JP5515574B2 - Thermosetting composition for paint - Google Patents

Description

  The present invention relates to a thermosetting composition for paints. More specifically, the present invention relates to a thermosetting composition for paint that is excellent in both smoothness and blocking resistance of the resulting coating film and is easy to produce.

Conventionally, solvent-type paints have been often used as paints applied to articles such as automobiles.
However, with the recent increase in interest in the global environment, solvent-based paints, in which a large amount of solvent volatilizes, tend to be avoided. As a paint, it is required to change to a high solid state and further to a powder paint.
However, when a high solid paint or a powder paint with a coating composition containing a vinyl copolymer is used, the chemical properties and the storage stability are not sufficiently satisfactory, and the obtained coating film also has an appearance. The properties, physical properties, and particularly smoothness and blocking properties were not satisfactory.
Therefore, in order to improve the smoothness of the resulting coating film, a method of reducing the melt viscosity has been performed. However, in order to reduce the melt viscosity, it is necessary to lower the glass transition temperature of the vinyl copolymer, and this method cannot satisfy both smoothness and blocking properties. It was.
As a method for solving these problems, for example, Patent Documents 1 and 2 disclose the molecular weight distribution of a vinyl polymer, that is, the weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography. There is disclosed a thermosetting composition for paints in which the ratio (Mw / Mn) is reduced, the melt viscosity of the polymer is lowered, and both smoothness and blocking properties are achieved.

WO96 / 03464 WO02 / 30995

  This invention is made in view of the said problem, Comprising: It is excellent in both the smoothness of a coating film and blocking resistance, and provides the thermosetting composition for coating materials which is easy to manufacture. Objective.

  As a result of intensive studies in view of the above-mentioned problems, the present inventors have produced (A) a production method comprising a polymerization step of subjecting a vinyl monomer to a radical polymerization reaction in the presence of an organic halogen compound, and an epoxy group. A thermosetting composition for paints, comprising: a vinyl polymer having at least one functional group selected from a carboxyl group and a hydroxyl group; and (B) a curing agent. Was found to express.

The present invention is as follows.
1. (A) It is produced by a production method comprising a polymerization step in which a vinyl monomer is radically polymerized in the presence of an organic halogen compound, and has at least one functional group selected from an epoxy group, a carboxyl group and a hydroxyl group. And
The halogen atom in the organic halogen compound is an iodine atom,
The organic halogen compound is a bifunctional initiator having two carbon-halogen bonds, or is formed from a radical polymerization initiator and iodine,
The number average molecular weight is 1000 to 10,000, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is less than 2.0.
The average number of the functional group, and 1.0 to 6.5 der Ru vinyl polymer,
(B) a curing agent ,
The curing agent (B) is a compound having two or more functional groups that can react with the functional group of the vinyl polymer (A).
Content of the said hardening | curing agent (B) is the range whose molar ratio of the functional group which the said hardening | curing agent (B) has with respect to the said functional group which the said vinyl polymer (A) has is 0.5-2.0. coating the thermosetting composition characterized der Rukoto.
2. The above-mentioned 1. The organic halogen compound is an iodine-containing compound having a structure in which the organic halogen compound has two iodine atoms and the iodine atom is bonded to a carbon atom bonded to an aromatic ring. The thermosetting composition for paints described in 1.
3. The vinyl polymer (A) is produced by a production method further comprising a terminal modification step. Or 2. The thermosetting composition for paints described in 1.
4 . 1. The vinyl polymer (A) having the functional group at the molecular end. Thru 3 . The thermosetting composition for paints according to any one of the above.
5 . 1. The vinyl polymer (A) is a (meth) acrylic polymer. To 4 . The thermosetting composition for paints according to any one of the above.

  The thermosetting composition for coatings of the present invention is produced by a production method comprising a polymerization step in which a vinyl monomer is subjected to radical polymerization reaction in the presence of an organic halogen compound (A), and an epoxy group, a carboxyl group. And a vinyl polymer having at least one functional group selected from hydroxyl groups, and (B) a curing agent, it is a thermosetting composition for paints, and is therefore excellent in both smoothness and blocking resistance. A coating film can be obtained.

Hereinafter, the thermosetting composition for paints of the present invention will be described in detail.
The thermosetting composition for coatings of the present invention is produced by a production method comprising a polymerization step in which a vinyl monomer is subjected to radical polymerization reaction in the presence of an organic halogen compound (A), and an epoxy group, a carboxyl group. and have at least one functional group selected from hydroxyl group, a halogen atom in the organic halide compound is an iodine atom, the organic halogen compound, carbon - or a difunctional initiators having two halogen bond Alternatively, it is formed from a radical polymerization initiator and iodine, the number average molecular weight is 1000 to 10,000, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is less than 2.0, the average number of the functional group, and 1.0 to 6.5 der Ru vinyl polymer (hereinafter also referred to as "vinyl polymer (a)"), Containing B) a curing agent, and the curing agent (B) is a compound having two or more functional groups capable of reacting with the functional group of the vinyl polymer (A) has, the curing agent ( the content of B) is for the functional group which the vinyl polymer (a) has a molar ratio of functional groups of the curing agent (B) has the 0.5 to 2.0 range der Rukoto of It is characterized by.
In the present specification, “(meth) acryl” is used to mean one or both of acryl and methacryl, and “(meth) acrylate” is used to mean one or both of acrylate and methacrylate. .

  The vinyl polymer (A) is produced by a production method including a polymerization step in which a vinyl monomer is subjected to radical polymerization reaction in the presence of an organic halogen compound, and at least one selected from an epoxy group, a carboxyl group, and a hydroxyl group. It is a vinyl polymer having a functional group. One type of the same functional group may be sufficient as the said functional group with which a vinyl type polymer (A) is equipped, and two or more types of different functional groups may be sufficient as it.

Examples of the vinyl polymer (A) include the following embodiments.
(1) A vinyl polymer (A1) having the functional group obtained by radical polymerization reaction of a monomer mixture containing the vinyl monomer having the functional group in the presence of an organic halogen compound.
(2) A radical polymerization reaction of a vinyl monomer using an initiator precursor (a) described later having the above functional group and an initiator precursor (b) composed of a halogen alone as the organic halogen compound. The obtained vinyl polymer (A2) having the functional group.
(3) By modifying the terminal of a vinyl polymer (first polymer) obtained by radical polymerization reaction of a vinyl monomer in the presence of the organic halogen compound, the functional group is converted to a molecular terminal. A vinyl polymer (A3).
(4) A vinyl polymer obtained by combining a plurality of the above embodiments.

  The vinyl polymer (A1) in the embodiment (1) has the functional group derived from the vinyl monomer having the functional group in the polymer molecule. This vinyl polymer (A1) is a polymerization in which a vinyl polymer (A1) is obtained by radical polymerization of a monomer composition containing a vinyl monomer having the functional group in the presence of the organic halogen compound. Obtained by the process.

The position of the functional group of the vinyl polymer (A1) is not particularly limited as long as it is in the molecule of the vinyl polymer (A1), but it is preferably near the terminal (this terminal includes the terminal). The same applies hereinafter).
The vinyl polymer (A1) having the functional group in the vicinity of the terminal is, for example, after the polymerization reaction of a certain amount of the vinyl monomer having no functional group is completed in the polymerization step, that is, polymerization It can be produced by adding a vinyl monomer having the above functional group to the reaction system at a later stage of the reaction.

  The vinyl polymer (A2) in the embodiment (2) uses, as an organic halogen compound, an initiator precursor (a) described later having the functional group and an initiator precursor (b) composed of a halogen alone. Can be obtained. This vinyl polymer (A2) has the functional group derived from the initiator precursor (a) at one of the molecular terminals. And the other molecular terminal is equipped with the halogen atom derived from the halogen simple substance which consists of an initiator precursor (b).

  The vinyl polymer (A3) in the aspect (3) has the functional group at the molecular end. This vinyl polymer (A3) is obtained by radically polymerizing a vinyl monomer in the presence of the organic halogen compound, and the vinyl polymer (first polymer) obtained by the polymerization reaction. A polymer obtained by modifying the terminal of the first polymer and having the functional group at the molecular terminal.

In addition, the vinyl polymer (A3) is obtained by radical polymerization of a vinyl monomer in the presence of the organic halogen compound, and the first polymer obtained by the polymerization reaction is compared with the first polymer. It is a polymer obtained by modifying the terminal and having the functional group at the molecular terminal.
In this case, the monomer used may include a monomer having the above functional group, or may be only a monomer having no functional group. The polymer obtained by the polymerization reaction can be converted into a vinyl polymer (A3) having the functional group at the molecular end by modifying the terminal.
Furthermore, in this case, an initiator precursor (a) described later having the functional group may or may not be used as the organic halogen compound.

The method for producing the vinyl polymer (A3) is obtained by a production method including a polymerization step (hereinafter, also referred to as “first step”) in which a vinyl monomer is radically polymerized in the presence of the organic halogen compound. be able to. By using an organic halogen compound in the polymerization reaction in the polymerization step, the resulting polymer can be made into a polymer having a dispersity (Mw / Mn) of less than 2.0.
And the vinyl polymer (henceforth a "1st polymer") obtained by a superposition | polymerization process has a halogen atom derived from an organic halogen compound in a molecular terminal.
In the present specification, the polymer obtained by the polymerization step is referred to as a first polymer, and the first polymer includes the vinyl polymer (A1) and the vinyl polymer (A2). included.

In the polymerization step, a vinyl polymer having the functional group in the molecule is obtained by using the monomer having the functional group.
Moreover, even if it is a case where it is a case where it is a case where it superposes | polymerizes without using the vinyl polymer which has the said functional group in a molecule | numerator in this superposition | polymerization process, the initiator precursor (a) which has the said functional group is used as an organic halogen compound. Thereby, it can be set as the vinyl polymer which has the said functional group derived from an initiator precursor (a) in the molecular terminal of a vinyl polymer.

  As a manufacturing method of a vinyl type polymer (A), the terminal modification process (henceforth "the 2nd process") can be further provided after the said polymerization process. This terminal modification step is a step of performing a chemical reaction in which the halogen atom at the molecular end of the first polymer obtained in the polymerization step is replaced with the functional group by a general chemical reaction. By this terminal modification step, the vinyl polymer (A) having the functional group at the molecular terminal can be obtained.

The organic halogen compound used in the polymerization step is a compound having a function as an initiator. This organic halogen compound (hereinafter also referred to as “initiator”) has at least one bond between a carbon atom and a halogen atom (hereinafter also referred to as “carbon-halogen bond”).
When the above organic halogen compound is used as an initiator, a first polymer in which a halogen atom derived from an organic halogen compound (hereinafter referred to as “halogen atom (a)”) is formed by polymerization of a vinyl monomer. It will be located at the end of the growing chain. In the polymerization step, the halogen atom (a) at the end of the growing chain moves to the polymer end in the polymerization process, and also serves as a protecting group for protecting the growing chain during the reaction in radical polymerization.
The halogen atom in the organic halogen compound used in the present invention is an iodine atom, and the organic halogen compound used in the present invention is a bifunctional initiator having two carbon-halogen bonds, or radical polymerization is initiated. Formed from an agent and iodine.

