromonomer can be obtained by reacting the polymer with a compound having an epoxy group and a polymerizable unsaturated group. If a hydroxyl group is introduced, a comb-type macromonomer can be obtained by reacting the polymer with the above-mentioned isocyanate group and a compound having a polymerizable unsaturated group (step 3).
Further, NAD can be obtained by reacting the comb-type macromonomer obtained in this step 3 with an unsaturated group-containing monomer (step 4).
In the polymerization reaction in Steps 2 and / or Step 4, it is preferable to use a monomer having two or more polymerizable unsaturated groups, or a monomer having an epoxy group and a monomer having a carboxyl group in combination. As a result, a crosslinked chain is formed and the solubility of the resin in the solvent is reduced, so that a more suitable NAD can be obtained.

That is, NAD can be obtained by the above steps 1 and 2, or NAD can be obtained by steps 1, 2, 3 and 4, but among these, the NAD obtained in the steps 1, 2, 3 and 4 is obtained. More preferred.

In the above-mentioned reaction, the reaction of the isocyanate group-hydroxyl group is combined with the polymerization of the unsaturated bond, but the same reaction can be combined with the reaction of the epoxy group-carboxyl group with the polymerization of the unsaturated bond.
That is, a polymer having an unsaturated group is obtained by reacting a resin having a carboxyl group with a compound having both an unsaturated group and an epoxy group, and the polymerization reaction of the unsaturated group is carried out. , It may have a step of introducing a network structure into the resin. The reaction in this case can be carried out in the same manner as in Steps 1 to 4 described above, except that the monomer used is a combination of an epoxy group-containing monomer and a carboxyl group-containing monomer.
In the case of such a method, it may be used in combination with the above-mentioned reaction of isocyanate and hydroxyl group, or only the reaction of the monomer having a carboxyl group and the monomer having an epoxy group has a network structure. It may be a reaction for forming.

When carrying out such a reaction, it is preferable to use an unsaturated polymerizable monomer having an alkyl ester group in all or any of the steps 1 to 4.
Further, the alkyl ester group needs to be one that easily causes a transesterification reaction. As such an alkyl ester group, as described above,
(1) Tertiary alkyl ester group (2) Any of the ester groups having a long side chain as represented by the above-mentioned general formulas (1) and (3) is preferable.
Of these, an ester group having the long side chain of (2) is preferable. Further, it may be a monomer corresponding to any of (1) and (2), which is a tertiary alkyl ester group having a long side chain, or the monomer of (1) and the monomer of (2). A monomer may be used in combination.

When NAD is produced by the method described above, the monomer having an alkyl ester group represented by (E-1) and (E-2) described above is used in the production at a ratio of 1 to 50% by weight based on the total amount of the raw material. It is preferable to use it. Further, it is more preferable to have an alkyl ester group on the outside of the core because it reacts with other components of NAD during heat curing.

When NAD is produced by the above-mentioned method, in the production method, in addition to the above-mentioned monomer having an alkyl ester group, (H) hydroxyl group-containing monomer, (I) isocyanate group and polymerizable unsaturated group It is required to use a compound having (J), a monomer having two or more polymerizable unsaturated groups, a monomer having an epoxy group, and a monomer having a carboxyl group. Further, for the purpose of enhancing the ability to disperse as NAD in an organic solvent, a monomer having a (K) long-chain aliphatic side chain can also be used. Furthermore, other unsaturated functional group-containing monomers may be used in combination.
However, it is not necessary to stick to the above method as NAD, and the core portion does not have to be three-dimensionally crosslinked. Further, the dispersant / dispersion stabilizer does not have to react with the core portion, and there is no problem as long as the particles are stably present.
Those that can be used as these monomers are illustrated below.

(H) Hydroxyl-containing monomer 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 5- Various hydroxyl group-containing vinyl ethers such as hydroxypentyl vinyl ethers or 6-hydroxyhexyl vinyl ethers; or addition reaction products of these various vinyl ethers listed above with ε-caprolactone;
2-Hydroxyethyl (meth) allyl ether, 3-hydroxypropyl (meth) allyl ether, 2-hydroxypropyl (meth) allyl ether, 4-hydroxybutyl (meth) allyl ether, 3-hydroxybutyl (meth) allyl ether, Various hydroxyl-containing allyl ethers, such as 2-hydroxy-2-methylpropyl (meth) allyl ether, 5-hydroxypentyl (meth) allyl ether or 6-hydroxyhexyl (meth) allyl ether; or any of these listed above. Addition reaction product of allyl ether and ε-caprolactone;
Alternatively, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl Various hydroxyl group-containing (meth) acrylates such as (meth) acrylates, polyethylene glycol mono (meth) acrylates or polypropylene glycol mono (meth) acrylates; or the various (meth) acrylates listed above and ε-caprolactone. It is the main component of the addition reaction of.

Further, for the non-aqueous dispersion resin particles having a hydroxyl group as described above, the amount of the (H) hydroxyl group-containing monomer used described above may be adjusted to be excessive, or the step which is the final step in the method described above. It can be obtained by a method such as using a hydroxyl group-containing monomer in No. 4.

(I) Compound having an isocyanate group and a polymerizable unsaturated group Examples of the compound represented by the following general formula (6) can be mentioned.

（式中、Ｒ_２２は、炭素数１〜２０の炭化水素基。
Ｒ_２３は、Ｈ又はメチル基）

(In the formula, R ₂₂ is a hydrocarbon group having 1 to 20 carbon atoms.
R ₂₃ is an H or methyl group)

More specifically, 2-isocyanatoethylacryllate and the like sold under the trade name of Showa Denko Corporation Calends AOI (registered trademark) can be mentioned.

(J) Monomer having 2 or more polymerizable unsaturated groups (J) Monomer having 2 or more polymerizable unsaturated groups is used in the steps (2) and / or (3) of the above production method. It is preferably used. By using such a monomer as a part, a crosslinked chain is appropriately formed in the molecule, and it has an effect of reducing the solubility of the resin in a solvent.

As the monomer having two or more polymerizable unsaturated groups, for example, those exemplified below can be used.

(Monomer having two or more (meth) acryloyl groups)
Such a monomer preferably has a relatively low molecular weight of 180 to 800, and any compound having two or more (meth) acryloyl groups can be used. A large number of such compounds are known, but any of these can be used in the present application. In addition, these two or more types can be used in combination. These specific ones are illustrated below.

Examples of (meth) acrylates having 2 functional groups are 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and ethylene glycol. 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, 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) Contains 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. Of these, 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 4 or more functional groups include pentaerythritol tetra (meth) acrylate, pentaerythritol ethylene oxide-modified tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol tetra (meth) acrylate. Dipentaerythritol penta (meth) acrylate, ditrimethylolpropanpenta (meth) acrylate, propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropanhexa (meth) acrylate, dipenta Examples thereof include polyfunctional (meth) acrylates such as hexa (meth) acrylates, which are modified caprolactones of erythritol.

Monomer having an epoxy group and monomer having a carboxyl group Acrylic acid, a carboxyl group-containing polymerizable unsaturated monomer such as methacrylic acid, an epoxy group-containing polymerizable unsaturated monomer such as glycidyl acrylate and glycidyl methacrylate, and the like can be mentioned. Can be done.

(K) Monomer having a long-chain aliphatic side chain A (meth) acrylate monomer having a long-chain alkyl group having 12 to 16 carbon atoms [For example, light ester L-7 (alkyl) under the trade name of Kyoeisha Chemical Co., Ltd. (12 to 13 carbon atoms) methacrylate), light ester L (n-lauryl methacrylate), Blemmer LMA (n-lauryl methacrylate) trade name of Nichiyu Co., Ltd., Blemmer SLMA-S or SH (alkyl (12 to 13 carbon atoms) 13) methacrylates), Blemmer CMA (cetyl methacrylate), Blemmer LA (lauryl acrylate), Blemmer CA (cetyl acrylate) and the like.

Further, in the method for producing NAD according to the above-mentioned steps (1) to (3), other monomers may be used in combination.

The other ethylenically unsaturated monomers are not particularly limited, and for example, esters of acrylic acid or methacrylic acid such as cyclohexyl (meth) acrylate and benzyl methacrylate; All of the above are manufactured by Osaka Organic Chemical Co., Ltd., trade name), fluorocyclohexyl (meth) acrylate, fluorovinyl-containing monomer such as vinyl fluoride; N, N-dimethylaminoethyl (meth) acrylate, N, N- Nitrogen-containing vinyl-based monomers such as diethylaminoethyl (meth) acrylate and N, N-diethylmethacrylate; Vinyl ether-based monomers such as vinyl ethyl ether and vinyl butyl ether; Fragrances such as styrene, α-methylstyrene and vinyltoluene Group vinyl monomer; Acrylonitrile, methacrylonitrile, divinylbenzene, ethylene glycol di (meth) acrylate; carboxyl group-containing polymerizable unsaturated monomer such as acrylic acid and methacrylic acid; epoxy group-containing polymerization such as glycidyl acrylate and glycidyl methacrylate Sexual unsaturated monomer; Isocyanato group-containing polymerizable unsaturated monomer such as isocyanatoethyl methacrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate and the like can be mentioned.

The organic solvent preferably dissolves the polymerizable unsaturated monomer to be polymerized, but substantially does not dissolve the polymer formed from the polymerizable unsaturated monomer, and preferably has a small polarity. For example, relatively low-dissolving aliphatic or aromatic hydrocarbons such as VM & P naphtha, mineral spirit, solvent kerosene, aromatic naphtha, solvent naphtha; n-butane, n-hexane, n-heptane, n- Aliphatic hydrocarbons such as octane, isononan, n-decane, and n-dodecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and cyclobutane are used. If necessary, polar solvents such as ester-based, ether-based, ketone-based, and alcohol-based solvents can be used in combination in a small proportion.

In the steps (1) to (4) in the above method, in the polymerization using the polymerizable unsaturated monomer, a polymerization initiator is blended and the polymerization temperature is set to 30 to 150 ° C., preferably 50 to 110 ° C. The polymerization time is usually preferably about 2 to 10 hours.

Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide, lauroyl peroxide, caproyl peroxide, t-butyl peroxide, and diacetyl peroxide; azobisisobutyronitrile and azobisdimethylvaleronitrile. , Azo-based initiators such as dimethyl α, α'-azoisobutyrate; dialkylperoxydicarbonates such as diisopropylperoxydicarbonate; and redox initiators. The concentration of the polymerization initiator is preferably in the range of 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the polymerizable unsaturated monomer.

