JP2011074326A - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition, which contains a vinyl polymer having a functional group at a molecular end, has a narrow dispersion degree, and gives a cured product excellent in strength and elasticity. <P>SOLUTION: The curable composition contains a vinyl polymer having a functional group at a molecular end. The vinyl polymer is obtained through a step of subjecting vinyl monomers to living radical polymerization in the presence of a catalyst, which comprises a compound containing a central atom consisting of at least one element selected from phosphorus, nitrogen, carbon, oxygen, germanium, tin, and antimony, and a halogen atom bonded to the center atom, and also in the presence of an initiator comprising an organic halogen compound, so as to obtain a first polymer having a halogen atom derived from the catalyst or the initiator at a molecular end; and then a step of modifying the molecular end of the first polymer so as to substitute the halogen atom included in the first polymer by the functional group. The vinyl polymer has the dispersion degree of less than 2.0. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a curable composition. More specifically, the present invention contains a vinyl polymer having at least one functional group selected from a (meth) acryloyl group, a hydroxyl group, a carboxyl group, and an amino group at the molecular end and having a low degree of dispersion. And a curable composition that gives a cured product having excellent strength and elasticity.

A polymer having a functional group such as a (meth) acryloyl group, a hydroxy group and an amino group at the end of the molecular chain forms a crosslink by curing the polymer alone or by using a catalyst or an initiator. It becomes a thing. Such a polymer is known to cure quickly and the resulting cured product is excellent in heat resistance and durability.
For example, a polymer having a hydroxyl group or an amino group at the terminal is cross-linked by using an isocyanate compound or the like that reacts with these functional groups as a curing agent to give a cured product having excellent heat resistance and durability. The main chain skeleton of these polymers includes polyether polymers such as polyethylene oxide, polypropylene oxide and polytetramethylene oxide, polybutadiene, polyisoprene, polychloroprene, polyisobutylene and hydrogenated products thereof. There are polymers such as hydrocarbon polymers, polysiloxane polymers such as polydimethylsiloxane, and vinyl polymers such as polyacrylate, which are used in various applications depending on the properties of the main chain skeleton.
Among these, a cured product obtained from a vinyl polymer in particular has excellent weather resistance, heat resistance, oil resistance, and transparency, and has characteristics that cannot be obtained with the other polymers described above. Accordingly, curable compositions containing a curable polymer having a vinyl polymer as a main chain skeleton have been proposed in various fields.

  For example, in Patent Document 1 below, an acrylic polymer having a hydroxyl group at the molecular chain end is produced using a hydroxyl group-containing sulfide as a chain transfer agent, and further reacted with a hydroxyl group to form a metal at the molecular chain end. An acrylic polymer having an acryloyl group is disclosed.

  Further, in Patent Document 2 below, a vinyl polymer having an acryloyl group at the molecular chain terminal is produced by using a living radical polymerization method using a transition metal complex as a catalyst. And it is disclosed that a rubber-like cured product can be obtained by blending an initiator or the like with the obtained vinyl polymer and photocuring it.

  Further, in Patent Document 3 below, a vinyl polymer having a hydroxyl group at the molecular chain terminal is produced by using a living radical polymerization method using a transition metal complex as a catalyst. It is disclosed that a rubber-like cured product can be obtained by blending and curing an isocyanate compound in the obtained vinyl polymer.

JP-A-5-262808 JP 2000-72816 A JP-A-11-116617

  However, in the method described in Patent Document 1, it cannot be said that the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polymer is sufficiently small. And the cured | curing material characteristics, such as intensity | strength and elasticity which the cured | curing material obtained using the composition containing this polymer has, are not fully satisfied.

The living radical polymerization methods described in Patent Documents 2 and 3 are methods using a transition metal complex as a catalyst, and the transition metal complex may remain in the obtained polymer. Then, from the viewpoint of safety and the like, when removing the transition metal complex remaining in the polymer, the production process becomes complicated, requiring a great deal of labor and economic burden.
Moreover, the catalyst which consists of this transition metal complex requires the compound used as the ligand which comprises a complex, and a manufacturing process is complicated.
Moreover, the present condition is that the balance of hardened | cured material characteristics, such as intensity | strength and elasticity which the hardened | cured material obtained from the polymer disclosed by patent document 2 and 3 has, is not fully satisfied.
Moreover, in the manufacturing method of patent document 2 and 3, when the monomer which has functional groups, such as carboxylic acid, is used, the activity fall of the catalyst which consists of a copper compound (copper complex) may be caused. Therefore, in Patent Documents 2 and 3, a copolymer having a monomer unit having such a functional group may have inferior cured product characteristics.