In the organic group of the organic halogen compound, the number of hydrogen atoms bonded to the carbon to which the halogen atom is bonded (hereinafter referred to as “carbon (X)”) is preferably 2 or less, more preferably 1 or less. , 0 (having no hydrogen atom) is more preferable.
Further, the number of halogen atoms bonded to the carbon (X) is preferably 3 or less, more preferably 2 or less, and even more preferably 1.
The carbon (X) preferably has a carbon atom bonded thereto. The number of carbon atoms bonded to carbon (X) is preferably 1 or more, more preferably 2 or more, and still more preferably 3.

Examples of the halogen atom (a) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom . In the present invention, it is an iodine atom . These organic halogen compounds can be used alone or in combination of two or more.

The carbon-halogen bond of the initiator acts as a functional group in the polymerization of the vinyl monomer. That is, an initiator having two or more carbon-halogen bonds is a polyfunctional initiator, and an initiator having two carbon-halogen bonds is a bifunctional initiator. An initiator having one carbon-halogen bond is a monofunctional initiator.
In the polymerization step, when the initiator used is a monofunctional initiator, the first polymer obtained has a halogen atom only at one end. In this case, the other end not having the halogen atom has a remaining structure obtained by removing the halogen atom from the initiator. Moreover, when a bifunctional initiator is used, the first polymer obtained has halogen atoms at both ends.

The bifunctional initiator is not particularly limited as long as it is an organic halogen compound having two carbon-halogen bonds. Preferably, the carbon atom having a carbon-halogen bond is a compound composed of different carbon atoms. For example, the compounds represented by the following general formulas (1) to (10) may be mentioned. As the organic halogen compound used in the present invention, X in the following general formulas (1) to (10) is an iodine atom. is there. These compounds can be used alone or in combination of two or more.

上記一般式（１）において、Ｒ^１及びＲ^２は、炭素数１〜５の二価のアルキレン基であり、好ましくは炭素数１〜３の直鎖の二価のアルキレン基であり、より好ましくは、メチレン基（−ＣＨ_２−）であり、Ｒ^１及びＲ^２は同一であっても、異なっていてもよい。
また、上記一般式（１）において、Ｘは塩素原子、臭素原子及びヨウ素原子から選ばれるハロゲン原子であり、好ましくはヨウ素原子であり、複数のハロゲン原子は同一であっても、異なっていてもよい。

In the general formula (1), R ¹ and R ² is a divalent alkylene group having 1 to 5 carbon atoms, preferably a divalent alkylene group having a straight chain of 1 to 3 carbon atoms, more preferably Is a methylene group (—CH ₂ —), and R ¹ and R ² may be the same or different.
In the general formula (1), X is a halogen atom selected from a chlorine atom, a bromine atom and an iodine atom, preferably an iodine atom, and a plurality of halogen atoms may be the same or different. Good.

上記一般式（２）において、Ｒ^３及びＲ^４は、炭素数１〜５の二価のアルキレン基であり、好ましくは炭素数１〜３の直鎖の二価のアルキレン基であり、より好ましくは、メチレン基（−ＣＨ_２−）であり、Ｒ^３及びＲ^４は同一であっても、異なっていてもよい。
また、上記一般式（２）において、Ｘは塩素原子、臭素原子及びヨウ素原子から選ばれるハロゲン原子であり、好ましくはヨウ素原子であり、複数のハロゲン原子は同一であっても、異なっていてもよい。

In the general formula (2), R ³ and R ⁴ are a divalent alkylene group having 1 to 5 carbon atoms, preferably a linear divalent alkylene group having 1 to 3 carbon atoms, and more preferably. Is a methylene group (—CH ₂ —), and R ³ and R ⁴ may be the same or different.
In the general formula (2), X is a halogen atom selected from a chlorine atom, a bromine atom and an iodine atom, preferably an iodine atom, and a plurality of halogen atoms may be the same or different. Good.

上記一般式（３）において、Ｒ^６及びＲ^７は、水素原子又は炭素数１〜５のアルキル基であり、このアルキル基は分岐を有するものでも、直鎖状のものでも構わない。また、このアルキル基は好ましくは炭素数１〜３のアルキル基であり、より好ましくはメチル基である。Ｒ^６及びＲ^７は同一であっても、異なっていてもよい。
また、上記一般式（３）において、Ｒ^５は、炭素数１〜２０の二価のアルキレン基であり、分岐を有するものでも、直鎖状のものでも構わない。
また、上記一般式（３）において、Ｒ^８及びＲ^９は、炭素数１〜２０のアルキル基、アリール基又はアラルキル基であり、アルキル基の場合は、分岐を有するものでも、直鎖状のものでも構わない。Ｒ^８及びＲ^９は同一であっても、異なっていてもよい。
また、上記一般式（３）において、Ｘは塩素原子、臭素原子及びヨウ素原子から選ばれるハロゲン原子であり、好ましくはヨウ素原子であり、複数のハロゲン原子は同一であっても、異なっていてもよい。

In the general formula (3), R ⁶ and R ⁷ are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and this alkyl group may be branched or linear. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. R ⁶ and R ⁷ may be the same or different.
In the general formula (3), R ⁵ is a divalent alkylene group having 1 to 20 carbon atoms, and may be branched or linear.
In the general formula (3), R ⁸ and R ⁹ are each an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group. It does n’t matter. R ⁸ and R ⁹ may be the same or different.
In the general formula (3), X is a halogen atom selected from a chlorine atom, a bromine atom and an iodine atom, preferably an iodine atom, and a plurality of halogen atoms may be the same or different. Good.

上記一般式（４）において、Ｒ^１１及びＲ^１２は、水素原子又は炭素数１〜５のアルキル基であり、このアルキル基は分岐を有するものでも、直鎖状のものでも構わない。また、このアルキル基は好ましくは炭素数１〜３のアルキル基であり、より好ましくはメチル基である。Ｒ^１１及びＲ^１２は同一であっても、異なっていてもよい。
また、上記一般式（４）において、Ｒ^１０は、炭素数１〜２０の二価のアルキレン基であり、分岐を有するものでも、直鎖状のものでも構わない。
また、上記一般式（４）において、Ｒ^１３及びＲ^１４は、炭素数１〜２０のアルキル基、アリール基又はアラルキル基であり、アルキル基の場合は、分岐を有するものでも、直鎖状のものでも構わない。Ｒ^１３及びＲ^１４は同一であっても、異なっていてもよい。
また、上記一般式（４）において、Ｘは塩素原子、臭素原子及びヨウ素原子から選ばれるハロゲン原子であり、好ましくはヨウ素原子であり、複数のハロゲン原子は同一であっても、異なっていてもよい。

In the general formula (4), R ¹¹ and R ¹² are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and this alkyl group may be branched or linear. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. R ¹¹ and R ¹² may be the same or different.
In the general formula (4), R ¹⁰ is a divalent alkylene group having 1 to 20 carbon atoms and may be branched or linear.
Similarly, the general formula (4), R ¹³ and R ^14, an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group, in the case of alkyl group, even those having a branched, straight-chain It does n’t matter. R ¹³ and R ¹⁴ may be the same or different.
In the general formula (4), X is a halogen atom selected from a chlorine atom, a bromine atom and an iodine atom, preferably an iodine atom, and a plurality of halogen atoms may be the same or different. Good.

上記一般式（５）において、Ｒ^１５、Ｒ^１６、Ｒ^１７、及びＲ^１８は、水素原子又は炭素数１〜５のアルキル基であり、このアルキル基は分岐を有するものでも、直鎖状のものでも構わない。また、このアルキル基は好ましくは炭素数１〜３のアルキル基であり、より好ましくはメチル基である。Ｒ^１５、Ｒ^１６、Ｒ^１７、及びＲ^１８は同一であっても、異なっていてもよい。
また、上記一般式（５）において、Ｘは塩素原子、臭素原子及びヨウ素原子から選ばれるハロゲン原子であり、好ましくはヨウ素原子であり、複数のハロゲン原子は同一であっても、異なっていてもよい。

In the general formula (5), R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and this alkyl group may be branched or linear. It does n’t matter. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ may be the same or different.
In the general formula (5), X is a halogen atom selected from a chlorine atom, a bromine atom and an iodine atom, preferably an iodine atom, and a plurality of halogen atoms may be the same or different. Good.

上記一般式（６）において、Ｒ^２０、Ｒ^２１、Ｒ^２２、及びＲ^２３は、水素原子又は炭素数１〜５のアルキル基であり、このアルキル基は分岐を有するものでも、直鎖状のものでも構わない。また、このアルキル基は好ましくは炭素数１〜３のアルキル基であり、より好ましくはメチル基である。Ｒ^２０、Ｒ^２１、Ｒ^２２、及びＲ^２３は同一であっても、異なっていてもよい。
また、上記一般式（６）において、Ｒ^１９は、炭素数１〜２０の二価のアルキレン基であり、分岐を有するものでも、直鎖状のものでも構わない。
また、上記一般式（６）において、Ｘは塩素原子、臭素原子及びヨウ素原子から選ばれるハロゲン原子であり、好ましくはヨウ素原子であり、複数のハロゲン原子は同一であっても、異なっていてもよい。

In the general formula (6), R ²⁰ , R ²¹ , R ²² , and R ²³ are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the alkyl group may be branched or linear. It does n’t matter. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. R ²⁰ , R ²¹ , R ²² , and R ²³ may be the same or different.
In the general formula (6), R ¹⁹ is a divalent alkylene group having 1 to 20 carbon atoms, and may be branched or linear.
In the general formula (6), X is a halogen atom selected from a chlorine atom, a bromine atom and an iodine atom, preferably an iodine atom, and a plurality of halogen atoms may be the same or different. Good.

上記一般式（７）において、Ｒ^２６、Ｒ^２７、Ｒ^２８、及びＲ^２９は、水素原子又は炭素数１〜５のアルキル基であり、このアルキル基は分岐を有するものでも、直鎖状のものでも構わない。また、このアルキル基は好ましくは炭素数１〜３のアルキル基であり、より好ましくはメチル基である。Ｒ^２６、Ｒ^２７、Ｒ^２８、及びＲ^２９は同一であっても、異なっていてもよい。
また、上記一般式（７）において、Ｒ^２５は、炭素数１〜２０の二価のアルキレン基であり、分岐を有するものでも、直鎖状のものでも構わない。
また、上記一般式（７）において、Ｘは塩素原子、臭素原子及びヨウ素原子から選ばれるハロゲン原子であり、好ましくはヨウ素原子であり、複数のハロゲン原子は同一であっても、異なっていてもよい。

In the general formula (7), R ²⁶ , R ²⁷ , R ²⁸ , and R ²⁹ are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and this alkyl group may be branched or linear. It does n’t matter. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. R ²⁶ , R ²⁷ , R ²⁸ , and R ²⁹ may be the same or different.
In the general formula (7), R ²⁵ is a divalent alkylene group having 1 to 20 carbon atoms, and may be branched or linear.
In the general formula (7), X is a halogen atom selected from a chlorine atom, a bromine atom and an iodine atom, preferably an iodine atom, and a plurality of halogen atoms may be the same or different. Good.