In the non-aqueous dispersion resin particles used in the present invention, the content of the alkyl ester group is not particularly limited, and for example, it is preferably introduced at a ratio of 1 to 80 wt%. Introducing at such a ratio is preferable in that good curing performance can be obtained.

(Block copolymer)
In the present invention, a block copolymer may be used as the film property modifier.
Since the block copolymer has two or more polymers having different properties, it is excellent in the property of changing the physical characteristics of the film at the time of curing, and by using this as a part, the thermosetting resin of the present invention can be used. The physical characteristics of the cured product obtained by using the composition can be improved. For example, in the case of block copolymerization of ABA, A has crosslinkability (reactivity), but B has no reactivity (and vice versa), and the part B is also designed with a very hard resin. Alternatively, it can be designed with a soft resin. It also makes it possible to have molecular weight, polarity, curability, and functionality. When it is blended in a large amount, it becomes a film property improving agent, but when it is mixed in a small amount, it can be used as an additive in various forms such as leveling property, defoaming property, and pigment dispersant.

The block copolymer of the present invention is preferably a polymer obtained by using a polymerizable unsaturated functional group. The block polymer refers to a resin structure in which a structure composed of A and a structure composed of B appear alternately when a structural unit A having a specific resin composition and a structural unit B having another resin composition are used. These structures are not particularly limited, and any combination can be obtained.

As the above-mentioned monomer for obtaining the block copolymer, the above-mentioned "monomer having an alkyl ester group" is used, and the block copolymer also contributes to the curing of the resin by the transesterification reaction. May be good.

The method for producing the block copolymer is not particularly limited. For example, after polymerizing the monomer constituting the constituent unit A, the monomer constituting the constituent unit B is added in the state of a living polymer. And polymerize. After that, it can be obtained by repeating the steps of further adding the monomer constituting the constituent unit A in the state of the living polymer and performing the polymerization. There is also a method in which the acrylate is first polymerized and then the methacrylate is polymerized by utilizing the difference in the growth reaction rate.

Further, the block copolymer can also have an alkyl ester group and a hydroxyl group.
Further, in this case, the alkyl ester group is any of the above-mentioned (1) tertiary alkyl ester group (2) ester group having a long side chain as represented by the above-mentioned general formulas (1) and (3). It is preferable that it is introduced by the ester.
As the hydroxyl group-containing monomer, those described above can also be used. Further, as the monomer constituting the block copolymer, other unsaturated group-containing monomers described above may be used in combination.

(Polyester resin)
In the thermosetting resin composition of the present invention, a polyester resin may be blended as a film physical characteristic modifier. When a polyester resin is blended, it is preferable in that it can be made into a high solid and the physical characteristics of the film can be modified. Polyester resin is generally soft, and when it is made into a cured film, it has good followability. In particular, it is particularly advantageous when processing after curing such as PMC.

In the present invention, examples of the polyester resin that can be used as the film property modifier include the following.

The polyester resin can usually be produced by dehydration condensation or transesterification reaction of 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 anhydrides and esterified products thereof.

The aliphatic polybasic acid and its anhydrides and esterified products generally include 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. Fats such as succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanedioic acid, brassic acid, octadecanedioic acid, citric acid, butanetetracarboxylic acid. Examples thereof include group polyvalent carboxylic acids; anhydrides of the above aliphatic polyvalent carboxylic acids; esterified products of lower alkyls having about 1 to about 4 carbon atoms of the above aliphatic polyvalent carboxylic acids, and any combinations 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. The alicyclic polyvalent carboxylic acid of the above; the anhydride of the alicyclic polyvalent carboxylic acid; the 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 its 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, their anhydrides and esterified products 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 esterifieds of the aromatic polyvalent carboxylic acid 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, cotton seed oil fatty acid, hemp seed 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 acids, linolenic acids, benzoic acids, p-tert-butyl benzoic acids, cyclohexanoic acids, 10-phenyloctadecanoic acids; lactic acids, 3-hydroxybutanoic acids, 3-hydroxy-4-ethoxybenzoic acids Such as hydroxycarboxylic acids, etc., as well as any combination thereof.

Examples of the alcohol component include 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 pentyl glycol ester, hydrogenated bisphenol A, hydrogenated bisphenol F, dimethylol propionic acid; polylactone diol obtained by adding a lactone compound such as ε-caprolactone to the above dihydric alcohol; bis (hydroxyethyl) terephthalate, etc. 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, and mannit; the above trihydric alcohol is added with a lactone compound such as ε-caprolactone. 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 Specialy Chemicals Co., Ltd. with an acid.

The polyester resin is not particularly limited and 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 a dehydration condensation or transesterification reaction between the acid component and the alcohol component. Therefore, a polyester resin can be produced.

(Other resin components (A-2))
In the present invention, the above-mentioned film physical characteristic modifier (A-1) is used as a part of the resin composition, but it further contains another resin component (A-2).
In the present invention, it is essential that the resin component (A) has an alkyl ester group and a hydroxyl group. Then, these functional groups may be present in the above-mentioned film physical characteristic modifier (A-1) or in other resin components (A-2). .. More preferably, these functional groups are present in both the film physical characteristic modifier (A-1) and the other resin component (A-2). By setting the condition in such a state, a reaction occurs between the film physical characteristic modifier (A-1) and the other resin component (A-2), and the integration of these causes better physical characteristics. Can be obtained.

When the film physical characteristic modifier (A-1) is NAD particles, it preferably has an alkyl ester group as described above. Therefore, in this case, the other resin component (A-2) is preferably a resin containing at least a hydroxyl group.

The other resin component (A-2) is not particularly limited, and various hydroxyl group-containing resins widely used in the coating field can be used.
Examples of the resin that can be used include, but the resin is not limited thereto.

Acrylic polyol The acrylic polyol is, for example, a known method of using a hydroxyl group-containing polymerizable unsaturated monomer (a ₁ ) and another polymerizable unsaturated monomer (a ₂ ) copolymerizable with the above (a _1). It can be produced by copolymerizing with. More specifically, polymerization methods such as a solution polymerization method in an organic solvent, an emulsion polymerization method in water, a miniemulsion polymerization method in water, and an aqueous solution polymerization method can be mentioned.

The hydroxyl group-containing polymerizable unsaturated monomer (a ₁ ) is a compound having one or more hydroxyl groups and one or more polymerizable unsaturated bonds in one molecule. The hydroxyl group-containing polymerizable unsaturated monomer (a ₁ ) is not particularly limited, and examples thereof include a hydroxyl group-containing vinyl monomer. Particularly representative examples of such hydroxyl group-containing vinyl monomers are shown below. 2-Hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 5-hydroxypentyl vinyl ether or 6-hydroxyhexyl Various hydroxyl group-containing vinyl ethers such as vinyl ethers; or addition reaction products of these various vinyl ethers listed above with ε-caprolactone;
2-Hydroxyethyl (meth) allyl ether, 3-hydroxypropyl (meth) allyl ether, 2-hydroxypropyl (meth) allyl ether, 4-hydroxybutyl (meth) allyl ether, 3-hydroxybutyl (meth) allyl ether, Various hydroxyl-containing allyl ethers, such as 2-hydroxy-2-methylpropyl (meth) allyl ether, 5-hydroxypentyl (meth) allyl ether or 6-hydroxyhexyl (meth) allyl ether; or any of these listed above. Addition reaction product of allyl ether and ε-caprolactone;
Alternatively, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl Various hydroxyl group-containing (meth) acrylates such as (meth) acrylates, polyethylene glycol mono (meth) acrylates or polypropylene glycol mono (meth) acrylates; or the various (meth) acrylates listed above and ε-caprolactone. It is the main component of the addition reaction of.

Further, the hydroxyl group-containing monomer as a monomer does not have a hydroxyl group at a position close to the unsaturated bond (specifically, the number of atoms between the hydroxyl group and the unsaturated bond is 2 or less). When a hydroxyl group is formed via a connecting chain having 3 or more atoms and 50 or less atoms, the hydroxyl group easily moves in the resin, which is preferable in that an ester exchange reaction is likely to occur.

That is, when the hydroxyl group-containing monomer has a hydroxyl group via a connecting chain having 3 or more atoms and 50 or less atoms, it is assumed to have both this and a structure derived from an unsaturated group-containing ester compound. As a result, low temperature curing performance can be obtained. It is preferable to use the above-mentioned hydroxyl group-containing monomer in that such an unexpected effect can be obtained. It is presumed that such an effect can be obtained by easily causing a transesterification reaction because both the alkyl ester group and the hydroxyl group have a high degree of freedom in the resin.

More specifically, it is preferable to use a hydroxyl group-containing monomer having a structure represented by the following general formula (7) for a part or all of the hydroxyl groups.

ｍ_１：１〜１０、
（式中、Ｒ_３１、Ｒ_３２、Ｒ_３３は、同一又は異なって、水素、アルキル基、カルボキシル基、アルキルエステル基又は下記Ｒ_３４−［ＯＨ］_ｍ１で表される構造を表す。
Ｒ_３４は、主鎖の原子数が３以上５０以下であり、主鎖中にエステル基、エーテル基、アミド基、ウレタンからなる群より選択される１又は２以上の官能基を有していてもよく、側鎖を有していてもよい脂肪族、脂環族又は芳香族アルキレン基。）

m ₁ : 1-10,
_{(Wherein, R 31, R 32, R} 33 are the same or different, hydrogen, an alkyl group, a carboxyl group, an alkyl ester group or the following _R 34 - represents the _[OH] a structure represented by _m1.
R ₃₄ has a main chain having 3 or more and 50 or less atoms, and has 1 or 2 or more functional groups selected from the group consisting of an ester group, an ether group, an amide group, and urethane in the main chain. It may also have an aliphatic, alicyclic or aromatic alkylene group which may have a side chain. )

Further, the compound represented by the general formula (7) is preferably a derivative of (meth) acrylic acid represented by the following general formula (8).

ｍ_２：１〜１０、
Ｒ_３５は、Ｈ又はＣＨ_３
Ｒ_３６は、主鎖の原子数が３以上４９以下であり、主鎖中にエステル基、エーテル基、アミド基、ウレタンからなる群より選択される１又は２以上の官能基を有していてもよく、側鎖を有していてもよい脂肪族、脂環族又は芳香族アルキレン基。）

m ₂ : 1-10,
R ₃₅ is H or CH ₃
R ₃₆ has 3 or more and 49 or less atoms in the main chain, and has 1 or 2 or more functional groups selected from the group consisting of an ester group, an ether group, an amide group, and urethane in the main chain. It may also have an aliphatic, alicyclic or aromatic alkylene group which may have a side chain. )

Specific examples of such a main chain having a hydroxyl group via a connecting chain having a number of molecules of 3 or more and 50 or less are 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 1,4-cyclohexane. (Meta) acrylates such as dimethanol mono (meth) acrylates, polyethylene glycol mono (meth) acrylates or polypropylene glycol mono (meth) acrylates; or the various (meth) acrylates listed above and ε-caprolactone. The main component of the addition reaction and the like can be mentioned.