  This invention is made | formed in view of the said problem, and it aims at providing the curable composition which gives the hardened | cured material which contains a vinyl polymer with a small dispersion degree, and is excellent in intensity | strength and elasticity.

That is, the present invention is as follows.
1. A curable composition containing a vinyl polymer having at least one functional group selected from a (meth) acryloyl group, a hydroxyl group, a carboxyl group, and an amino group at the molecular end,
The vinyl polymer includes a catalyst comprising a compound including a central atom composed of at least one element selected from phosphorus, nitrogen, carbon, oxygen, germanium, tin, and antimony, and a halogen atom bonded to the central atom. The first polymer having a terminal halogen atom derived from the catalyst or the initiator was obtained by living radical polymerization of the vinyl monomer in the presence of an initiator composed of an organic halogen compound. Thereafter, the first polymer is terminal-modified, and the halogen atom contained in the first polymer is substituted with the functional group,
A curable composition, wherein a ratio (Mw / Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) of the vinyl polymer is less than 2.0.
2. 1. The vinyl polymer is a (meth) acrylic polymer. The curable composition according to 1.
3. 1. The number average molecular weight of the vinyl polymer is 3000 to 50000. Or 2. The curable composition according to 1.
4). The vinyl monomer forming the first polymer contains a methacrylic acid ester compound and an acrylic acid ester compound, and the ratio of the amount of the methacrylic acid ester compound and the acrylic acid ester compound used is the sum of both. The above 1. is 50 to 100% by mass and 0 to 50% by mass, respectively. The curable composition in any one of thru | or 3.
5). Furthermore, the above-mentioned 1. containing a curing agent. The curable composition in any one of thru | or 4.
6). Above 1. To 5. A sealing material composition comprising the curable composition according to any one of the above.
7). Above 1. To 5. An adhesive composition comprising the curable composition according to any one of the above.
8). Above 1. To 5. A pressure-sensitive adhesive composition comprising the curable composition according to any one of the above.

Since the curable composition of the present invention contains a vinyl polymer having at least one functional group selected from a (meth) acryloyl group, a hydroxyl group, a carboxyl group, and an amino group at the molecular end, And a cured product having excellent elasticity. The vinyl polymer is obtained by modifying the terminal of a vinyl polymer obtained using a specific catalyst, and efficiently has a vinyl polymer having a high proportion of the functional groups at the molecular ends. The curable composition of the present invention containing this vinyl polymer can give a cured product having excellent strength and elasticity. Moreover, since the said vinyl polymer is a polymer obtained using said catalyst, it can be set as the hardened | cured material which the transition metal derived from a catalyst does not remain | survive.
Moreover, when the vinyl polymer is a (meth) acrylic polymer, a cured product having more excellent strength and elasticity can be provided.
Furthermore, the vinyl monomer forming the first polymer contains a methacrylic acid ester compound and an acrylic acid ester compound, and the ratio of the amount of the methacrylic acid ester compound and the acrylic acid ester compound used is the sum of both. When it is 100 mass%, when it is 50-100 mass% and 0-50 mass%, respectively, the hardened | cured material which is excellent in intensity | strength and elasticity can be given.
Moreover, when it contains a hardening | curing agent, the hardened | cured material excellent in intensity | strength and elasticity can be obtained efficiently.

Hereinafter, the curable composition of the present invention will be described in detail.
The curable composition of the present invention is a curable composition containing a vinyl polymer having at least one functional group selected from a (meth) acryloyl group, a hydroxyl group, a carboxyl group, and an amino group at the molecular end. There,
The vinyl polymer includes a central atom composed of at least one element selected from phosphorus, nitrogen, carbon, oxygen, germanium, tin, and antimony and a halogen atom bonded to the central atom (hereinafter referred to as “halogen atom (a ) ”)) In the presence of a catalyst comprising a compound (hereinafter also referred to as“ compound (a) ”) and an initiator comprising an organic halogen compound. After obtaining a first polymer having a terminal halogen atom derived from the catalyst or the initiator by polymerization, the first polymer is terminal-modified, and the first polymer contained in the first polymer A halogen atom is a polymer substituted with the functional group,
The ratio (Mw / Mn) (hereinafter also referred to as “dispersion degree”) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the vinyl polymer is less than 2.0. To do.
In this 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. .
Furthermore, “(meth) acryloyl” is used to mean including one or both of acryloyl and methacryloyl.
“Ph” means a phenyl group or a phenylene group.