上記一般式（８）において、Ｒ^３０、Ｒ^３１、Ｒ^３２、及びＲ^３３は、水素原子又は炭素数１〜５のアルキル基であり、このアルキル基は分岐を有するものでも、直鎖状のものでも構わない。また、このアルキル基は好ましくは炭素数１〜３のアルキル基であり、より好ましくはメチル基である。Ｒ^３０、Ｒ^３１、Ｒ^３２、及びＲ^３３は同一であっても、異なっていてもよい。
また、上記一般式（８）において、Ｘは塩素原子、臭素原子及びヨウ素原子から選ばれるハロゲン原子であり、好ましくはヨウ素原子であり、複数のハロゲン原子は同一であっても、異なっていてもよい。

In the general formula (8), R ³⁰ , R ³¹ , R ³² , and R ³³ are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the alkyl group may be branched or linear. It does n’t matter. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. R ³⁰ , R ³¹ , R ³² , and R ³³ may be the same or different.
In the general formula (8), X is a halogen atom selected from a chlorine atom, a bromine atom and an iodine atom, preferably an iodine atom, and a plurality of halogen atoms may be the same or different. Good.

上記一般式（９）において、Ｒ^３４、Ｒ^３５、Ｒ^３６、及びＲ^３７は、水素原子又は炭素数１〜５のアルキル基であり、このアルキル基は分岐を有するものでも、直鎖状のものでも構わない。また、このアルキル基は好ましくは炭素数１〜３のアルキル基であり、より好ましくはメチル基である。Ｒ^３４、Ｒ^３５、Ｒ^３６、及びＲ^３７は同一であっても、異なっていてもよい。
また、上記一般式（９）において、Ｘは塩素原子、臭素原子及びヨウ素原子から選ばれるハロゲン原子であり、好ましくはヨウ素原子であり、複数のハロゲン原子は同一であっても、異なっていてもよい。

In the general formula (9), R ³⁴ , R ³⁵ , R ³⁶ , and R ³⁷ are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the alkyl group may be branched or linear. It does n’t matter. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. R ³⁴ , R ³⁵ , R ³⁶ , and R ³⁷ may be the same or different.
In the general formula (9), X is a halogen atom selected from a chlorine atom, a bromine atom and an iodine atom, preferably an iodine atom, and the plurality of halogen atoms may be the same or different. Good.

上記一般式（１０）において、Ｒ^３９、Ｒ^４０、Ｒ^４１、及びＲ^４２は、水素原子又は炭素数１〜５のアルキル基であり、このアルキル基は分岐を有するものでも、直鎖状のものでも構わない。また、このアルキル基は好ましくは炭素数１〜３のアルキル基であり、より好ましくはメチル基である。Ｒ^３９、Ｒ^４０、Ｒ^４１、及びＲ^４２は同一であっても、異なっていてもよい。
また、上記一般式（１０）において、Ｒ^３８は、炭素数１〜２０の二価のアルキレン基であり、分岐を有するものでも、直鎖状のものでも構わない。
また、上記一般式（１０）において、Ｘは塩素原子、臭素原子及びヨウ素原子から選ばれるハロゲン原子であり、好ましくはヨウ素原子であり、複数のハロゲン原子は同一であっても、異なっていてもよい。

In the general formula (10), R ³⁹ , R ⁴⁰ , R ⁴¹ , and R ⁴² are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and this alkyl group may be branched or linear. It does n’t matter. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. R ³⁹ , R ⁴⁰ , R ⁴¹ , and R ⁴² may be the same or different.
In the general formula (10), R ³⁸ is a divalent alkylene group having 1 to 20 carbon atoms, and may be branched or linear.
In the general formula (10), X is a halogen atom selected from a chlorine atom, a bromine atom and an iodine atom, preferably an iodine atom, and the plurality of halogen atoms may be the same or different. Good.

  Specific examples of the bifunctional initiator include diiodoxylene and diethyl-2,5-diiododipate.

上記一般式（１１）において、Ｒ^４１は、水素原子、又は炭素数１〜５のアルキル基を示し、Ｒ^４２は、水素原子、又は炭素数１〜５のアルキル基を示し、Ｘは、塩素原子、臭素原子及びヨウ素原子から選ばれるハロゲン原子を示す。

上記一般式（１２）において、Ｒ^４３は、水素原子、又は炭素数１〜５のアルキル基を示し、Ｒ^４４は、炭素数１〜５の二価のアルキレン基を示し、Ｒ^４５は、水素原子、ヒドロキシル基、カルボキシル基又はアミノ基を示し、Ｘは、塩素原子、臭素原子及びヨウ素原子から選ばれるハロゲン原子を示す。 The monofunctional initiator is an organic halogen compound having one carbon-halogen bond. For example, CH (CH ₃ ) (Ph) I represented by the following general formula (11), C (CH ₃ ) ₂ (CN) I represented by the following general formula (12), and the following formula (13c) ) And the like.

In the general formula (11), R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁴² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X represents chlorine. A halogen atom selected from an atom, a bromine atom and an iodine atom is shown.

In the general formula (12), R ⁴³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁴⁴ represents a divalent alkylene group having 1 to 5 carbon atoms, and R ⁴⁵ represents hydrogen. An atom, a hydroxyl group, a carboxyl group or an amino group, and X represents a halogen atom selected from a chlorine atom, a bromine atom and an iodine atom;

Examples of the organic halogen compound include diiodomethane, 1,1-diiodoethane, 1,2-diiodoethane, 1,2-diiodoethylene, bromoiodomethane, 1-bromo-2-iodoethane, iodomethylbenzene, and iodomethyl. Naphthalene, 1,3-diiodoxylene, 1,4-diiodoxylene, 1,3,5-tris (iodomethyl) benzene, diphenyldiiodomethane, 4,4′-bis (iodomethyl) biphenyl, bis (4- Iodomethylphenyl) methane, 4,4′-bis (iodomethyl) diphenyl ether, 1,5-bis (iodomethyl) naphthalene, 2,6-bis (iodomethyl) naphthalene, 2,4,6,8-tetrakis (iodomethyl) naphthalene 2,6-bis (iodomethyl) anthracene, 9,10- Iodine compounds such as s (iodomethyl) anthracene and 1,4,5,8-tetrakis (iodomethyl) anthracene; chloromethylbenzene, chloromethylnaphthalene, 1,3-dichloroxylene, 1,4-dichloroxylene, 1,3,3 5-tris (chloromethyl) benzene, diphenyldichloromethane, 4,4′-bis (chloromethyl) biphenyl, bis (4-chloromethylphenyl) methane, 4,4′-bis (chloromethyl) diphenyl ether, 1,5- Bis (chloromethyl) naphthalene, 2,6-bis (chloromethyl) naphthalene, 2,4,6,8-tetrakis (chloromethyl) naphthalene, 2,6-bis (chloromethyl) anthracene, 9,10-bis ( Chloromethyl) anthracene, 1,4,5,8-tetrakis (chloromethyl) a Chlorine compounds such as tracene; dibromomethane, 1,1-dibromoethane, 1,2-dibromoethane, 1,2-dibromopropane, 1,3-dibromopropane, 1,3-dibromobutane, 1,4-dibromobutane 1,5-dibromopentane, 1,6-dibromohexane, 1,7-dibromohexane, 1,8-dibromooctane, 1,2-dibromoethylene, 2,3-dibromopropene, bromomethylbenzene, bromomethyl Naphthalene, 1,3-dibromoxylene, 1,4-dibromoxylene, 1,3,5-tris (bromomethyl) benzene, diphenyldibromomethane, 4,4′-bis (bromomethyl) biphenyl, bis (4-bromomethylphenyl) ) Methane, 4,4′-bis (bromomethyl) diphenyl ether, 1,5-bis (bromomethyl) ) Naphthalene, 2,6-bis (bromomethyl) naphthalene, 2,4,6,8-tetrakis (bromomethyl) naphthalene, 2,6-bis (bromomethyl) anthracene, 9,10-bis (bromomethyl) anthracene, 1, Bromine compounds such as 4,5,8-tetrakis (bromomethyl) anthracene and the like can be mentioned. Examples of the organic halogen compound in the present invention include the above iodine compounds . These organic halogen compounds may be used alone or in combination of two or more. Among these organohalogen compounds, it contains two iodine atoms per molecule in terms of high reactivity and a linear polymer having (meth) acryloyl groups at both ends. An iodine-containing compound having a structure in which an atom is bonded to a carbon atom bonded to an aromatic ring is preferable.

  In the polymerization step, the above organic halogen compound can be used as it is as an initiator. In addition, one or more compounds (hereinafter referred to as “initiator precursor”) that form the above-described organic halogen compound can also be used. Here, the initiator precursor is a material that can form the initiator before or during the reaction when the initiator precursor is present in the reaction system. That is, the initiator precursor does not correspond to the initiator in a state before being charged into the reaction vessel (polymerization of the first polymer), but in the reaction vessel (during polymerization), a chemical change (chemical reaction) Thus, the initiator can be formed. Even when this initiator precursor is used, the first polymer can be formed efficiently.

The initiator precursor is not particularly limited as long as it forms the organic halogen compound described above. For example, an initiator precursor composed of an organic compound such as an azo compound that is a radical polymerization initiator (hereinafter referred to as “initiator precursor (a)”) and an initiator precursor composed of a single halogen (hereinafter referred to as “start”). Agent precursor (b) "). Specifically, as shown in the following formula (13), as the initiator precursor (a), 4,4-azobis-4-cyanovaleric acid (13a) as an azo compound, and an initiator precursor (b) ) To form an initiator (13c) from an initiator precursor of iodine (13b). This initiator (13c) is a monofunctional initiator included in the general formula (12).

A radical polymerization initiator can be used as the initiator precursor (a). Examples of the radical polymerization initiator include azo compounds and organic peroxides. These can be used alone or in combination of two or more.
Examples of the azo compound include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis ( 2,4-dimethylvaleronitrile), 2,2'-azobis (isobutyronitrile), 2,2'-azobis-2-methylbutyronitrile, 1,1-azobis (1-cyclohexanecarbonitrile), 2 2,2'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (methylisobutyrate), and the like.
Examples of the organic peroxide include benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, t-butylperoxyisopropyl monocarbonate, and di (4-t-butylcyclohexyl). ) Peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, and dicumyl peroxide.

Moreover, the radical polymerization initiator which has the said functional group can be used as an initiator precursor (a). By using the radical polymerization initiator having the functional group as an initiator precursor (a) in the polymerization step, the above-mentioned vinyl polymer (A2) can be obtained as the first polymer. Examples of the compound having the functional group include an azo compound having the functional group and an organic peroxide having the functional group. Specific examples of the azo compound having the functional group include 4,4-azobis-4-cyanovaleric acid, 2,2′-azobis- {2-methyl-N- [1,1-bis (hydroxy). Methyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N- [2- (1-hydroxybutyl)] propionamide}, and the like. These can be used alone or in combination of two or more.
Specific examples of the organic peroxide having the above functional group include Disuccinic acid peroxide (Perroyl SA, manufactured by NOF Corporation). These can be used alone or in combination of two or more.