Further, the other resin component (A-2) may have an alkyl ester group. In this case, the alkyl ester group is preferably derived from the compound exemplified as being usable in the above-mentioned non-aqueous dispersion resin particles. In particular, it is a structural unit that easily causes a transesterification reaction.
(1) Tertiary alkyl ester group (2) It is preferable that the ester group is introduced by any of the ester groups having a long side chain as represented by the above-mentioned general formulas (1) and (3).

Examples of the other polymerizable unsaturated monomer (a ₂ ) copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer (a ₁ ) include the following monomers (i) to (xix) and any combination thereof. Can be mentioned.

(I) Alkyl or cycloalkyl (meth) acrylate:
For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (Meta) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, tricyclodecanyl (meth) acrylate, etc.

(Ii) Polymerizable unsaturated monomer having an isobornyl group:
Isobornyl (meth) acrylate, etc. (iii) Polymerizable unsaturated monomer having an adamantyl group:
Adamantane (meth) acrylate, etc.

(Iv) Polymerizable unsaturated monomer having a tricyclodecenyl group:
Tricyclodecenyl (meth) acrylate, etc. (v) Aromatic ring-containing polymerizable unsaturated monomer:
Benzyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, etc. (vi) Polymerizable unsaturated monomer having an alkoxysilyl group:
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, etc.

(Vii) Polymerizable unsaturated monomer having an alkyl fluorinated group:
Perfluoroalkyl (meth) acrylates such as perfluorobutylethyl (meth) acrylates and perfluorooctylethyl (meth) acrylates; polymerizable unsaturated monomers having photopolymerizable functional groups such as fluoroolefins (viii) maleimide groups (viii) ix) Vinyl compound:
N-vinylpyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate, etc.

(X) Carboxyl group-containing polymerizable unsaturated monomer:
(Meta) Acrylic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate, etc. (xi) Nitrogen-containing polymerizable unsaturated monomer:
(Meta) acrylonitrile, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, methylenebis (meth) acrylamide , Ethylenebis (meth) acrylamide, adducts of glycidyl (meth) acrylate and amine compounds, etc.

(Xii) Polymerizable unsaturated monomer having two or more polymerizable unsaturated groups in one molecule:
Allyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, etc. (xiii) Epoxide group-containing polymerizable unsaturated monomer:
Glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate , Allyl glycidyl ether, etc.

(Xiv) Polymerizable unsaturated monomer having a (meth) acrylate (xv) sulfonic acid group having a polyoxyethylene chain whose molecular end is an alkoxy group:
2-acrylamide-2-methylpropanesulfonic acid, 2-sulfoethyl (meth) acrylate, allylsulfonic acid, 4-styrenesulfonic acid, etc .; sodium and ammonium salts of these sulfonic acids, etc.

(Xvi) Polymerizable unsaturated monomer having a phosphate group:
Acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, acid phosphooxypoly (oxyethylene) glycol (meth) acrylate, acid phosphooxypoly (oxypropylene) glycol (meth) acrylate, etc.

(Xvii) Polymerizable unsaturated monomer with UV-absorbing functional group:
2-Hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2-hydroxy-4- (3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2,2'-dihydroxy-4- (3-) Methacryloyloxy-2-hydroxypropoxy) benzophenone, 2,2'-dihydroxy-4- (3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2- (2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H -Benzotriazole, etc.

(Xviii) UV-stable polymerizable unsaturated monomer:
4- (Meta) acryloyloxy-1,2,2,6,6-pentamethylpiperidin, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-cyano-4- (meth) ) Acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl- 4-Cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2, 2,6,6-tetramethylpiperidin, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidin, etc.

(Xix) Polymerizable unsaturated monomer having a carbonyl group:
Acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formyl styrene, vinyl alkyl ketone having about 4 to about 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone), etc.

As used herein, the term "polymerizable unsaturated group" means an unsaturated group capable of radical polymerization or ionic polymerization. Examples of the polymerizable unsaturated group include a vinyl group and a (meth) acryloyl group.

The proportion of the hydroxyl group-containing polymerizable unsaturated monomer (a ₁ ) in producing the acrylic polyol is preferably 0.5 to 50% by weight based on the total amount of the monomer components. Within such a range, an appropriate cross-linking reaction can be generated, and excellent coating film physical characteristics can be obtained.
The lower limit is more preferably 1.0% by weight, further preferably 1.5% by weight. The upper limit is more preferably 40% by weight.

The hydroxyl value of the acrylic polyol is preferably 1 to 200 mgKOH / g from the viewpoint of water resistance of the formed coating film and the like. The lower limit is more preferably 2 mgKOH / g, and even more preferably 5 mgKOH / g. The upper limit is more preferably 180 mgKOH / g, and even more preferably 170 mgKOH / g.

As such an acrylic polyol, a commercially available one can also be used. The commercially available product is not particularly limited, and for example, Acrydic A-801-P, A-817, A-837, A-848-RN, A-814, 57-773, A-829 manufactured by DIC Corporation. , 55-129, 49-394-IM, A-875-55, A-870, A-871, A-859-B, 52-668-BA, WZU-591, WXU-880, BL-616, CL -1000, CL-408 and the like can be mentioned.

Further, in the thermosetting resin composition of the present invention, the ester group in the ester compound can be arbitrarily blended with respect to the number of hydroxyl groups derived from the acrylic polyol, but it is preferably 1 to 200% (number ratio).

Low molecular weight polyol The other resin component (A-2) is not limited to the above-mentioned resin, and a low molecular weight polyol (specifically, a molecular weight of 2,000 or less) should be used. You can also.
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-. Butanediol, 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, hydroxypivalate neopentyl glycol ester, hydrogenated bisphenol A, hydrogenated bisphenol F, di Divalent alcohols such as methylolpropionic acid; polylactone diols obtained by adding a lactone compound such as ε-caprolactone to the above dihydric alcohols; ester diol compounds such as bis (hydroxyethyl) terephthalate; alkylene oxide adducts of bisphenol A, polyethylene glycol , Polyetherdiol compounds such as polypropylene glycol and polybutylene glycol; glycerin, trimethylolethane, trimethylolpropane, diglycerin, triglycerin, 1,2,6-hexanetriol, pentaerythritol, dipentaerythritol, tris (2- Hydroxylethyl) isocyanuric acid, sorbitol, mannitt and other trihydric or higher alcohols can be mentioned.

Thermosetting resin compositions using such low molecular weight polyols are known as general-purpose products and can be obtained at low cost. Further, the small molecule polyol has strong water solubility and can be suitably used as a cross-linking agent for the purpose of curing in an aqueous system. In recent years, environmental problems have been called for, and it can be suitably used as a cross-linking agent which is very important for promoting the reduction of VOC.

As the other resin component (A-2), an ester compound having two or more ester groups can also be used. The ester compound is not particularly limited, and examples thereof include those exemplified below.

A 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 (9) has 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, a compound having a halogen group, etc.). The compound obtained by such a reaction can also be used as the compound (A) of the present invention.

（式中、Ｒ_４０は炭素数５０以下の１〜３級のアルキル基を表す。
Ｘは、ＯＲ_４０基又は炭素数５以下の炭化水素基を表す。なお1分子中に２のＲ_４０が存在する場合、これらのＲ_４０は同一であっても相違するものであってもよい。）

(In the formula, R ₄₀ represents a primary to tertiary alkyl group having 50 or less carbon atoms.
X represents an OR ₄₀ group or a hydrocarbon group having 5 or less carbon atoms. When 2 R _40s are present in _{one molecule, these R 40s} may be the same or different. )

The _{structure of R 40} is not particularly limited, but known components such as methyl group, ethyl group, benzyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and sec-butyl group are known. Those having an ester 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 adding these compounds to a vinyl compound or a halogen group-containing compound can be used. Each of these will be described below.

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 shown by the following formula.

In the above reaction, a compound represented by the following general formula (10-1) 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 (10) and / or a structure represented by the general formula (10-1), 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,

との反応を生じることとなる。
上記一般式中、Ｒ_４０は、炭素数５０以下の１〜３級のアルキル基を示す。
Ｒ_４５は、水素又はメチル基を示す。
Ｒ_４６は、特に限定されず、目的に応じて任意の官能基とすることができる。

Will cause a reaction with.
In the above general formula, R ₄₀ represents a 1st to 3rd class alkyl group having 50 or less carbon atoms.
R ₄₅ represents a hydrogen or methyl group.
R ₄₆ is not particularly limited and may be any functional group depending on the intended purpose.

In the above reaction, a compound represented by the following general formula (12) 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 (12) 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 adjusting these molar ratios, it can also be obtained as a mixture of the compound represented by the general formula (11) and the compound represented by the general formula (12).
The ester compound obtained by such a reaction is

の構造で表される構成単位を分子中に有することとなる。

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 (13) and / or the structure represented by (14) can be molecularly formed. It can also be an ester compound having two or more in it.
That is, it has the functional group.

の一般式で表される構造を有する化合物を本発明において好適に使用することができる。このような化合物は、エステル交換反応性が高く、多くのＣＯＯＲ基を分子中に有するために良好な硬化性を得ることができる点で好ましいものである。
上記一般式におけるｎ_５，ｎ_６は、２〜１２であることが最も好ましい。また、Ｌ，Ｍ，Cは、当該化合物の分子量が３０００以下となるような構造であれば特に限定されえず、水酸基、エステル基、エーテル基、ウレタン基、アミド基等の任意の官能基を有していてもよい炭化水素基を表す。

A compound having a structure represented by the general formula of can be preferably used in the present invention. Such a compound is preferable because it has high transesterification reactivity and has many COOR groups in the molecule, so that good curability can be obtained.
_{Most preferably, n 5} and n ₆ 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 any functional group such as a hydroxyl group, an ester group, an ether group, a urethane group, or an amide group can be used. Represents a hydrocarbon group that may have.

Further, the above-mentioned "compound obtained by an addition reaction between a compound having an active methylene group and a vinyl group" uses a compound having two or more unsaturated bonds in one molecule as a raw material, and has the above general formula. One molecule may have two or more of the structure represented by (15) and / or the structure represented by the general formula (16).