Examples of the initiator precursor (b) include simple substances of fluorine, chlorine, bromine and iodine . In the present invention, they are simple substances of iodine .

The vinyl monomer forming the vinyl polymer (A) is not particularly limited as long as it is a vinyl unsaturated compound having radical polymerizability. As a vinyl type unsaturated compound, the vinyl type unsaturated compound which has the said functional group can be used. A vinyl polymer (A1) having the functional group is obtained by radical polymerization of the monomer composition containing the vinyl unsaturated compound having the functional group in a polymerization step. Examples of the vinyl unsaturated compound having the functional group include an epoxy group-containing unsaturated compound, an unsaturated carboxylic acid compound, and a hydroxyl group-containing unsaturated compound. These compounds can be used alone or in combination of two or more.
Moreover, the vinyl type unsaturated compound which does not have the said functional group can also be used. Examples of the vinyl unsaturated compound having no functional group include (meth) acrylic compounds, aromatic vinyl compounds, conjugated diene compounds, maleimide compounds, vinyl esters, which are unsaturated compounds having a (meth) acryloyl group. Compound, vinyl ether compound, alkene compound, unsaturated acid anhydride, monoalkyl ester of unsaturated dicarboxylic acid, dialkyl ester of unsaturated dicarboxylic acid and the like. These compounds can be used alone or in combination of two or more.
The (meth) acrylic compound includes (meth) acrylic acid ester compounds, amino group-containing unsaturated compounds, amide group-containing unsaturated compounds, alkoxyl group-containing unsaturated compounds, cyano group-containing unsaturated compounds, and nitrile groups. Examples thereof include unsaturated compounds. Although a compound is illustrated below, the unsaturated compound which does not have a (meth) acryloyl group is also included.

上記一般式（１４）において、Ｒ^５１は水素原子又はメチル基であり、Ｒ^５２はあってもなくてもよく、Ｒ^５２を有する場合は、Ｒ^５２は−Ｃ（Ｏ）−Ｏ−、−ＯＣ（Ｏ）−、−ＮＨ−又は−Ｃ_６Ｈ_４−であり、Ｒ^５３は−Ｒ^５４−Ｏ−（Ｒ^５４は炭素数２〜４のアルキレン基）、−Ｒ^５５−Ｃ（Ｏ）−Ｏ−（Ｒ^５５は炭素数１〜８のアルキレン基）、−Ｒ^５６−Ｏ−Ｃ（Ｏ）−Ｒ^５７−（Ｒ^５６は炭素数１〜８のアルキレン基、Ｒ^５７は炭素数１〜８のアルキレン基）、−Ｃ_６Ｈ_４−又は−ＣＨ_２＝ＣＨ_２−であり、ｎは０〜４である。 The epoxy group-containing unsaturated compound is represented by the following general formula (14). Specific examples include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl methacrylate.

In the general formula ^{(14), R 51} is a hydrogen atom or a methyl ^group, may or may not be ^{R 52} is ^a, if having a ^{R 52 are, R 52} is -C (O) -O -, - OC (O) —, —NH—, or —C ₆ H ₄ —, wherein R ⁵³ is —R ⁵⁴ —O— (R ⁵⁴ is an alkylene group having 2 to 4 carbon atoms), —R ⁵⁵ —C (O). —O— (R ⁵⁵ is an alkylene group having 1 to 8 carbon atoms), —R ⁵⁶ —O—C (O) —R ⁵⁷ — (R ⁵⁶ is an alkylene group having 1 to 8 carbon atoms, R ⁵⁷ is 1 carbon atom) 8 alkylene group), _- C 6 _{H 4 -} or _{-CH 2} = CH 2 - a and, n represents 0-4.

上記一般式（１５）において、Ｒ^５８は水素原子又はメチル基であり、Ｒ^５９はあってもなくてもよく、Ｒ^５９を有する場合は、Ｒ^５９は−Ｃ（Ｏ）−Ｏ−、−ＯＣ（Ｏ）−、−ＮＨ−又は−Ｃ_６Ｈ_４−であり、Ｒ^６０は−Ｒ^６１−Ｏ−（Ｒ^６１は炭素数２〜４のアルキレン基）、−Ｒ^６２−Ｃ（Ｏ）−Ｏ−（Ｒ^６２は炭素数１〜８のアルキレン基）、−Ｒ^６３−Ｏ−Ｃ（Ｏ）−Ｒ^６４−（Ｒ^６３は炭素数１〜８のアルキレン基、Ｒ^６４は炭素数１〜８のアルキレン基）、−Ｃ_６Ｈ_４−又は−ＣＨ_２＝ＣＨ_２−であり、ｎは０〜４である。 The unsaturated carboxylic acid compound is represented by the following general formula (15). Specific examples include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, and 4-carboxylstyrene.

In the general formula ^{(15), R 58} is a hydrogen atom or a methyl ^group, may or may not be ^{and R 59 a,} when having ^{and R 59, and R 59} -C (O) -O -, - OC (O) —, —NH— or —C ₆ H ₄ —, wherein R ⁶⁰ is —R ⁶¹ —O— (R ⁶¹ is an alkylene group having 2 to 4 carbon atoms), —R ⁶² —C (O). —O— (R ⁶² is an alkylene group having 1 to 8 carbon atoms), —R ⁶³ —O—C (O) —R ⁶⁴ — (R ⁶³ is an alkylene group having 1 to 8 carbon atoms, R ⁶⁴ is 1 carbon atom) 8 alkylene group), _- C 6 _{H 4 -} or _{-CH 2} = CH 2 - a and, n represents 0-4.

上記一般式（１６）において、Ｒ^６６は水素原子又はメチル基であり、Ｒ^６７はあってもなくてもよく、Ｒ^６７を有する場合は、Ｒ^６７は−Ｃ（Ｏ）−Ｏ−、−ＯＣ（Ｏ）−、−ＮＨ−又は−Ｃ_６Ｈ_４−であり、Ｒ^６８は−Ｒ^６９−Ｏ−（Ｒ^６９は炭素数２〜４のアルキレン基）、−Ｒ^７０−Ｃ（Ｏ）−Ｏ−（Ｒ^７０は炭素数１〜８のアルキレン基）、−Ｒ^７１−Ｏ−Ｃ（Ｏ）−Ｒ^７２−（Ｒ^７１は炭素数１〜８のアルキレン基、Ｒ^７２は炭素数１〜８のアルキレン基）、−Ｃ_６Ｈ_４−又は−ＣＨ_２＝ＣＨ_２−であり、ｎは０〜４である。 The hydroxyl group-containing unsaturated compound is represented by the following general formula (16). Specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate And hydroxyalkyl (meth) acrylates such as pentaerythritol tri, di or mono (meth) acrylate and trimethylolpropane di or mono (meth) acrylate.

In the general formula ^{(16), R 66} is a hydrogen atom or a methyl ^group, may or may not be ^{R 67} is ^a, if having ^{R 67 is, R 67} is -C (O) -O -, - OC (O) —, —NH—, or —C ₆ H ₄ —, R ⁶⁸ is —R ⁶⁹ —O— (R ⁶⁹ is an alkylene group having 2 to 4 carbon atoms), —R ⁷⁰ —C (O) -O- ^{(R 70} represents an alkylene group having 1 to 8 carbon ^{atoms), - R 71 -O-C} (O) -R 72 - (R 71 represents an alkylene group having 1 to 8 carbon ^{atoms, R 72} is C 1 -C 8 alkylene group), _- C 6 _{H 4 -} or _{-CH 2} = CH 2 - a and, n represents 0-4.

  Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, (Meth) acrylic acid 2-methylpentyl, (meth) acrylic acid n-octyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid n-decyl, (meth) acrylic acid n-dodecyl, (meth) acrylic N-octadecyl acid, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) Phenyl acrylic acid, (meth) toluyl acrylate include benzyl (meth) acrylate and the like. These compounds can be used alone or in combination of two or more.

  Examples of the amino group-containing unsaturated compound include dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, (meth ) 2- (di-n-propylamino) ethyl acrylate, 2-dimethylaminopropyl (meth) acrylate, 2-diethylaminopropyl (meth) acrylate, 2- (di-n-propylamino) (meth) acrylate ) Propyl, (meth) acrylic acid 3-dimethylaminopropyl, (meth) acrylic acid 3-diethylaminopropyl, (meth) acrylic acid 3- (di-n-propylamino) propyl, and the like. These may be used alone or in combination of two or more.

  Examples of the amide group-containing unsaturated compound include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-methylol (meth) acrylamide and the like. These may be used alone or in combination of two or more.

  Examples of the alkoxyl group-containing unsaturated compound include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n-propoxy) ethyl (meth) acrylate, (meth) acrylic acid 2 -(N-butoxy) ethyl, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 2- (n-propoxy) propyl (meth) acrylate, 2- (meth) acrylic acid 2- ( n-butoxy) propyl and the like. These may be used alone or in combination of two or more.

  Examples of the cyano group-containing unsaturated compound include cyanomethyl (meth) acrylate, 1-cyanoethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, 1-cyanopropyl (meth) acrylate, and (meth) acrylic acid. 2-cyanopropyl, 3-cyanopropyl (meth) acrylate, 4-cyanobutyl (meth) acrylate, 6-cyanohexyl (meth) acrylate, 2-ethyl-6-cyanohexyl (meth) acrylate, (meth ) Acrylic acid 8-cyanooctyl and the like. These may be used alone or in combination of two or more.

  Examples of the nitrile group-containing unsaturated compound include (meth) acrylonitrile, ethacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile and the like. These compounds can be used alone or in combination of two or more.

  Examples of the aromatic vinyl compound include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, and 4-tert-butylstyrene. Tert-butoxystyrene, vinyltoluene, vinylnaphthalene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene, fluorostyrene, styrenesulfonic acid and its salt, α-methylstyrenesulfonic acid and its salt, etc. Can be mentioned. These compounds may be used alone or in combination of two or more.

  Examples of the conjugated diene compound include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3 butadiene, and chloroprene (2-chloro-1,3-butadiene). Etc.

  Examples of the maleimide compound include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methyl). Phenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) ) Maleimide, N-naphthylmaleimide, N-cyclohexylmaleimide and the like. These compounds can be used alone or in combination of two or more.

  Examples of the vinyl ester compound include methylene aliphatic monocarboxylic acid ester, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl butyrate, vinyl benzoate, vinyl formate, and vinyl cinnamate. These compounds can be used alone or in combination of two or more.

  Examples of the vinyl ether compound include vinyl methyl ether, vinyl ethyl ether, vinyl n-butyl ether, vinyl isobutyl ether, vinyl phenyl ether, vinyl cyclohexyl ether and the like. These may be used alone or in combination of two or more.

Examples of the alkene compound include ethylene, propylene, butene, pentene, hexene and the like. These may be used alone or in combination of two or more.
Examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These compounds can be used alone or in combination of two or more.
Examples of monoalkyl esters of unsaturated dicarboxylic acids include monoalkyl esters such as maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride, itaconic anhydride, and citraconic anhydride. These compounds can be used alone or in combination of two or more.
Examples of the dialkyl ester of unsaturated dicarboxylic acid include dialkyl esters such as maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride, itaconic anhydride, and citraconic anhydride. These compounds can be used alone or in combination of two or more.
Examples of other vinyl monomers include vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. These compounds can be used alone or in combination of two or more.

  The ratio of the amount of the vinyl monomer having the functional group and the other monomer used to form the vinyl polymer (A1) is the total amount of monomers forming the vinyl polymer (A1). When it is 100 mass%, 0.5-15 mass% and 85-99.5 mass% are respectively preferable, 1-10 mass% and 90-99 mass% are more preferable, 2-8 mass% and 92- 98 mass% is still more preferable. When the use ratio of the vinyl monomer having the functional group and the other monomer is within the above range, a thermosetting composition for coating is obtained which can obtain a cured product having excellent strength, elasticity and durability. be able to.

The other monomer is preferably an aromatic vinyl compound (more preferably styrene) and a (meth) acrylic compound (more preferably a (meth) acrylic acid ester compound, particularly preferably styrene, Methyl (meth) acrylate, ethyl (meth) acrylate and n-butyl (meth) acrylate).
As a use ratio of the aromatic vinyl compound and the (meth) acrylic compound, when the total amount of the vinyl monomer forming the first polymer is 100% by mass, the aromatic vinyl compound and the (meth) acrylic compound are used. The total amount of the compounds is preferably 40 to 100% by mass, more preferably 60% by mass or more, and still more preferably 80% by mass or more.
Moreover, the ratio of the usage-amount of an aromatic vinyl compound and a (meth) acrylic-type compound is 0-50 mass% and 50, respectively, when the sum total of an aromatic vinyl compound and a (meth) acrylic-type compound is 100 mass%. -100 mass% is preferable, 0-30 mass% and 70-100 mass% are more preferable, 0-10 mass% and 90-100 mass% are still more preferable. When the ratio of the compound used is within the above range, a cured product having excellent strength and elasticity can be provided.

Moreover, when it is set as the 1st polymer which does not have the said functional group, the preferable usage example of a vinyl-type monomer is shown below.
The vinyl monomer is preferably an aromatic vinyl compound (more preferably styrene) and a (meth) acrylic compound (more preferably a (meth) acrylic acid ester compound, particularly preferably styrene, ( (Meth) methyl acrylate, ethyl (meth) acrylate and n-butyl (meth) acrylate).
As a use ratio of the aromatic vinyl compound and the (meth) acrylic compound, when the total amount of the vinyl monomer forming the first polymer is 100% by mass, the aromatic vinyl compound and the (meth) acrylic compound are used. The total amount of the compounds is preferably 40 to 100% by mass, more preferably 60% by mass or more, and still more preferably 80% by mass or more.
Moreover, the ratio of the usage-amount of an aromatic vinyl compound and a (meth) acrylic-type compound is 0-50 mass% and 50, respectively, when the sum total of an aromatic vinyl compound and a (meth) acrylic-type compound is 100 mass%. -100 mass% is preferable, 0-30 mass% and 70-100 mass% are more preferable, 0-10 mass% and 90-100 mass% are still more preferable. When the ratio of the compound used is within the above range, a cured product having excellent strength and elasticity can be provided.

  In the polymerization step, a halogen atom derived from an initiator (or initiator precursor) is terminated (having a terminal halogen) by radical polymerization from a vinyl monomer in the presence of an initiator or an initiator precursor. A first polymer is obtained. In the polymerization step, a radical generator can be further used as necessary.

  In the polymerization step, when the initiator and initiator precursor used are a bifunctional initiator or an initiator precursor that forms a bifunctional initiator, the resulting first polymer has halogen atoms at both ends. Have On the other hand, when the initiator and initiator precursor used are monofunctional initiators or initiator precursors that form monofunctional initiators, the resulting first polymer has a halogen atom only at one end. Have.

  The amount of the initiator used is preferably 0.01 to 10 mol, more preferably 0.05 to 5 mol, and still more preferably 0.1 to 3 mol, with respect to 100 mol of the total amount of vinyl monomers. . When the usage-amount of an initiator exists in the said range, a 1st polymer with small dispersion degree is obtained efficiently.

  Moreover, the usage-amount in the case of using an initiator precursor as an initiator is as follows. The used amount of the initiator precursor (a) composed of an organic compound is preferably 0.01 to 10 mol, more preferably 0.05 to 5 mol, still more preferably with respect to 100 mol of the total amount of vinyl monomers. 0.1 to 3 mol. Moreover, the usage-amount of the initiator precursor (b) which consists of a halogen simple substance becomes like this with respect to 100 mol of vinyl monomers whole quantity, Preferably it is 0.01-10 mol, More preferably, it is 0.05-5 mol, Furthermore, Preferably it is 0.1-3 mol. When the usage-amount of an initiator precursor exists in the said range, a 1st polymer with a small dispersion degree is obtained efficiently.

  In the polymerization step, a polymerization catalyst can also be used. Examples of the polymerization catalyst include group 14-16 metal compounds. By using a group 14-16 metal compound, radical dissociation of carbon-halogen is more likely to occur and the polymerization rate is increased, so that the polymerization time is shortened and the degree of polymerization is improved. Moreover, since the metal compound of 14-16 group can act also as a catalyst at the time of substituting the halogen atom of the polymerization terminal mentioned later to a (meth) acryloyl group, in the case of substitution to a (meth) acryloyl group. Therefore, it is not necessary to add a new catalyst.

  Examples of the group 14-16 metal compound include compounds such as tin, lead, antimony, bismuth, tellurium and polonium. Specifically, tin fluoride, tin chloride, tin bromide, tin iodide, tin oxide, bis (2-ethylhexanoate) tin, bis (neodecanoate) tin, n-butyltris (2-ethylhexanoate) ) Tin, tin acetate, di-n-butylbis (dodecylthio) tin, di-n-butylbis (2-ethylhexanoate) tin, di-n-butyldiacetoxytin, di-t-butyldiacetoxytin, di -N-butylmethoxytin, di-n-butyl-S, S'-bis (isooctylmercaptoacetate) tin, dimethyldineodecanoate tin, dioctyldilauratetin, dioctyldinedecanoatetin, tetra -T-butoxy tin, tetra-n-butyl tin, tetraethyl tin, tetraisopropyl tin, tetra-n-octyl tin, tetra-n-pentyl tin, tetraphenyl tin, tetra- -Tin compounds such as tolyltin, tri-n-butylethoxytin, tri-n-butylmethoxytin, tri-n-butylmethyltin, tri-n-butyltin; lead fluoride, lead chloride, lead bromide, iodine Lead compounds such as lead fluoride, lead tetraacetate, bis (2-ethylhexanoate) lead, bis (2,4-pentaneionate) lead, tetraphenyllead; tellurium compounds such as tellurium ethoxide; bismuth chloride, tris Examples thereof include bismuth compounds such as (tetramethylheptanedionate) bismuth, tris (t-pentoxide) bismuth, tris (2-ethylhexanoate) bismuth, and the like. These 14-14 group metal compounds may be used alone or in combination of two or more.

  Although the addition amount of the said 14-16 group metal compound is based also on the kind of metal compound, it is preferable that it is 0.001-10 mol with respect to 1 mol of organic halogen compounds. If the amount of the 14-14 group metal compound added is less than 0.001 mol per 1 mol of the organic halogen compound, a sufficient catalytic effect may not be obtained. If it exceeds 10 mol, it may be difficult to remove the metal compound during purification. More preferably, it is 0.05-1 mol with respect to 1 mol of halogen compounds.

  Furthermore, in the polymerization step, a necessary amount of radical reaction initiator (radical polymerization initiator) can be used as necessary. This radical reaction initiator is the same as the initiator precursor (a) described above. As specific compounds, the compounds mentioned as the initiator precursor (a) can be applied as they are.

When using a radical reaction initiator, the amount of the radical reaction initiator used is preferably 0.01 to 10 mol, more preferably 0.05 to 5 mol, relative to 100 mol of the total amount of vinyl monomers. More preferably, it is 0.1-3 mol.
In addition, the usage-amount of the said radical reaction initiator includes the usage-amount of an initiator precursor (a), when using the said radical initiator as an initiator precursor (a). When the amount of the radical generator used is within the above range, a first polymer having a low degree of dispersion can be obtained efficiently.

  In the polymerization step, the radical polymerization can be performed by any process such as a batch process, a semi-batch process, a tubular continuous polymerization process, and a continuous stirred tank process (CSTR). Among these polymerization processes, a batch process, a semi-batch process and a tubular continuous polymerization process are preferable, and a batch process is more preferable. The polymerization format may be bulk polymerization without using a solvent or solution polymerization using a polymerization solvent.

When the polymerization is based on solution polymerization using a polymerization solvent, the polymerization solvent is preferably a hydrocarbon compound. Specifically, cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, and orthoformate Examples thereof include alcohols such as methyl, methyl orthoacetate, methanol, ethanol and isopropanol. These can be used alone or in combination of two or more.
The amount of the polymerization solvent used is preferably 0 to 200 parts by mass, more preferably 0 to 100 parts by mass, and still more preferably 0 to 50 parts by mass with respect to 100 parts by mass of the total amount of vinyl monomers. It is. When the polymerization solvent exceeds 200 parts by mass, a chain transfer reaction due to the polymerization solvent occurs, and it may be difficult to control polymerization such as molecular weight control and molecular weight distribution (dispersion degree) control.

  The polymerization temperature in the polymerization step is preferably 30 ° C to 130 ° C, more preferably 40 ° C to 110 ° C, and still more preferably 50 ° C to 110 ° C. When the polymerization temperature is less than 30 ° C, the polymerization rate may be remarkably slowed. On the other hand, if the polymerization temperature is higher than 110 ° C., the heating equipment may be costly.

  The number average molecular weight (Mn) of the first polymer is preferably 3000 to 50000, more preferably 6000 to 25000, and still more preferably 8000 to 15000 in terms of polystyrene by gel permeation chromatography (GPC). When the number average molecular weight is in the above range, a thermosetting composition for coatings that gives a cured product having excellent strength and elasticity can be obtained.

  The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the first polymer is less than 2.0 (usually 1.05 or more), preferably 1.3 to 1. .8, more preferably less than 1.6. If ratio (Mw / Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn) is the said range, it can be set as the thermosetting composition for coatings which gives the hardened | cured material excellent in intensity | strength and elasticity. .

  The first polymer includes a halogen atom derived from the catalyst or the organic halogen compound at a molecular end. The molecular terminal provided with the halogen atom may be at least one of the first polymer, and it is more preferable that the halogen atom is provided at both terminals of the first polymer.