Many compounds having a structure derived from a compound ester having an active methylene group are known, but the compound having the above structure can easily undergo an addition reaction of a malonic acid ester or an acetoacetic ester with 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 resin after curing can be easily adjusted.
Specifically, dimethyl malonate, diethyl malonate, di-butyl malonate, methyl acetoacetate, ethyl acetoacetate and the like can be preferably used.
Among them, the one obtained by adding Michael dimethyloltricyclodecaneacrylate to diethyl malonate has a low viscosity, and the overall viscosity can be lowered by blending it with a thermosetting resin. This is preferable in that it aims at high solid differentiation (high solidification).

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 two 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 having 1 functional group are methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, 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) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and ethylene glycol. 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, 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) Contains 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. Of these, 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 4 or more functional groups include pentaerythritol tetra (meth) acrylate, pentaerythritol ethylene oxide-modified tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol tetra (meth) acrylate. Dipentaerythritol penta (meth) acrylate, ditrimethylolpropanpenta (meth) acrylate, propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropanhexa (meth) acrylate, dipenta Examples thereof include polyfunctional (meth) acrylates such as hexa (meth) acrylates, which are modified caprolactones of erythritol.

A 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 a compound obtained by the reaction formula represented by the following general formula (17).

Ｒ_１、Ｒ_２は炭素数５０以下の１級又は２級アルキル基（Ｒ_１とＲ_２は同一でも良い）、Ｘは炭素数５以下の炭化水素基又は−ＯＲ_１基、Ｙはハロゲン、ｎは１又は２

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), X is a hydrocarbon group or −OR ₁ group having 5 or less carbon atoms, and Y is a halogen. n is 1 or 2

Specific examples of the compounds corresponding to the above-mentioned compounds are shown below.

式中Ｒは同一または異なるアルキル基を表す。ｎ_７は１から１０を表す。

In the formula, R represents the same or different alkyl groups. n ₇ represents 1 to 10.

The above compound preferably has two or more 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 resin after curing, which is preferable in that the hardness of the cured product becomes good and a cured product having excellent physical properties can be obtained.
It is more preferable that the above alkyl ester is 3 or more in the molecule.

A compound having two or more functional groups represented by the general formula (31) A compound having two or more functional groups represented by the general formula (31) described above can also be used in the present invention.

The functional group represented by the general formula (31) has been described in detail. Such a functional group is formed by reacting a compound represented by the general formula (32) with a carboxylic acid. Therefore, when various known polycarboxylic acids are reacted with the compound represented by the above general formula (32), a compound having two or more functional groups represented by the above general formula (31) can be obtained. Further, when it is reacted with a hydroxycarboxylic acid having a hydroxyl group, it becomes a compound having a hydroxyl group and the general formula (32), which can also be used as a component of a thermosetting resin composition that undergoes a curing reaction by transesterification. ..

The above compound is preferably a compound having two or more functional groups for use in the thermosetting resin composition of the present invention, and contains a polycarboxylic acid having two or more carboxyl groups, a carboxyl group and a hydroxyl group. A hydroxycarboxylic acid or the like can be used.

Various polycarboxylic 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 many other applications. A compound obtained by converting such a polycarboxylic acid into a functional group represented by the general formula (32) described above by a known method can also be used in the present invention.

When such a compound is used as a compound having a functional group represented by the general formula (32), 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. can. Further, esterification is preferable in that the compatibility with the organic solvent is improved and the product can be preferably used.

The polycarboxylic 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, undecanoic acid, dodecanedic acid, brushic acid, octadecaneic 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 Alicyclic polyvalent carboxylic acids 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.

The compound in which the carboxylic acid group of the polycarboxylic acid is replaced with the structure represented by the general formula (31) preferably has a molecular weight of 10,000 or less. Such a structure 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.

A compound having two or more functional groups represented by the general formula (41) and / or a functional group represented by the general formula (42). A functional group represented by the general formula (41) and / or a general formula. The compound having a functional group represented by (42) 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 in which a transesterification reaction is a curing reaction.

The compound having a functional group represented by the general formula (41) and / or a functional group represented by the general formula (42) 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 (41) and / or functional groups represented by the general formula (42), or may have two or more functional groups represented by the above general formula (41). In addition to the functional group represented by) and / or the functional group represented by the general formula (42), it may further have a hydroxyl group or the like.

As described above, the functional group represented by the general formula (41) is formed by carrying out a reaction represented by the general formula (51) or a reaction represented by the general formula (54) on various epoxy compounds. And / or a functional group represented by the general formula (42) can be introduced.
Therefore, a compound obtained by carrying out a reaction represented by the above general formula (54) with a known epoxy compound can also be used in the present invention.
The epoxy compound that can be used in 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 novolac 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 (53) with a carboxylic acid or a derivative thereof.
Then, by carrying out the reaction represented by the general formula (51) with respect to the epoxy compound, the functional group represented by the general formula (41) and / or the functional group represented by the general formula (42) 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 (41) and / or a functional group represented by the general formula (42) by the above reaction is particularly limited. For example, one having 50 or less carbon atoms can be used.
More specifically, various polycarboxylic acids and hydroxycarboxylic acids described as raw materials for obtaining the compound having the structure of the general formula (31) can be mentioned.
In addition, 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, saflower Fatty acids such as oil fatty acids; monocarboxylic 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, etc. Acids can also be mentioned.

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

(Alkyl esterified product of polyfunctional carboxylic acid)
A compound obtained by reacting a polyfunctional carboxylic acid or a derivative thereof with an alcohol can also be used as the above-mentioned ester compound. Such a reaction can be expressed by the following general formula.

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 many other applications. A compound obtained by alkyl esterifying such a polyfunctional carboxylic acid by a known method can also be used in the present invention. Esterification can be carried out by the above-mentioned alkyl group having 50 or less carbon atoms.

When such a compound is used as an ester compound, 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, the esterification improves the compatibility with the organic solvent and can be preferably used.
It is preferable in that.

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, various polycarboxylic acids and hydroxycarboxylic acids described as raw materials for obtaining the compound having the structure of the general formula (31) can be mentioned.

In the present invention, the above-mentioned compounds having two or more alkyl ester groups may be used in combination. Moreover, you may use the acid anhydride of these compounds as a raw material.

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. In addition, a method of alkyl esterifying a derivative of a polyfunctional carboxylic acid can also be mentioned.

The ester compound preferably has a molecular weight of 10,000 or less. Such a structure 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, 4,000 or less, and 2,000 or less.

As the other resin component (A-2) of the present invention, two or more of the above-mentioned compounds may be used in combination.

Further, in the thermosetting resin composition of the present invention, the ester group in the non-aqueous dispersion resin particles can be arbitrarily blended with respect to the number of hydroxyl groups derived from the other resin component (A-2), but 1 to 200% (1 to 200%). The number ratio) is preferable.

(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 generate 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 capable of activating the transesterification reaction can be used.
Specifically, various acidic compounds such as, for example, hydrochloric acid, sulfuric acid, nitrate, acetic acid, phosphoric acid or sulfonic acid, heteropolyacids; various basics such as LiOH, KOH or NaOH, amines, phosphines and the like. Compounds; PbO, magnesium oxide, zinc acetate, zinc acrylate, zinc acetylacetonate, zinc oxide, lead acetate, manganese acetate, copper acetate, nickel acetate, palladium acetate, aluminum isopropylate, alumina, zirconium acetylacetonate, zirconium oxide , Iron chloride, cobalt chloride, palladium chloride, zinc dithiocarbamate, antimony trioxide, tetraisopropyl titanate, titanium oxide, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin diacetate, monobutyltin oxide or monobutyltin acid, etc. Metal compounds; tetramethylammonium chloride, dodecyltrimethylammonium bromide, triethylbenzylammonium chloride, tetramethylammonium hydroxide, quaternary ammonium salts such as trimethylbenzylammonium methylcarbonate, etc., tetrabutylphosphonium bromide, tetrabutylphosphonium hydroxide, etc. Phosnium salt and the like, strong bases such as 1,8-diazabicyclo [5.4.0] undecene-7 and the like can be mentioned. Further, a photoresponsive catalyst and a thermal latent catalyst that generate an acid by light or heat can also be used. Further, a zinc cluster catalyst (for example, ZnTAC24 (trade name) manufactured by Tokyo Chemical Industry Co., Ltd.) or the like can also be used.
In the present invention, two or more kinds of the transesterification catalyst (B) described above may be used in combination.

In the present invention, it is most preferable to use a metal compound catalyst as the transesterification catalyst. The transesterification reactivity of the metal compound catalyst can be obtained by selecting a metal species, using it in combination with other compounds, or the like. Further, it is preferable that the required performance can be appropriately obtained by combining with the resin composition.

The metal compound catalyst is preferably a compound (B-1) containing at least one metal element selected from the group consisting of zinc, tin, titanium, aluminum, zirconium and iron. Such compounds are preferred because they have suitable transesterification reactivity. Among these, zinc, tin, and zirconium are preferable because they have particularly excellent transesterification reactivity.

As the metal compound, it is preferable to use a metal acetylacetonate as an anion component because a transesterification ability that is superior to that of the same metal compound tends to be obtained. For example, zinc acetylacetoneate and zirconium acetylacetoneate can be used particularly preferably. In particular, zirconium acetylacetoneate exhibits extremely good catalytic performance.

When the above metal compound is used as a catalyst, further, when at least one compound (B-2) selected from the group consisting of an organophosphorus compound, urea, an alkylated urea, a sulfoxide compound, a pyridine and a pyridine derivative is used in combination, a catalyst is used. It is more preferable in terms of improving performance.
The use of a metal compound activated by using these compounds in combination is particularly preferable in that the above-mentioned curing start temperature and gel fraction can be obtained.

Although the action of obtaining such an effect is not clear, it is presumed that the coordination of the compound (B-2) with the metal compound improves the catalytic activity. Therefore, as the compound (B-2), it is preferable to select a compound that can be coordinated with the metal compound.

The organic phosphorus compound is not particularly limited, and examples thereof include phosphoric acid, phosphoric acid, phosphonic acid, phosphinic acid, subphosphonic acid, organic phosphine oxide, organic phosphine compound, and various esters, amides, and salts thereof. Can be done. The ester may be an ester of an alkyl, a branched alkyl, a substituted alkyl, a bifunctional alkyl, an alkyl ether, an aryl, and a substituted aryl. The amide may be an amide of alkyl, branched alkyl, substituted alkyl, bifunctional alkyl, alkyl ether, aryl, and substituted aryl.

Among these, at least one compound selected from the group consisting of phosphonic acid ester, phosphoric acid amide and organic phosphine oxide compound is particularly preferable. When these organophosphorus compounds are used, the transesterification catalytic function is the best. More specifically, organic phosphine oxide compounds such as triphenylphosphine oxide, trioctylphosphine oxide, and tricyclohexylphosphine oxide; phosphorus such as hexamethylphosphate triamide and tris (N, N-tetramethylene) phosphate triamide. Organic phosphine sulfide compounds such as acid amide compounds, triphenylphosphine sulfide, tributylphosphine sulfide, and trioctylphosphine sulfide can be preferably used.

The alkylated urea is not particularly limited, and examples thereof include urea, dimethylurea, and dimethylpropylene urea. In addition, it may have a cyclic structure such as dimethylpropylene urea and the like.

The alkylated thiourea is not particularly limited, and examples thereof include dimethyl thiourea.
Examples of the sulfoxide compound include dimethyl sulfoxide and diphenyl sulfoxide.

Examples of the pyridine derivative include quinoline, isoquinoline, nicotinic acid ester and the like.

The transesterification catalyst of the present invention contains compound (B-1) and compound (B-2) in a ratio of (B-1) :( B-2) = 100: 1 to 1: 100 (weight ratio). It is preferable to do so. By blending in such a ratio, particularly suitable results can be obtained. The lower limit is more preferably 50: 1 and even more preferably 10: 1. The upper limit is more preferably 1:50 and even more preferably 1:10.

The compound (B-1) is preferably contained in a proportion of 0.01 to 50% by weight with respect to the amount of the compound involved in the reaction in the reaction system when causing the reaction.
The compound (B-2) is preferably contained in a proportion of 0.01 to 50% by weight with respect to the amount of the compound involved in the reaction in the reaction system when causing the reaction.

Further, in the thermosetting resin composition of the present invention, since a good curing reaction can be caused without using an acid catalyst, it is possible to prepare a thermosetting resin composition to which a basic compound is added. It is also preferable in that it can be done.

That is, an amine compound may be used as an additive such as a pigment dispersant. Further, when the coating material is made water-based, it is widely practiced to introduce an acid group such as a carboxylic acid group or a sulfonic acid group into the resin and neutralize the acid group with an amine compound or the like to make the paint water-soluble. In this case, it was difficult to use it in combination with an acidic catalyst. This has been a problem that hinders the water-based conversion of the thermosetting resin composition in which the transesterification catalyst is used as the curing reaction. In the present invention, it can be cured even under basic conditions.

In the present invention, the alkyl ester group is not limited. Further, in the thermosetting resin composition of the present invention, since a good curing reaction can be caused without using an acid catalyst, it is possible to prepare a thermosetting resin composition to which a basic compound is added. It is also preferable in that it can be done.

That is, an amine compound may be used as an additive such as a pigment dispersant. Further, when the coating material is made water-based, it is widely practiced to introduce an acid group such as a carboxylic acid group or a sulfonic acid group into the resin and neutralize the acid group with an amine compound or the like to make the paint water-soluble. In this case, it was difficult to use it in combination with an acidic catalyst. This has been a problem that hinders the water-based conversion of the thermosetting resin composition in which the transesterification catalyst is used as the curing reaction. In the present invention, since it can be cured even under basic conditions, it can be made water-based.

Further, even when the thermosetting resin composition of the present invention is used as a solvent-based coating composition, a water-based coating material may be used in combination as a part of the multilayer coating film. In this case, when the multilayer coating film is heat-cured at the same time, amines, ammonia and the like may be generated from other layers forming the multilayer coating film. Even in such a case, it is preferable in that good curing can be performed.

The amount of the transesterification catalyst (B) used is 0.01 to 50% by weight with respect to the total weight of the film physical characteristic modifier (A-1) and the other resin component (A-2). Is preferable. It is preferable that the content is within such a range because a good curing reaction can be performed at a low temperature.

(Mixing ratio)
The above-mentioned film physical characteristic modifier (A-1) and the other resin component (A-2) are mixed at a ratio of (A-1) :( A-2) = 3: 100 to 100: 3. Is preferable. Further, it is preferably 3: 100 to 100: 100. Mixing in such a range is preferable in that a cured product having good properties can be obtained.

In addition to the above-mentioned components, the thermosetting resin composition of the present invention may be used in combination with other cross-linking agents generally used in the fields of paints and adhesives. The cross-linking agent that can be used is not particularly limited, and examples thereof include isocyanate compounds, blocked isocyanate compounds, melamine resins, epoxy resins, and silane compounds. Further, vinyl ether, anionic polymerizable monomer, cationically polymerizable monomer, radically polymerizable monomer and the like may be used in combination. A curing agent for accelerating the reaction of these combined cross-linking agents may be used in combination.

However, in the present invention, it is preferable not to use the above-mentioned other cross-linking agent, and even if it is used, the amount used is preferably 30% by weight or less. That is, when the above-mentioned cross-linking agent is used, this may cause problems such as a decrease in storage stability, a sick house syndrome due to formaldehyde, and an increase in price due to the use of an isocyanate compound. In the present invention, stable curability can be ensured without causing these problems, and excellent coating film performance can also be obtained. The amount used is more preferably 25% by weight or less, further preferably 22% by weight or less. These may not be substantially contained. In addition, "substantially not contained" means that another cross-linking agent performs main cross-linking and determines the physical characteristics of the film, and when it is simply used as an auxiliary, it means outside the range.

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

Since the thermosetting resin composition of the present invention contains the above-mentioned film physical characteristic modifier, it is also preferable in that high solid differentiation (high solidification) of the coating material can be achieved. In the field of thermosetting resin compositions such as paints, it is preferable to increase the content of solid components in the composition from the viewpoint of coating efficiency and reduction of the amount of discharged solvent. In this case, it is preferable that the viscosity is such that it can be applied to a general coating method such as spraying even if the solid content is increased. That is, in order to achieve high solid differentiation, it is necessary to have a low molecular weight, which causes deterioration of the physical characteristics of the paint. In order to supplement the physical characteristics, it is desired that the film physical property adjusting agent as in the present invention is contained, the viscosity does not increase, and the film physical characteristics are maintained.

In the thermosetting resin composition of the present invention, when the above-mentioned film physical characteristic modifier is blended, it is also preferable in that high solid differentiation can be performed while maintaining a low viscosity. Specifically, by using such a film property modifier, high solidification can be achieved.

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% by weight. The upper limit is more preferably 400% by weight, still more preferably 300% by weight.

Examples of the coloring pigments include titanium oxide, zinc flower, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolin pigments, slene pigments, and perylene pigments. , 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 brilliant 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 sedimentation inhibitors. 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 coating material 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; Maleic anhydride-based thickeners such as partial esters of vinyl methyl 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, trade names) manufactured by Roam & Haas, and manufactured by San Nopco Ltd. Examples thereof include "SN thickener 613", "SN thickener 618", "SN thickener 630", "SN thickener 634", and "SN thickener 636" (hereinafter, product names).

Further, the above-mentioned association type thickeners are commercially available, and for example, "UH-420", "UH-450", "UH-462", "UH-472", "UH-540" manufactured by ADEKA, Inc. "UH-752", "UH-756VF", "UH-814N" (above, trade name), "ACRYSOLRM-8W", "ACRYSOLRM-825", "ACRYSOLRM-2020NPR", "ACRYSOLRM" manufactured by Roam & Hearth. -12W ”,“ ACRYSOLSCT-275 ”(above, product name), San Nopco“ 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 object to be coated to which the above thermosetting paint can be applied is not particularly limited, and for example, the outer panel of an automobile body such as a passenger car, a truck, a motorcycle, a bus; an automobile part; a mobile phone, an audio device, etc. There are various examples such as household electric appliances, 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 paint, a base paint, and a clear paint.

The object to be coated may be a metal surface of the metal material and a car body formed from the metal surface, 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 in which an undercoat film is formed by an electrodeposition paint is preferable, and a car body in 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.

The coating method of the heat-curable coating material is not particularly limited, and examples thereof include air spray coating, airless spray coating, rotary atomization coating, curtain coat coating, and the like, and air spray coating, rotary atomization coating, and the like are 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 about 80 to about 180 ° C., more preferably about 100 to about 170 ° C., and even more preferably about 120 to about 160 ° C., preferably for about 10 to about 60 minutes. And more preferably, it can be cured by heating for about 15 to about 40 minutes. Further, it is preferable in that it can cope with low temperature curing at 80 to 140 ° C.

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 curing performance 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, adhesives, and the like. May be available.

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

The present invention is a non-aqueous dispersion resin particle having an alkyl ester group.
The alkyl ester group is also a non-aqueous dispersion resin particle characterized in that at least a part thereof is a skeleton derived from a monomer represented by the following general formula (1).

ｎ_１：１〜１０
（式中、Ｒ_１、Ｒ_２，Ｒ_３は、同一又は異なって、水素、アルキル基、カルボキシル基、アルキルエステル基又は下記Ｒ_４−［ＣＯＯＲ_５］ｎ_１で表される構造を表す
Ｒ_４は、主鎖の原子数が５０以下であり、主鎖中にエステル基、エーテル基、アミド基、ウレタンからなる群より選択される１又は2以上の官能基を有していてもよく、側鎖を有していてもよい脂肪族、脂環族又は芳香族アルキレン基。
Ｒ_５は、炭素数５０以下のアルキル基。）

n ₁ : 1-10
_{(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 - [COOR 5] R} 4 representing a structure represented by _{n 1} Has a main chain having 50 or less atoms, and may have one or more functional groups selected from the group consisting of an ester group, an ether group, an amide group, and a urethane in the main chain. An aliphatic, alicyclic or aromatic alkylene group which may have a chain.
R ₅ is an alkyl group having 50 or less carbon atoms. )

The non-aqueous dispersion resin is as described in detail as a film physical characteristic modifier (A-1). Such non-aqueous dispersions are new. Further, it can be suitably used as a compounding component of the thermosetting resin composition of the present invention described above.

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 part.

Synthesis example 1
150 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester NB), 150 parts of t-butyl acrylate (Kyoeisha Chemical Co., Ltd .: light acrylate TB), hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd. product: light) 150 parts of ester HO-250) and 50 parts of styrene are used as a monomer mixture, and 25 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical V-65) are aromatic as an initiator. It was dissolved in hydrocarbon (T-SOL100) to prepare an initiator solution.
250 parts of aromatic hydrocarbon (T-SOL100) and 250 parts of propylene glycol monomethyl ether acetate were 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 130 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 130 ° C. for 4 hours to obtain a polymer solution A.