Next, the second step will be described. In this second step, the halogen atom (terminal halogen) at the molecular terminal of the first polymer is modified by terminal modification described later to modify the terminal halogen, and the vinyl polymer (A) having the functional group at the molecular terminal It is a process to do.
The vinyl polymers (A1) and (A2) also have a halogen atom (terminal halogen) at the molecular end. Accordingly, the vinyl polymers (A1) and (A2) can also be made into a vinyl polymer having the functional group at the molecular end by subjecting them to the second step below.

Examples of the modification method of the first polymer in the second step include a method in which a terminal halogen atom is modified with a compound having a functional group (molecular terminal modifier) using a general chemical reaction. In this step, for example, the following modes (methods) are mentioned.
(1) Introduction of a hydroxyl group or the like using a hydroxide compound such as sodium hydroxide by direct substitution of terminal halogen substitution.
(2) Introduction of a carboxyl group, a hydroxyl group, an amino group, and an isocyanate group using an amine compound such as aminoethanol, glycine, ethylenediamine, and cadaverine by a halogen-amino substitution reaction.
(3) Introduction of carboxyl group, hydroxyl group, isocyanate group, amine group, etc. using mercapto compounds such as mercaptoethanol, mercaptopropionic acid, mercaptoisocyanate and mercaptoamine by halogen-mercapto substitution reaction. Introduction of a carboxyl group or the like by hydrolysis after substitution with sulfonic acid.
(5) Introduction of a carboxyl group or the like using succinic acid monosodium salt or the like by halogen-carboxylate substitution reaction.
(6) The functional group in the case where the first polymer has a functional group, and the functional group introduced by the above (1) to (5) and an epoxy group, a carboxyl group, and a hydroxyl group using a general chemical reaction. Introduction.

In the method (1), the first polymer and the hydroxide are reacted. A vinyl-based heavy atom in which a hydroxyl group derived from a hydroxide is arranged at the elimination site of the terminal halogen atom in the first polymer by a substitution reaction between the halogen atom at the molecular end of the first polymer and a hydroxide. Coalescence is obtained.
Examples of the hydroxide include potassium hydroxide and sodium hydroxide.
The reaction may be performed in a solvent, and in that case, the solvent to be used is not particularly limited. Solvents include cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, and methyl orthoformate. And alcohols such as methyl orthoacetate, methanol, ethanol and isopropanol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric triamide, acetonitrile and the like.
In addition, the reaction temperature in this reaction is usually preferably 0 ° C to 80 ° C, more preferably 25 ° C to 70 ° C.

In the method (2), the first polymer is reacted with an amine compound. A vinyl system in which a functional group derived from an amine compound is arranged at a terminal halogen atom elimination site in the first polymer by a halogen-amino substitution reaction between the halogen atom at the molecular end of the first polymer and the amine compound. A polymer is obtained.
Examples of the amine compound include aminoethanol, glycine, (aminoisocyanate), ethylenediamine, and cadaverine.
The reaction may be performed in a solvent, and in that case, the solvent to be used is not particularly limited. Solvents include cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, and methyl orthoformate. And alcohols such as methyl orthoacetate, methanol, ethanol and isopropanol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric triamide, acetonitrile and the like.
In addition, the reaction temperature in this reaction is usually preferably 0 ° C to 80 ° C, more preferably 25 ° C to 70 ° C.

In the method (3), the first polymer and the mercapto compound are reacted. A vinyl group in which a functional group derived from a mercapto compound is arranged at the elimination portion of the terminal halogen atom in the first polymer by a halogen-mercapto substitution reaction between the halogen atom at the molecular end of the first polymer and a mercapto compound. A polymer is obtained.
Examples of the mercapto compound include mercaptoethanol, mercaptopropionic acid, mercaptoisocyanate, and mercaptoamine.
The reaction may be performed in a solvent, and in that case, the solvent to be used is not particularly limited. Solvents include cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, and methyl orthoformate. And alcohols such as methyl orthoacetate, methanol, ethanol and isopropanol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric triamide, acetonitrile and the like.
Moreover, although reaction temperature in this reaction is not limited, 0 to 80 degreeC is preferable normally and 25 to 70 degreeC is more preferable.

In the method (4), the first polymer and chlorosulfonic acid are reacted and further hydrolyzed. A vinyl polymer in which a carboxyl group is arranged at the terminal halogen atom elimination site in the first polymer by hydrolysis after the substitution reaction between the halogen atom at the molecular end of the first polymer and chlorosulfonic acid. As a substitution reaction with chlorosulfonic acid, the solvent to be used is not particularly limited. Solvents include cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, and methyl orthoformate. And alcohols such as methyl orthoacetate, methanol, ethanol and isopropanol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric triamide, acetonitrile and the like.
Moreover, although reaction temperature in this reaction is not limited, 0 to 80 degreeC is preferable normally and 25 to 70 degreeC is more preferable.
In the hydrolysis reaction, the solvent used is not particularly limited. Solvents include cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, and methyl orthoformate. And alcohols such as methyl orthoacetate, methanol, ethanol and isopropanol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric triamide, acetonitrile and the like.
Moreover, although reaction temperature in this reaction is not limited, 0 to 80 degreeC is preferable normally and 25 to 70 degreeC is more preferable.

In the method (5), the first polymer and the carboxylic acid compound are reacted. By the halogen-carboxylate substitution reaction between the halogen atom at the molecular end of the first polymer and the carboxylic acid compound, the carboxyl group derived from the carboxylic acid compound is arranged at the elimination site of the terminal halogen atom in the first polymer. The obtained vinyl polymer is obtained.
Examples of the carboxylic acid compound include succinic acid monosodium salt.
The reaction may be performed in a solvent, and in that case, the solvent to be used is not particularly limited. The solvent is preferably a polar solvent, and examples thereof include tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric triamide, and acetonitrile.
Moreover, although reaction temperature in this reaction is not limited, Usually, 0-80 degreeC is preferable and 25 degreeC-70 degreeC is more preferable.

  In the method of (6) above, an epoxy group is obtained by reacting the resulting vinyl polymer having an epoxy group, carboxyl group, hydroxyl group, amine group or isocyanate group with a compound having an epoxy group, carboxyl group or hydroxyl group. , A vinyl polymer having at least one of a carboxyl group and a hydroxyl group per molecule is obtained. These reactions can utilize general chemical reactions, and the compound having an epoxy group, a carboxyl group, or a hydroxyl group to be used is not limited.

In the present invention, as a method for producing the vinyl polymer having the functional group, in addition to the first step and the second step, a desolvation step (third step) for removing residual volatiles after these steps. ).
Although it does not specifically limit as this demelting process, The demelting method (demelting process) generally performed can be used. For example, the method of using a falling evaporator, a thin film evaporator, an extruder dryer, etc. is mentioned.
The temperature condition for desorption is preferably 250 ° C. or lower (usually 10 ° C. or higher), more preferably 170 ° C. or lower, and still more preferably 100 ° C. or lower. If it is 250 degrees C or less, the said functional group which a vinyl type polymer does not dissociate from a vinyl type polymer, and decomposition | disassembly of a vinyl type polymer does not arise easily. On the other hand, when it exceeds 250 ° C., the functional group of the vinyl polymer may be dissociated, and the vinyl polymer may be partially decomposed to generate a low molecular weight product. Coloring may also occur.

If the number of the said functional groups which the vinyl polymer (A) of this invention has is one or more, it will not specifically limit. The number of functional groups possessed by the vinyl polymer (A) can be the average number (number f) of functional groups calculated by the following formula. The average number (number f) of functional groups of the vinyl polymer (A) is 1 . 0 to 6.5, preferably from 1.4 to 7.0, more preferably from 1.8 to 5.0.
Average number (number f) = concentration of the functional group in the vinyl polymer [mol / kg] / (1000 / number average molecular weight)
If the average number (number f) is less than 1.0, the crosslink density of the cured product (film) obtained from the thermosetting composition for paints is reduced, and the rupture strength of the cured product may be weakened. . On the other hand, when it is larger than 10.0, the crosslink density becomes high, and a cured product such as a coating film that is brittle and does not stretch may be obtained.

The number average molecular weight of the vinyl polymer (A) is 1000 to 10000 in terms of polystyrene by gel permeation chromatography (GPC), preferably 2000 to 8000 , and more preferably 3000 to 7000. When Mn is less than 1000, the coating film properties may be deteriorated. On the other hand, when Mn exceeds 10,000, melt viscosity becomes very high, and the smoothness and workability of the coating film may deteriorate.

  The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the vinyl polymer (A) is less than 2.0 (usually 1.05 or more), preferably 1. It is 3-1.8, More preferably, it is less than 1.6. If the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is in the above range, the viscosity when used as a thermosetting composition for a coating film is kept low and handling is facilitated. In addition, sufficient film properties can be obtained.

  The glass transition temperature of the vinyl polymer is preferably 10 to 100 ° C, more preferably 20 to 70 ° C. Storage stability may fall that a glass transition temperature is less than 10 degreeC. Moreover, when it exceeds 100 degreeC, melt viscosity will become low too much and a coating-film external appearance may worsen.

The said hardening | curing agent (B) is a compound which reacts with the said functional group which the said vinyl polymer (A) has, and has the effect | action which hardens the thermosetting composition for coating materials of this invention.
As the curing agent (B), a compound having two or more functional groups capable of reacting with the functional group of the vinyl polymer (A) can be used as the curing agent. As this hardening | curing agent (B), the polyvalent carboxylic acid compound, polyvalent glycidyl compound, polyvalent isocyanate compound etc. which have a 2 or more carboxyl group, an epoxy group, and an isocyanate group in 1 molecule are mentioned, for example. These curing agents may be used alone or in combination of two or more.
By using these curing agents, the curable composition can be uniformly cured. Moreover, when preparing hardened | cured material using these hardening | curing agents, a suitable hardening catalyst can be used, respectively.

  Examples of the polyvalent carboxylic acid compound include glutamic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,12-dodecanoic acid, 1,20-icosane diacid, and 1,24-tetraicosane 2 Acid, maleic acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, cyclohexene 1,2-dicarboxylic acid, aliphatic dibasic carboxylic acid linear linear acid anhydride, succinic anhydride , Dibasic carboxylic acid anhydrides such as sebacic anhydride, phthalic anhydride, itaconic anhydride, 1,3,5-tris (2-carboxyethyl) -isocyanurate, and the like.

  Examples of the polyvalent glycidyl compound include polyepoxides such as triglycidyl isocyanate, β-hydroxyalkylamides such as (bis (N, N ′)-dihydroxy) azibamide, and the like.

  Examples of the polyvalent isocyanate compound include toluene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methyl 2,4- Cyclohexane diisocyanate, methyl 2,6-cyclohexane diisocyanate, diphenylmethane diisocyanate, 1,4-bis (isocyanatemethyl) cyclohexane, 1,3-bis (isocyanatemethyl) cyclohexane, carbodiimide modified 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, xylene Diisocyanate, hydrogenated xylene diisocyanate, p-phenylene diisocyanate Diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, adducts of these polyisocyanate compounds and polyol compounds such as trimethylolpropane, these poly Examples thereof include burettes and isocyanurates of isocyanate compounds. Moreover, the terminal isocyanate product of polyalkylene ether, the terminal isocyanate product of polyester, the terminal isocyanate product of polycarbonate, block isocyanates, such as the epsilon caprolactam block body of isophorone diisocyanate, polyalkoxy compounds, such as tetramethoxymethylglycolyl, etc. are mentioned.