Synthesis example 2
240 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester NB), 105 parts of t-butyl acrylate (Kyoeisha Chemical Co., Ltd .: light acrylate TB), hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd. product: light) After mixing 110 parts of ester HO-250), 30 parts of styrene, and 15 parts of reactive emulsifier (Chemical of Daiichi Kogyo: Aqualon KH-10), 200 parts of ion-exchanged water is mixed and room temperature is used using a homomixer. Was emulsified for 1 hour to prepare a monomer emulsified solution. As an initiator, 15 parts of ammonium peroxodisulfate and 10 parts of sodium bisulfite were dissolved in ion-exchanged water to prepare an initiator solution.
400 parts of ion-exchanged water was placed in a stirable flask, and a monomer solution and an initiator solution were added dropwise while filling with nitrogen to carry out polymerization. The polymerization temperature at this time was 80 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 80 ° C. for 4 hours to obtain a polymer solution B.

Synthesis example 3
54 parts of ethylene glycol monoacetacetate monomethacrylate, 58 parts of t-butyl acrylate, 38 parts of potassium carbonate, 2 parts of 18-crown-6 ether, and 112 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 saturated aqueous ammonium chloride solution, washed twice with water, and the obtained organic layer was concentrated under reduced pressure to obtain Monomer A.

Synthesis example 4
54 parts of ethylene glycol monoacetate acetate monomethacrylate, 40 parts of methyl acrylate, 38 parts of potassium carbonate, 2 parts of 18-crown-6 ether, and 112 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 saturated aqueous ammonium chloride solution, washed twice with water, and the obtained organic layer was concentrated under reduced pressure to obtain Monomer B.

Synthesis example 5
180 parts of succinic anhydride and 173 parts of methanol are placed in a four-necked flask to dissolve succinic anhydride at 60 to 70 ° C. It was confirmed by NMR that the peak of succinic anhydride had disappeared, and methanol was removed under reduced pressure at 60 ° C. or higher to produce monomethyl succinate.
190 parts of monomethyl succinate, 205 parts of glycidyl methacrylate, triethylbenzylammonium chloride, and a polymerization inhibitor were added and reacted at 90 ° C. for 10 hours or more to obtain Monomer C.

Synthesis example 6
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 to the mixed solution at 30 to 40 ° C. 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 D.

Synthesis example 7
150 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester NB), 150 parts of monomer A, 150 parts of hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester HO-250), and 50 parts of styrene as a monomer. A mixed solution was prepared, and 25 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries V-65) was dissolved in an aromatic hydrocarbon (T-SOL100) as an initiator solution to prepare an initiator solution. ..
250 parts of aromatic hydrocarbon (T-SOL100) and 250 parts of propylene glycol monomethyl ether acetate were 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 110 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 110 ° C. for 4 hours to obtain a polymer solution C.

Synthesis example 8
150 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester NB), 150 parts of monomer B, 150 parts of hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester HO-250), and 50 parts of styrene as a monomer. A mixed solution was prepared, and 25 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries V-65) was dissolved in an aromatic hydrocarbon (T-SOL100) as an initiator solution to prepare an initiator solution. ..
250 parts of aromatic hydrocarbon (T-SOL100) and 250 parts of propylene glycol monomethyl ether acetate were 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 110 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 110 ° C. for 4 hours to obtain a polymer solution D.

Synthesis example 9
A monomer mixture of 150 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd .: Lightester NB), 150 parts of monomer C, 150 parts of hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd .: Lightester HO-250), and 50 parts of styrene. Then, 25 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries V-65) was dissolved in an aromatic hydrocarbon (T-SOL100) as an initiator solution to prepare an initiator solution.
250 parts of aromatic hydrocarbon (T-SOL100) and 250 parts of propylene glycol monomethyl ether acetate were 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 110 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 110 ° C. for 4 hours to obtain a polymer solution E.

Synthesis example 10
A monomer mixture of 150 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd .: Lightester NB), 150 parts of monomer D, 150 parts of hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd .: Lightester HO-250), and 50 parts of styrene. Then, 25 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries V-65) was dissolved in an aromatic hydrocarbon (T-SOL100) as an initiator solution to prepare an initiator solution.
250 parts of aromatic hydrocarbon (T-SOL100) and 250 parts of propylene glycol monomethyl ether acetate were 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 110 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 110 ° C. for 4 hours to obtain a polymer solution F.

Synthesis example 11
250 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester NB), 175 parts of hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester HO-250), and 75 parts of styrene were used as a monomer mixture. As an initiator, 25 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries V-65) was dissolved in an aromatic hydrocarbon (T-SOL100) to prepare an initiator solution.
250 parts of aromatic hydrocarbon (T-SOL100) and 250 parts of propylene glycol monomethyl ether acetate were 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 130 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 130 ° C. for 4 hours to obtain a polymer solution G.

Synthesis example 12
24 parts of t-butyl acrylate, 40 parts of di-t-butyl malonic acid, 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 13
80 parts of trimethylolpropane triacrylate, 37 parts of di-t-butyl malonic acid, 56 parts of potassium carbonate, 1.5 parts of 18-crown-6 ether, and 117 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 saturated aqueous ammonium chloride solution, washed twice with water, and the obtained organic layer was concentrated under reduced pressure to obtain ester compound B.

Synthesis example 14
31 parts of 1,6-hexanediol diacrylate, 37 parts of dimethyl malonate, 42 parts of potassium carbonate, 1.1 parts of 18-crown-6 ether, and 91 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 C.

Synthesis example 15
80 parts of trimethylolpropane triacrylate, 23 parts of dimethyl malonate, 56 parts of potassium carbonate, 1.5 parts of 18-crown-6 ether, and 117 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 an ester compound D.

Synthesis example 16
120 parts of stearyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester S), 120 parts of n-lauryl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester L), tertiary butyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester) 60 parts of TB) and 9 parts of 2-mercaptoethanol were used as a monomer mixture, and 3 parts of azobisisobutyronitrile as an initiator was dissolved in toluene to prepare an initiator solution.
300 parts of toluene 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 85 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 85 ° C. for 4 hours. Then, 18 parts of 2-isocyanatoethylacryllate (Showa Denko KK: Karens AOI) and 0.15 parts of dibutyltin dilaurate were added and reacted at 60 ° C. for 4 hours to obtain a macromonomer solution A.

Synthesis example 17
120 parts of stearyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester S), 120 parts of n-lauryl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester L), 60 parts of monomer A, and 9 parts of 2-mercaptoethanol. A mixed solution was prepared, and 3 parts of azobisisobutyronitrile as an initiator was dissolved in toluene to prepare an initiator solution.
300 parts of toluene 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 85 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 85 ° C. for 4 hours. Then, 18 parts of 2-isocyanatoethylacryllate (Showa Denko KK: Karens AOI) and 0.15 parts of dibutyltin dilaurate were added and reacted at 60 ° C. for 4 hours to obtain a macromonomer solution B.

Synthesis example 18
120 parts of stearyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester S), 120 parts of n-lauryl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester L), 60 parts of monomer B, and 9 parts of 2-mercaptoethanol. A mixed solution was prepared, and 3 parts of azobisisobutyronitrile as an initiator was dissolved in toluene to prepare an initiator solution.
300 parts of toluene 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 85 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 85 ° C. for 4 hours. Then, 18 parts of 2-isocyanatoethylacryllate (Showa Denko KK: Karens AOI) and 0.15 parts of dibutyltin dilaurate were added and reacted at 60 ° C. for 4 hours to obtain a macromonomer solution C.

Synthesis example 19
Stearyl Methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester S) 40 parts, n-lauryl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester L) 40 parts, Monomer B 20 parts, Hydrocarbon Methacrylate Kyoeisha Chemical Co., Ltd .: 20 parts of light ester HO-250) and 3 parts of α-methylstyrene dimer (Nippon Oil Co., Ltd .: Nofmer MSD) are used as a monomer mixture, and 3 parts of tertiary butyl peroxyoctate is used as an initiator. It was dissolved in hydrocarbon (T-SOL100) to prepare an initiator solution. 100 parts of aromatic hydrocarbon (T-SOL100) 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 130 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 130 ° C. for 4 hours. A macromonomer solution D was obtained.

Synthesis example 20
120 parts of n-lauryl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester L), 120 parts of isobornyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester IB-X), 60 parts of monomer B, 2-hydroxyethyl acrylate (Product of Kyoeisha Chemical Co., Ltd .: Light ester HOA (N)) 6 parts was used as a monomer mixed solution, and 12 parts of azobisisobutyronitrile was dissolved in 30 parts of butyl acetate as an initiator to prepare an initiator solution.
150 parts of xylene and 120 parts of butyl acetate were 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 85 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 85 ° C. for 4 hours. Then, 7 parts of 2-isocyanatoethylacryllate (Showa Denko KK Karens AOI) and 0.15 parts of dibutyltin dilaurate were added and reacted at 60 ° C. for 4 hours to obtain a macromonomer solution E.

Synthesis example 21
210 parts of n-lauryl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester L), 30 parts of methyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester M), and 60 parts of monomer C are used as a monomer mixture, and azobis as an initiator. 12 parts of isobutyronitrile was dissolved in 30 parts of butyl acetate to prepare an initiator solution.
150 parts of xylene and 120 parts of butyl acetate were 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 85 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 85 ° C. for 4 hours. Then, 7 parts of 2-isocyanatoethylacryllate (Showa Denko KK Karens AOI) and 0.15 parts of dibutyltin dilaurate were added and reacted at 60 ° C. for 4 hours to obtain a macromonomer solution F.

Synthesis example 22
174 parts of n-lauryl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester L), 60 parts of methyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester M), 60 parts of monomer D, 2-hydroxyethyl acrylate (Kyoeisha Chemical Co., Ltd.) ) Product: 6 parts of light ester HOA (N)) was used as a monomer mixed solution, and 12 parts of azobisisobutyronitrile as an initiator was dissolved in 30 parts of butyl acetate to prepare an initiator solution.
150 parts of xylene and 120 parts of butyl acetate were 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 85 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 85 ° C. for 4 hours. Then, 7 parts of 2-isocyanatoethylacryllate (Showa Denko KK Karens AOI) and 0.15 parts of dibutyltin dilaurate were added and reacted at 60 ° C. for 4 hours to obtain a macromonomer solution G.

Synthesis example 23
60 parts of macromonomeric solution A, 35 parts of methyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester M), and 5 parts of 2-hydroxymethacrylate (Kyoeisha Chemical Co., Ltd .: light ester HO-250) are used as a monomer mixture. As an initiator, 0.7 part of azobisisobutyronitrile was dissolved in toluene to prepare an initiator solution. 100 parts of toluene 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 85 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 85 ° C. for 4 hours. Then, 5 parts of 2-isocyanatoethylacryllate (Showa Denko KK: Karens AOI) and 0.1 part of dibutyltin dilaurate were added and reacted at 60 ° C. for 4 hours to obtain a macromonomer solution H.

Synthesis example 24
60 parts of macromonomeric solution B, 35 parts of methyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester M), and 5 parts of 2-hydroxymethacrylate (Kyoeisha Chemical Co., Ltd .: light ester HO-250) are used as a monomer mixture. As an initiator, 0.7 part of azobisisobutyronitrile was dissolved in toluene to prepare an initiator solution. 100 parts of toluene 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 85 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 85 ° C. for 4 hours. Then, 5 parts of 2-isocyanatoethylacryllate (Showa Denko KK: Karens AOI) and 0.1 part of dibutyltin dilaurate were added and reacted at 60 ° C. for 4 hours to obtain a macromonomer solution I.

Synthesis example 25
60 parts of macromonomer solution C, 50 parts of methyl acrylate, and 4 parts of 2-hydroxyacrylate (Kyoeisha Chemical Co., Ltd .: light acrylate HOA) were used as a monomer mixture, and 0.7 part of azobisisobutyronitrile was used as an initiator. Was dissolved in an aromatic hydrocarbon (T-SOL100) to prepare an initiator solution. 95 parts of aromatic hydrocarbon (T-SOL100) 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 80 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 80 ° C. for 4 hours. Then, 4 parts of 2-isocyanatoethylacryllate (Showa Denko KK: Karens AOI) and 0.1 part of dibutyltin dilaurate were added and reacted at 60 ° C. for 4 hours to obtain a macromonomer solution J.

Synthesis example 26
60 parts of macromonomer solution D, 50 parts of methyl acrylate, and 4 parts of 2-hydroxyacrylate (Kyoeisha Chemical Co., Ltd .: light acrylate HOA) were used as a monomer mixture, and 0.7 part of azobisisobutyronitrile was used as an initiator. Was dissolved in an aromatic hydrocarbon (T-SOL100) to prepare an initiator solution. 95 parts of aromatic hydrocarbon (T-SOL100) 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 80 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 80 ° C. for 4 hours. Then, 4 parts of 2-isocyanatoethylacryllate (Showa Denko KK: Karens AOI) and 0.1 part of dibutyltin dilaurate were added and reacted at 60 ° C. for 4 hours to obtain a macromonomer solution K.

Synthesis example 27
Macromonomeric solution A 30 parts, methyl methacrylate (Kyoeisha Chemical Co., Ltd. Product: light ester M) 18 parts, 2-hydroxyacrylate (Kyoeisha Chemical Co., Ltd. Product: light ester HOA) 12 parts, methyl acrylate 23 parts, styrene 6 parts , And 0.4 parts of ethylene glycol dimethacrylate (Kyoeisha Chemical Co., Ltd .: light ester EG) was used as a monomer mixture, and 0.7 parts of azobisisobutyronitrile was dissolved in heptane as an initiator solution. And said. 60 parts of heptane 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 80 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 80 ° C. for 4 hours to obtain a non-aqueous dispersion A.

Synthesis example 28
Macromonomeric solution B 30 parts, methyl methacrylate (Kyoeisha Chemical Co., Ltd. Product: light ester M) 18 parts, 2-hydroxyacrylate (Kyoeisha Chemical Co., Ltd. Product: light ester HOA) 12 parts, methyl acrylate 23 parts, styrene 6 parts , And 0.4 parts of ethylene glycol dimethacrylate (Kyoeisha Chemical Co., Ltd .: light ester EG) was used as a monomer mixture, and 0.7 parts of azobisisobutyronitrile was dissolved in heptane as an initiator solution. And said. 60 parts of heptane 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 80 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 80 ° C. for 4 hours to obtain a non-aqueous dispersion B.

Synthesis example 29
Macromonomeric solution C 30 parts, methyl methacrylate (Kyoeisha Chemical Co., Ltd. Product: light ester M) 18 parts, 2-hydroxyacrylate (Kyoeisha Chemical Co., Ltd. Product: light ester HOA) 12 parts, methyl acrylate 23 parts, styrene 6 parts , And 0.4 parts of ethylene glycol dimethacrylate (Kyoeisha Chemical Co., Ltd .: light ester EG) was used as a monomer mixture, and 0.7 parts of azobisisobutyronitrile was dissolved in heptane as an initiator solution. And said. 60 parts of heptane 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 80 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 80 ° C. for 4 hours to obtain a non-aqueous dispersion C.

Synthesis example 30
Macromonomeric solution D30 parts, methyl methacrylate (Kyoeisha Chemical Co., Ltd. Product: light ester M) 18 parts, 2-hydroxyacrylate (Kyoeisha Chemical Co., Ltd. Product: light ester HOA) 12 parts, methyl acrylate 23 parts, styrene 6 parts , And 0.4 parts of ethylene glycol dimethacrylate (Kyoeisha Chemical Co., Ltd .: light ester EG) was used as a monomer mixture, and 0.7 parts of azobisisobutyronitrile was dissolved in heptane as an initiator solution. And said. 60 parts of heptane 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 80 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 80 ° C. for 4 hours to obtain a non-aqueous dispersion D.

Synthesis example 31
Macromonomeric solution E 22 parts, methyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester M) 18 parts, 2-hydroxyacrylate (Kyoeisha Chemical Co., Ltd .: light ester HOA) 12 parts, methyl acrylate 23 parts, styrene 6 parts , Glycidyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester G) 2.4 parts, acrylic acid 1.2 parts as a monomer mixture, and 0.7 parts of azobisisobutyronitrile as an initiator dispersed in heptane. The starting agent solution was used. 75 parts of heptane 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 80 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 80 ° C. for 4 hours. After the reaction, 60 parts of xylene was added, 60 parts of heptane was distilled off by vacuum distillation, and then nitrogen filling was performed. 18 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester NB), 10 parts of monomer B, 3 parts of styrene, 0.5 part of azobisisobutyronitrile, and 15 parts of xylene were added dropwise as a monomer mixture. The polymerization temperature at this time was 80 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 80 ° C. for 4 hours to obtain a non-aqueous dispersion E.

Synthesis example 32
Macromonomeric solution F22 parts, methyl methacrylate (Kyoeisha Chemical Co., Ltd. Product: light ester M) 18 parts, 2-hydroxyacrylate (Kyoeisha Chemical Co., Ltd. Product: light ester HOA) 12 parts, methyl acrylate 23 parts, styrene 6 parts , Glycidyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester G) 2.4 parts, acrylic acid 1.2 parts as a monomer mixture, and 0.7 parts of azobisisobutyronitrile as an initiator dispersed in heptane. The starting agent solution was used. 75 parts of heptane 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 80 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 80 ° C. for 4 hours. After the reaction, 60 parts of xylene was added, 60 parts of heptane was distilled off by vacuum distillation, and then nitrogen filling was performed. 18 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester NB), 10 parts of monomer C, 3 parts of styrene, 0.5 part of azobisisobutyronitrile, and 15 parts of xylene were added dropwise as a monomer mixture. The polymerization temperature at this time was 80 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 80 ° C. for 4 hours to obtain a non-aqueous dispersion F.

Synthesis example 33
Macromonomeric solution G 22 parts, methyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester M) 18 parts, 2-hydroxyacrylate (Kyoeisha Chemical Co., Ltd .: light ester HOA) 12 parts, methyl acrylate 23 parts, styrene 6 parts , Glycidyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester G) 2.4 parts, acrylic acid 1.2 parts as a monomer mixture, and 0.7 parts of azobisisobutyronitrile as an initiator dispersed in heptane. The starting agent solution was used. 75 parts of heptane 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 80 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 80 ° C. for 4 hours. After the reaction, 60 parts of xylene was added, 60 parts of heptane was distilled off by vacuum distillation, and then nitrogen filling was performed. 18 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester NB), 10 parts of monomer D, 3 parts of styrene, 0.5 part of azobisisobutyronitrile, and 15 parts of xylene were added dropwise as a monomer mixture. The polymerization temperature at this time was 80 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 80 ° C. for 4 hours to obtain a non-aqueous dispersion G.

Synthesis example 34
Macromonomeric solution H30 parts, methyl methacrylate (Kyoeisha Chemical Co., Ltd. Product: light ester M) 18 parts, 2-hydroxyacrylate (Kyoeisha Chemical Co., Ltd. Product: light ester HOA) 12 parts, methyl acrylate 23 parts, styrene 6 parts , And 0.4 parts of ethylene glycol dimethacrylate (Kyoeisha Chemical Co., Ltd .: light ester EG) was used as a monomer mixture, and 0.7 parts of azobisisobutyronitrile was dissolved in heptane as an initiator solution. And said. 60 parts of heptane 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 80 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 80 ° C. for 4 hours to obtain a non-aqueous dispersion H.

Synthesis example 35
Macromonomeric solution I 30 parts, methyl methacrylate (Kyoeisha Chemical Co., Ltd. Product: light ester M) 18 parts, 2-hydroxyacrylate (Kyoeisha Chemical Co., Ltd. Product: light ester HOA) 12 parts, methyl acrylate 23 parts, styrene 6 parts , And 0.4 parts of ethylene glycol dimethacrylate (Kyoeisha Chemical Co., Ltd .: light ester EG) was used as a monomer mixture, and 0.7 parts of azobisisobutyronitrile was dissolved in heptane as an initiator solution. And said. 60 parts of heptane 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 80 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 80 ° C. for 4 hours to obtain a non-aqueous dispersion I.

Synthesis example 36
Macromonomeric solution J30 parts, methyl methacrylate (Kyoeisha Chemical Co., Ltd. Product: light ester M) 18 parts, 2-hydroxyacrylate (Kyoeisha Chemical Co., Ltd. Product: light ester HOA) 12 parts, methyl acrylate 23 parts, styrene 6 parts , And 0.4 parts of ethylene glycol dimethacrylate (Kyoeisha Chemical Co., Ltd .: light ester EG) was used as a monomer mixture, and 0.7 parts of azobisisobutyronitrile was dissolved in heptane as an initiator solution. And said. 60 parts of heptane 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 80 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 80 ° C. for 4 hours to obtain a non-aqueous dispersion J.