The amount of the curing agent (B), which is a polyvalent compound, is such that the molar ratio of the polyvalent functional group to the epoxy group, carboxyl group, and hydroxyl group in the vinyl polymer is in the range of 0.5 to 2.0 . The range is preferably 0.8 to 1.2. More preferably, it is the range of 0.9-1.1. When this molar ratio is less than 0.5, it may be uncured, and even when it exceeds 2.0, it may be uncured.

  In addition to the vinyl polymer (A) and the curing agent (B), the thermosetting composition for coatings according to the present invention may further include an epoxy resin, a polyester resin, a polyamide resin and the like as long as the object of the present invention is achieved. As well as natural resin or semi-synthetic resin composition including fibrin or a fibrin derivative or the like. By containing these compositions, the coating film appearance or coating film properties of the coating film obtained can be improved.

  Furthermore, the thermosetting composition for coatings according to the present invention comprises a curing catalyst, a pigment, a flow modifier, a thixotropic agent (thixotropic modifier), an antistatic agent, a surface modifier, a gloss imparting agent, and an antiblocking agent. An additive such as an agent, a plasticizer, an ultraviolet absorber, a wax inhibitor, a slip agent, and an antioxidant can also be contained.

  Any known method may be employed to adjust the thermosetting composition for paint. Examples of the adjustment method include a method in which the components are mixed and then melt-mixed by a melt kneader such as a heating roll or an excluder, or cooled and pulverized to obtain a powder coating material.

  The thermosetting composition for paints of the present invention can be used for high solid paints or powder paints.

  In the case of a powder coating material, the coating method is not particularly limited, but may be a well-known coating method such as electrostatic spraying or fluidized immersion. By these coating methods, the object to be coated can be coated and usually baked in a baking furnace at 150 to 210 ° C. to obtain a coating film by powder coating.

Moreover, when using as a high solid coating material, when the coating-material whole quantity is 100 mass%, an organic solvent can be contained 0-50 mass%, More preferably, 35 mass% can be contained.
Examples of the organic solvent include ether compounds, ester compounds, ketone compounds, aromatic and aliphatic hydrocarbon compounds, alcohol compounds, glycol ether compounds, glycol ether ester compounds, and mixtures thereof.

In the case of a high solid paint, the coating method is not particularly limited, but a known coating method such as spray coating can be used. By these coating methods, the object to be coated is coated, air-dried at room temperature for about 5 to 20 minutes, or heat-dried so as to be dried to the same extent, and then the solvent is evaporated, followed by heat-curing.
The heat curing is preferably performed at a temperature of 120 to 160 ° C. for about 20 to 40 minutes.

  The thermosetting composition for coatings of the present invention may be cured by a method using light irradiation. By irradiating with light, the carbon-halogen bond is easily selectively dissociated by radicals, so that a side reaction in the radical polymerization to be cured hardly occurs.

  The light source used for the light irradiation is not particularly limited as long as a bond other than a carbon-halogen bond, for example, a carbon-carbon bond, a carbon-hydrogen bond, or the like of the main chain is not cleaved. You may select it in consideration. Examples of the light source include a high-pressure mercury lamp, a low-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon-mercury lamp, an emmashima laser, and a xenon lamp.

Although the irradiation intensity | strength of the said light source is determined in the range which does not have a bad influence on the synthesis | combination of a polymer, it is preferable that it is 0.01-10 J / cm < ² > (365 nm). When the irradiation intensity is less than 0.01 J / cm ² , the polymerization reaction may be slowed because it does not act effectively on the carbon-halogen bond. On the other hand, if it exceeds 10 J / cm ² , the reaction intensity cannot be controlled because the irradiation intensity is too strong.

Synthesis example experimental example of the present invention will now be described together with comparative examples, the scope of the present invention is not limited to experimental examples of these course. In the following, “part” is based on mass unless otherwise specified. Experimental examples 1, 2, 3, 5 and 7 are examples, and other experimental examples are reference examples.
Further, synthesis examples, "Mn" in the Experimental Examples and Comparative Examples means a number average molecular weight, "Mw" means weight average molecular weight, Mw / Mn means the degree of dispersion. “Mn” and “Mw” are values calculated in terms of standard polystyrene by gel permeation chromatography (GPC) measurement under the following conditions.
<GPC measurement conditions>
Apparatus: HLC-8120 (manufactured by Tosoh Corporation)
Column: 4 TSKgel SuperMultipore HZ-M (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran 0.35ml / min
Detector: RI

Further, synthesis example, the polymer in the experimental examples and comparative examples, an epoxy group, functional groups of the carboxyl and hydroxyl groups is the average number calculated by the following equation.
Number of functional groups (number f) = concentration of the functional groups in the vinyl polymer [mol / kg] / (1000 / number average molecular weight)
And the density | concentration of the said functional group in the said vinyl polymer was computed from the functionality of each functional group by the following measurement.
"Epoxy group functionality"
It measured based on ASTM (D1652-73 Standard Test Method for EPOXY COTENT OF EPOXY RESINS).
"Functionality of hydroxyl group"
It was measured by the neutralization titration method of JIS K 0070.
"Functionality of carboxyl group"
It was measured by the neutralization titration method of JIS K 0070.

Further, synthesis examples, the glass transition temperature of the polymer in the experimental examples and comparative examples (hereinafter, also referred to as "Tg") was measured from the temperature change of the specific volume by DSC (differential scanning calorimetry).

<Preparation of vinyl polymer (A) having at least one functional group selected from epoxy group, carboxyl group and hydroxyl group>
Synthesis Example 1 (Preparation of Polymer A)
In a 1-liter brown separable flask, 46 parts by mass of methyl acrylate (hereinafter also referred to as “MA”), 22.6 parts by mass of 1,4-diiodylene xylene, azobis-2,4-dimethylvaleronitrile (hereinafter, Also referred to as “V-65”.) A mixed liquid consisting of 3.1 parts by mass and 100 parts by mass of butyl acetate was charged, and the mixed liquid was sufficiently deaerated by nitrogen bubbling. The internal temperature was raised to 60 ° C. to initiate the polymerization reaction, and after 5 hours, 152 parts by mass of methyl methacrylate (hereinafter also referred to as “MMA”) and 40 parts by mass of glycidyl methacrylate (hereinafter also referred to as “GMA”). In addition, the mixture was further reacted for 3 hours, and the polymerization was stopped by adding 50 parts by mass of sodium hydroxide. At this time, the polymerization rates of MA, MMA, and GMA were 93%, 95%, and 98%, respectively. After cooling, the reaction solution was extracted while filtering and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 200 parts by mass of Polymer A. The properties of the obtained polymer A were Mw4790, Mn3300, Mw / Mn1.45, the glass transition temperature was 65 ° C., and the number of functional groups of the epoxy group was 6.0. Table 1 shows the Mw, Mn, Mw / Mn, Tg, functional group type, and functional group number of the polymer A. Moreover, Mw, Mn, Mw / Mn, Tg, functional group type and functional group number of the acrylic polymer (A) obtained for the following Synthesis Examples 2 to 11 are also shown in Table 1.

Synthesis Example 2 (Preparation of polymer B)
In a 1-liter brown separable flask, 121 parts by mass of styrene (hereinafter also referred to as “St”), 78 parts by mass of MMA, 30 parts by mass of butyl acrylate (hereinafter also referred to as “BA”), 77 parts by mass of GMA, 19.7 iodine A mixed solution consisting of 2 parts by mass, 29.9 parts by mass of azobis-2-methylbutyronitrile (hereinafter also referred to as “V-59”) and 150 parts by mass of butyl acetate was prepared, and the mixture was sufficiently deaerated by nitrogen bubbling. . The internal temperature was raised to 80 ° C. to start the polymerization reaction, and after 7 hours, 50 parts by mass of sodium hydroxide was added to stop the polymerization. At this time, the polymerization rates of St, MMA, BA, and GMA were 90%, 92%, 87%, and 97%, respectively. After cooling, while filtering, the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 250 parts by mass of Polymer B. The properties of the obtained polymer B were Mw4830, Mn3400, Mw / Mn1.42, the glass transition temperature was 64 ° C., and the number of functional groups of the epoxy group was 6.5.

Synthesis Example 3 (Preparation of polymer C)
A 1 liter brown separable flask is charged with a mixed solution comprising 189 parts by mass of styrene MMA, 27 parts by mass of BA, 75 parts by mass of GMA, 26.7 parts by mass of iodine, 40.4 parts by mass of “V-59”, and 150 parts by mass of butyl acetate. The mixture was thoroughly degassed with nitrogen bubbling. The internal temperature was raised to 80 ° C. to start the polymerization reaction, and after 7 hours, 50 parts by mass of sodium hydroxide was added to stop the polymerization. At this time, the polymerization rates of MMA, BA, and GMA were 92%, 85%, and 97%, respectively. After cooling, while filtering, the reaction solution was extracted and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 250 parts by mass of a polymer C. The properties of the obtained polymer C were Mw3900, Mn2600, Mw / Mn1.50, the glass transition temperature was 64 ° C., and the number of functional groups of the epoxy group was 5.0.

Synthesis Example 4 (Preparation of polymer D)
A 1 liter brown separable flask is charged with a mixed liquid consisting of 227 parts by mass of styrene MMA, 26 parts by mass of BA, 73 parts by mass of GMA, 10.5 parts by mass of iodine, 15.9 parts by mass of “V-59”, and 147 parts by mass of butyl acetate. The mixture was thoroughly degassed with nitrogen bubbling. The internal temperature was raised to 80 ° C. to start the polymerization reaction, and after 7 hours, 50 parts by mass of sodium hydroxide was added to stop the polymerization. At this time, the polymerization rates of MMA, BA, and GMA were 91%, 90%, and 98%, respectively. After cooling, while filtering, the reaction solution was extracted and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 250 parts by mass of a polymer D. The properties of the obtained polymer D were Mw10220, Mn7300, Mw / Mn1.40, the glass transition temperature was 67 ° C., and the number of functional groups of the epoxy group was 12.0.

Synthesis Example 5 (Preparation of polymer E)
A 1 liter brown separable flask was charged with a mixed liquid consisting of 47 parts by weight of MA, 21.9 parts by weight of 1,4-diiodoxylene, 3.0 parts by weight of “V-65”, and 100 parts by weight of butyl acetate. Was thoroughly degassed with nitrogen bubbling. The internal temperature was raised to 60 ° C. to initiate the polymerization reaction, and after 5 hours, 147 parts by mass of MMA and 44 parts by mass of hydroxyethyl methacrylate (hereinafter also referred to as “HEMA”) were added, and the reaction was further continued for 3 hours. Thereafter, 2.7 parts by mass of aminopropanol was added and further reacted for 3 hours. At this time, the polymerization rates of MA, MMA, and HEMA were 92%, 94%, and 98%, respectively. After cooling, the reaction solution was extracted and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 200 parts by mass of a polymer E. The properties of the obtained polymer E were Mw4730, Mn3400, Mw / Mn1.39, the glass transition temperature was 66 ° C., and the number of functional groups of the hydroxyl group was 7.0.