Synthesis example 37
Macromonomeric solution K30 parts, methyl methacrylate (Kyoeisha Chemical Co., Ltd. Product: light ester M) 18 parts, 2-hydroxyacrylate (Kyoeisha Chemical Co., Ltd. Product: light ester HOA) 12 parts, methyl acrylate 23 parts, styrene 6 parts , And 0.4 parts of ethylene glycol dimethacrylate (Kyoeisha Chemical Co., Ltd .: light ester EG) was used as a monomer mixture, and 0.7 parts of azobisisobutyronitrile was dissolved in heptane as an initiator solution. And said. 60 parts of heptane 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 80 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 80 ° C. for 4 hours to obtain a non-aqueous dispersion K.

Synthesis example 38
160 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester NB), 100 parts of t-butyl acrylate (Kyoeisha Chemical Co., Ltd .: light acrylate TB), hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd. product: light) Ester HO-250) 100 parts, styrene 50 parts, tetraethylene glycol dimethacrylate (Kyoeisha Chemical Co., Ltd .: light ester 4EG) 15 parts, and reactive emulsifier (Daiichi Kogyo Chemicals: Aqualon KH-10) 15 After mixing the parts, 200 parts of ion-exchanged water was mixed and emulsified at room temperature for 1 hour using a homomixer to prepare a monomer emulsion. As an initiator, 15 parts of ammonium peroxodisulfate and 10 parts of sodium bisulfite were dissolved in ion-exchanged water to prepare an initiator solution.
500 parts of ion-exchanged water was placed in a stirable flask, and a monomer solution and an initiator solution were added dropwise while filling with nitrogen to carry out polymerization. The polymerization temperature at this time was 80 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 80 ° C. for 4 hours to obtain a polymer solution H.

Synthesis example 39
90 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester NB), 90 parts of t-butyl acrylate (Kyoeisha Chemical Co., Ltd .: light acrylate TB), hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd. product: light) 90 parts of ester HO-250) and 30 parts of styrene were used as a monomer mixture, and 15 parts of tertiary butyl peroxyoctate was dissolved in aromatic hydrocarbon (T-SOL100) as an initiator solution to prepare an initiator solution. 500 parts of aromatic hydrocarbon (T-SOL100), 500 parts of propylene glycol monomethyl ether acetate, and 67 parts of α-methylstyrene dimer (Nippon Oil Co., Ltd .: Nofmer MSD) are placed in a stirable flask and sealed with nitrogen. While, the monomer solution and the initiator solution were added dropwise. The polymerization temperature at this time was set to 130 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 130 ° C. for 2 hours.
Then, 400 parts of isobutyl methacrylate (Kyoeisha Chemical Co., Ltd .: Light Ester IB) and 20 parts of tertiary butyl peroxyoctate were added dropwise. The polymerization temperature at this time was set to 130 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 130 ° C. for 2 hours. Furthermore, 90 parts of n-butyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester NB), 90 parts of t-butyl acrylate (Kyoeisha Chemical Co., Ltd .: light acrylate TB), hydroxyethyl methacrylate (Kyoeisha Chemical Co., Ltd. product: 90 parts of light ester HO-250) and 30 parts of styrene were used as a monomer mixture, and 15 parts of tertiary butyl peroxyoctate was added dropwise as an initiator. The polymerization temperature at this time was set to 130 ° C. The dropping was carried out in 2 hours, and further aging was carried out at 130 ° C. for 2 hours to obtain a polymer solution I.

Synthesis example 40
100 parts of hexahydroxyphthalic anhydride, 200 parts of adipic acid, 55 parts of trimethylolpropane, and 200 parts of 1,6, -hexanediol were mixed in a stirable flask and reacted at 200 ° C. for 5 hours. At this time, the water that came out during the reaction was removed with a fractional distillation tube. Then, it was diluted with 110 parts of aromatic hydrocarbon (T-SOL100) and 110 parts of propylene glycol monomethyl ether propionate to obtain a polymer solution J.

Synthesis example 41
2-Ethylhexyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester EH) 120 parts, stearyl methacrylate (Kyoeisha Chemical Co., Ltd .: light ester S) 120 parts, n-butyl acrylate 120 parts, monomer A 60 parts, hydroxy acrylate ( Kyoeisha Chemical Co., Ltd. Light Ester HOA) 60 parts and styrene 120 parts were used as a monomer mixed solution, and 18 parts of azobisisobutyronitrile as an initiator was dissolved in xylene to prepare an initiator solution.
300 parts of xylene and 60 parts of propylene glycol monomethyl ether acetate were 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 was carried out at 100 ° C. for 4 hours. Then, 18 parts of 2-isocyanatoethylacryllate (Showa Denko KK: Karens AOI) and 0.15 parts of dibutyltin dilaurate were added and reacted at 60 ° C. for 4 hours to obtain a polymer solution K.

Synthesis example 42
2-Ethylhexyl methacrylate (Kyoeisha Chemical Co., Ltd. Product: Light ester EH) 120 parts, Stearyl methacrylate (Kyoeisha Chemical Co., Ltd. Product: Light ester S) 120 parts, n-butyl acrylate 120 parts, monomer B 60 parts, hydroxy acrylate ( Kyoeisha Chemical Co., Ltd. Light Ester HOA) 60 parts and styrene 120 parts were used as a monomer mixed solution, and 18 parts of azobisisobutyronitrile as an initiator was dissolved in xylene to prepare an initiator solution.
300 parts of xylene and 60 parts of propylene glycol monomethyl ether acetate were 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 was carried out at 100 ° C. for 4 hours. Then, 18 parts of 2-isocyanatoethylacryllate (Showa Denko KK: Karens AOI) and 0.15 parts of dibutyltin dilaurate were added and reacted at 60 ° C. for 4 hours to obtain a polymer solution L.

Examples 1-26, Comparative Examples 1-10
Mix as shown in the table below, apply the PET film (100 μm) to a PET film (100 μm) at 400 μm (wet) using an applicator, and bake at 150 ° C. for 30 minutes. The measurement of the elongation rate was evaluated. In addition, the gel fraction was measured in the same manner. Each physical property in the table was measured by the following method.

The gel fraction was measured by dissolving the film obtained in the example in acetone reflux using Soxhlet for 30 minutes, and measuring the residual weight% of the film 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 rated as ◯ as it could withstand practical use.
A gel fraction of 80 to 100% was rated as ⊚ as having excellent performance.

The breaking stress was taken as the maximum stress at the time of breaking from the stress-strain test of the obtained film.
The value at which the breaking stress was judged to be 0 to 20 MPaS was defined as −.
The value at which the breaking stress was judged to be 20 to 30 MPaS was defined as +.
The value at which the breaking stress was judged to be 30 <MPaS was defined as ++.

The elongation rate was determined from the stress-strain test of the obtained film as the maximum elongation rate at the time of fracture.
Those with an elongation rate of <5% were defined as-.
Those with an elongation rate of 5 to 10% were defined as +.
Those with an elongation rate of 10 to 20% were defined as ++.

ｐｈｓ：フェノールスルホン酸

phs: phenol sulfonic acid

Ｕ−８２０：ジオクチル錫ジアセテート（ネオスタンＵ−８２０、日東化成（株）品）
Ｚｎ（ａｃａｃ）_２：亜鉛アセチルアセトネート

U-820: Dioctyl tin diacetate (Neostan U-820, Nitto Kasei Co., Ltd. product)
Zn (acac) ₂ : Zinc Acetylacetone

From Tables 1 to 4, it was shown that the thermosetting resin composition of the present invention had good curing performance, and the obtained cured film had good breaking strength and elongation.

The thermosetting resin composition of the present invention can be used as various coating compositions, adhesive compositions, and pressure-sensitive adhesive compositions.

The present invention contains a resin component (A) containing non-aqueous dispersion resin particles (A-1) as an essential component, and the resin component (A) has an alkyl ester group and a hydroxyl group, and further, a transesterification catalyst. containing (B),
The non-aqueous dispersion resin particles are a skeleton derived from a monomer represented by the following general formula (1), at least in part.
It is a thermosetting resin composition characterized by substantially containing no melamine resin and an isocyanate compound.

The nonaqueous dispersion resin particles preferably is at least partially backbone derived from a monomer represented by the following general formula (1).

ｎ_１：１〜１０
（式中、Ｒ_１、Ｒ_２，Ｒ_３は、同一又は異なって、水素、アルキル基、カルボキシル基、アルキルエステル基又は下記Ｒ_４−［ＣＯＯＲ_５］ｎ_１で表される構造を表す。
Ｒ_４は、主鎖の原子数が５０以下であり、主鎖中にエステル基、エーテル基、アミド基、ウレタンからなる群より選択される１又は2以上の官能基を有していてもよく、側鎖を有していてもよい脂肪族、脂環族又は芳香族アルキレン基。
Ｒ_５は、炭素数１〜４のアルキル基。）

n ₁ : 1-10
_{(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 - represents a [COOR _5] structure represented by _{n 1.}
R ₄ has 50 or less atoms in the main chain, and may have one or more functional groups selected from the group consisting of an ester group, an ether group, an amide group, and urethane in the main chain. , An aliphatic, alicyclic or aromatic alkylene group which may have a side chain.
R ₅ is an alkyl group having 1 to 4 carbon atoms. )

Claims (5)

A resin component containing a resin component (A) containing at least one film property modifier (A-1) selected from the group consisting of non-aqueous dispersion resin particles, block copolymers and polyester resin as an essential component. (A) is a thermosetting resin composition having an alkyl ester group and a hydroxyl group, and further containing an ester exchange catalyst (B). The thermosetting resin composition according to claim 1, which does not substantially contain a melamine resin and an isocyanate compound. The thermosetting resin composition according to claim 1 or 2, wherein at least a part of the non-aqueous dispersion resin particles is a skeleton derived from a monomer represented by the following general formula (1).

n ₁ : 1-10
_{(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 - [COOR 5] R} 4 representing a structure represented by _{n 1} Has a main chain having 50 or less atoms, and may have one or more functional groups selected from the group consisting of an ester group, an ether group, an amide group, and a urethane in the main chain. An aliphatic, alicyclic or aromatic alkylene group which may have a chain.
R ₅ is an alkyl group having 50 or less carbon atoms. ) A cured film obtained by thermosetting the thermosetting resin composition according to claim 1, 2 or 3. Non-aqueous dispersion resin particles having an alkyl ester group.
The alkyl ester group is a non-aqueous dispersion resin particle characterized in that at least a part thereof is a skeleton derived from a monomer represented by the following general formula (1).

n ₁ : 1-10
_{(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 - represents a [COOR _5] structure represented by _{n 1.}
R ₄ has 50 or less atoms in the main chain, and may have one or more functional groups selected from the group consisting of an ester group, an ether group, an amide group, and urethane in the main chain. , An aliphatic, alicyclic or aromatic alkylene group which may have a side chain.
R ₅ is an alkyl group having 50 or less carbon atoms. )