Synthesis Example 6 (Preparation of polymer F)
A 1 liter brown separable flask is charged with a mixed solution consisting of 28 parts by mass of BA, 197 parts by mass of MMA, 64 parts by mass of HEMA, 27.7 parts by mass of iodine, 42.0 parts by mass of “V-59”, and 150 parts by mass of butyl acetate. The mixture was thoroughly degassed with nitrogen bubbling. The internal temperature was raised to 80 ° C. to initiate the polymerization reaction. After 7 hours, 4.9 parts by mass of aminopropanol was added, and the reaction was further continued for 3 hours. At this time, the polymerization rates of MMA, BA, and HEMA were 91%, 88%, and 97%, respectively. After cooling, the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 250 parts by mass of a polymer F. The properties of the obtained polymer F were Mw3570, Mn2500, Mw / Mn1.40, the glass transition temperature was 62 ° C., and the number of functional groups of the hydroxyl group was 5.5.

Synthesis Example 7 (Preparation of polymer G)
In a 1-liter brown separable flask, MMA 207 parts by mass, BA 29 parts by mass, methacrylic acid (hereinafter referred to as “MAA”) 49 parts by mass, iodine 29.1 parts by mass, “V-59” 44.1 parts by mass, butyl acetate A mixed solution consisting of 141 parts by mass was charged, and the mixed solution was sufficiently deaerated by nitrogen bubbling. The internal temperature was raised to 80 ° C. to start the polymerization reaction, and after 7 hours, 50 parts by mass of sodium hydroxide was added to stop the polymerization. At this time, the polymerization rates of MMA, BA, and GMA were 93%, 87%, and 97%, respectively. After cooling, while filtering, the reaction solution was extracted and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 250 parts by mass of a polymer G. The properties of the obtained polymer G were Mw3710, Mn2630, Mw / Mn1.41, the glass transition temperature was 64 ° C., and the number of functional groups of the carboxyl group was 4.9.

Synthesis Example 8 (Preparation of polymer H)
200 parts by mass of toluene was added to a 1 liter separable flask, and heated and stirred. When toluene began to reflux, MMA 160 parts by mass, BA 50 parts by mass, GMA 115 parts by mass, azobisisobutyronitrile (hereinafter “V-60”) 13 parts by mass were also added dropwise over 2 hours. After completion of the dropwise addition, the mixture was further refluxed for 3 hours, 10 parts by weight of “V-60” was added and refluxed for 1 hour, and then the reflux was stopped. At this time, the polymerization rates of MMA, BA, and HEMA were 91%, 90%, and 97%, respectively. After cooling, the reaction solution was taken out and dried under reduced pressure in an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 250 parts by mass of polymer H. The properties of the obtained polymer H were Mw5290, Mn2300, Mw / Mn2.30, the glass transition temperature was 69 ° C., and the number of functional groups of the epoxy group was 5.7.

Synthesis Example 9 (Preparation of polymer I)
200 parts by mass of toluene was added to a 1 liter separable flask, and the mixture was heated and stirred. When toluene started to reflux, 160 parts by mass of MMA, 50 parts by mass of BA, 115 parts by mass of GMA, and 9 parts by mass of “V-60” were taken over 2 hours. It was dripped. After completion of the dropwise addition, the mixture was further refluxed for 3 hours, 10 parts by mass of V-60 was added and refluxed for 1 hour, and then the reflux was stopped. At this time, the polymerization rates of MMA, BA, and HEMA were 92%, 93%, and 95%, respectively. After cooling, the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 250 parts by mass of a polymer I. The properties of the obtained polymer I were Mw 9860, Mn 3400, Mw / Mn 2.90, the glass transition temperature was 68 ° C., and the number of functional groups of the epoxy group was 5.6.

Synthesis Example 10 (Preparation of polymer J)
Add 200 parts by mass of toluene to a 1 liter separable flask, heat and stir. When toluene begins to reflux, add MMA 160 parts by mass, BA 50 parts by mass, HEMA 105 parts by mass, and “V-60” 13 parts by mass over 2 hours. It was dripped. After completion of the dropwise addition, the mixture was further refluxed for 3 hours, 10 parts by mass of V-60 was added and refluxed for 1 hour, and then the reflux was stopped. The polymerization rates of MMA, BA, and HEMA at this time were 92%, 89%, and 97%, respectively. After cooling, the reaction solution was extracted and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 250 parts by mass of a polymer J. The properties of the obtained polymer J were Mw5400, Mn2250, Mw / Mn2.40, the glass transition temperature was 68 ° C., and the number of functional groups of the hydroxyl group was 5.7.

Synthesis Example 11 (Preparation of polymer K)
Add 200 parts by mass of toluene to a 1 liter separable flask and heat and stir. When toluene begins to reflux, MMA 160 parts by mass, BA 50 parts by mass, HEMA 105 parts by mass, and “V-60” 9 parts by mass over 2 hours. It was dripped. After completion of the dropwise addition, the mixture was further refluxed for 3 hours, 10 parts by mass of V-60 was added and refluxed for 1 hour, and then the reflux was stopped. At this time, the polymerization rates of MMA, BA, and HEMA were 91%, 92%, and 95%, respectively. After cooling, the reaction solution was extracted and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 80 ° C. for 5 hours to obtain about 250 parts by mass of a polymer K. The properties of the obtained polymer K were Mw10010, Mn3500, Mw / Mn2.86, the glass transition temperature was 69 ° C., and the number of functional groups of the hydroxyl group was 5.7.

<Preparation of thermosetting composition for coating film>
Experimental Examples 1-5 and Comparative Examples 1 and 2 (Preparation of powder coating composition)
For experimental examples 1 to 5 and Comparative Examples 1 and 2 of the powder coating composition was prepared by the following method. In accordance with the raw materials and blending ratios shown in Table 2 below, a vinyl polymer (A to I) and a curing agent are blended and dry mixed for 3 minutes using “FM10B Henschel mixer” manufactured by Mitsui Miike Seisakusho Co., Ltd. did. Subsequently, it melt-kneaded at 110 degreeC using the extruder "PR46" by BUSS. Thereafter, the mixture was cooled to obtain each powder coating composition.
As described above, each of the obtained powder coating compositions was subjected to the following performance test and evaluated, and a 0.8T × 70 × 150 mm zinc phosphate-treated plate was used as an object to be coated. 5 and each of the compositions for powder coatings of Comparative Examples 1 and 2 were applied to the above-mentioned objects to be coated to a thickness of 50 to 70 μm and then baked at 180 ° C. for 15 minutes to form a coating film. About the coating film obtained by the above, the performance test shown to the following (1)-(4) was done. The performance test results are shown in Table 4.

<Preparation of composition for high solid paint>
Experimental Examples 6 and 7 and Comparative Examples 3 and 4, (a high solid coating composition)
For experimental example 6 and 7, as well as high solids coating compositions of Comparative Examples 3 and 4 were prepared by the following method. In accordance with the formulation shown in Table 3 below, a vinyl polymer (E to K) and a curing agent are blended, and the viscosity is adjusted to 20 seconds (Zahncup # 2) at 25 ° C. so that air spraying is possible. Each high solid paint was prepared.
Moreover, as a hardening | curing agent, Asahi Kasei Chemicals company make, brand name "Duranate TSS-100" was used.
As described above, Examples 6 and 7 were carried out using a 0.8T × 70 × 150 mm zinc phosphate-treated plate as a coating object in order to evaluate and evaluate the following performance test on the obtained high solid paint composition. In addition, each of the high-solid paint compositions of Comparative Examples 3 and 4 was spray-coated to a thickness of 50 to 70 μm on each of the above-mentioned objects, and this was naturally dried for 7 days to form a coating film.
About the coating film obtained by the above, the performance test shown to the following (1)-(4) was done. The performance test results are shown in Table 4.

<Performance test of coating film>
The coated film obtained as described above was placed in a cylindrical container having a bottom area of about 20 cm ^{2 so} that the height was 6 cm and allowed to stand at 30 ° C. for 7 days. Thereafter, the coating film was taken out from the cylindrical container, and the following performance test was performed on the coating film.
(1) Blocking resistance As described above, the coating film taken out from the cylindrical container after being allowed to stand at 30 ° C. for 7 days was observed visually and by touching the coating film, and evaluated according to the following criteria. did.
(Double-circle): The lump was not recognized at all.
◯: Rice granular lump was recognized.
X: It was hardened with the shape of a container.

(2) Visual appearance (smoothness and sharpness of coating film)
As described above, the appearance of the coating film taken out of the cylindrical container after being allowed to stand at 30 ° C. for 7 days was visually observed for gloss and smoothness, and evaluated according to the following criteria.
A: Particularly excellent.
○: Good.
X: It was inferior.

(3) Long wave (smoothness of coating film)
As described above, about the coating film taken out from the cylindrical container after static value at 30 ° C. for 7 days,
The long wave was measured with Wave Scan Plus (BYK). This long wave is an index representing the smoothness of the coating film, and the smaller the numerical value, the smoother the surface of the coating film.

(4) 60 degree surface gloss It measured at an angle of 60 degrees using a Murakami gloss meter. The larger the number, the higher the gloss.

  The present invention provides a thermosetting composition for paint that is easy to produce, excellent in coating film characteristics, and has both smoothness and blocking resistance of the coating film.

Claims (5)

(A) It is produced by a production method comprising a polymerization step in which a vinyl monomer is radically polymerized in the presence of an organic halogen compound, and has at least one functional group selected from an epoxy group, a carboxyl group and a hydroxyl group. And
The halogen atom in the organic halogen compound is an iodine atom,
The organic halogen compound is a bifunctional initiator having two carbon-halogen bonds, or is formed from a radical polymerization initiator and iodine,
The number average molecular weight is 1000 to 10,000, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is less than 2.0.
The average number of the functional group, and 1.0 to 6.5 der Ru vinyl polymer,
(B) a curing agent ,
The curing agent (B) is a compound having two or more functional groups that can react with the functional group of the vinyl polymer (A).
Content of the said hardening | curing agent (B) is the range whose molar ratio of the functional group which the said hardening | curing agent (B) has with respect to the said functional group which the said vinyl polymer (A) has is 0.5-2.0. coating the thermosetting composition characterized der Rukoto.   2. The thermosetting composition for paint according to claim 1, wherein the organic halogen compound is an iodine-containing compound having a structure in which the iodine atom has two iodine atoms and the iodine atom is bonded to a carbon atom bonded to an aromatic ring. object.   The thermosetting composition for paint according to claim 1 or 2, wherein the vinyl polymer (A) is produced by a production method further comprising a terminal modification step. The thermosetting composition for paint according to any one of claims 1 to 3 , wherein the vinyl polymer (A) has the functional group at a molecular end. The thermosetting composition for paint according to any one of claims 1 to 4 , wherein the vinyl polymer (A) is a (meth) acrylic polymer.