  The vinyl polymer has at least one functional group selected from a (meth) acryloyl group, a hydroxyl group, a carboxyl group, and an amino group at the molecular end. This vinyl polymer is obtained by modifying the terminal of the first polymer with respect to the first polymer obtained by living radical polymerization of the vinyl monomer in the presence of the catalyst. It is a polymer having a group at the molecular end.

  As the method for producing the vinyl polymer, a polymerization step (hereinafter referred to as “first step”) for obtaining the first polymer by living radical polymerization of the vinyl monomer, and the polymerization step are used. A method of sequentially providing a molecular terminal modification step (hereinafter referred to as “second step”) for modifying the molecular terminal of the obtained first polymer may be mentioned. According to this method, a first polymer having a dispersity of less than 2.0 is obtained in the first step, and then, in the second step, the (meth) acryloyl group, hydroxyl group is maintained while maintaining the dispersity. A vinyl polymer having at least one functional group selected from a group, a carboxyl group, and an amino group at the molecular end can be efficiently obtained. That is, by using the production method according to the first step and the second step, the functional group can be smoothly introduced into the molecular terminal of the vinyl polymer, and further, a (meth) acryloyl group, A vinyl polymer having at least one functional group selected from a hydroxyl group, a carboxyl group, and an amino group at the molecular end can be efficiently obtained.

  In the first step, the vinyl monomer is subjected to living radical polymerization in the presence of the catalyst to obtain a first polymer. This living radical polymerization refers to a polymerization reaction in which chain transfer reaction and termination reaction do not substantially occur in the radical polymerization reaction, and the chain growth terminal retains activity even after the monomer polymerization reaction. In this polymerization reaction, the polymerization activity is maintained at the end of the produced polymer even after the completion of the polymerization reaction, and when the monomer is added, the polymerization reaction can be started again.

The catalyst comprises a compound (a) comprising a central atom composed of at least one element selected from phosphorus, nitrogen, carbon, oxygen, germanium, tin, and antimony, and a halogen atom bonded to the central atom. .
The “central atom” means an atom that mainly binds to a halogen atom and exerts a catalytic action among atoms constituting the catalyst. In general, the term “catalyst” in the “catalyst” has the same meaning as the term “center metal”. However, since phosphorus, nitrogen, carbon, oxygen, and the like used in the present invention are not generally classified as metals, they are misunderstood. In order to avoid this, the term “center atom” is used instead of “center metal” which is generally used as the term in “catalyst”.
The compound (a) may have at least one central atom, and may have two or more central atoms. When the compound (a) has a plurality of central atoms, the types of the central atoms may be the same or different.
As said catalyst, it can use individually or in combination of 2 or more.
Moreover, as said catalyst used for manufacture of the 1st polymer in said 1st process, although said compound (a) can be used as it is, the compound (catalyst precursor) which forms compound (a) is used. You can also.

  In the polymerization reaction for obtaining the first polymer, the catalyst extracts a halogen from the organic halogen compound to generate a radical. As a result, the catalyst removes the group that suppresses the growth reaction of the first polymer derived from the organic halogen compound used as the dormant species and converts it to an active species to control the growth reaction.

In the compound (a) constituting the catalyst, the halogen atom is bonded to the central atom. When the compound (a) has two central atoms, at least one halogen atom is bonded to each central atom, and two or more halogen atoms are bonded to the central atom. Good.
Examples of the halogen atom bonded to the central atom include fluorine, chlorine, bromine and iodine atoms. Of these, an iodine atom is preferable. Two or more halogen atoms may be present in one molecule of the compound (a).
Further, when a plurality of halogen atoms are present in one molecule of the compound (a), the plurality of halogen atoms may be the same or different.

In the case of the compound (a) constituting the catalyst (hereinafter also referred to as “catalyst (p)”) in which the central atom in the catalyst is a phosphorus atom or a nitrogen atom, a central atom composed of a phosphorus atom or a nitrogen atom, and the center The compound is not particularly limited as long as it is a compound containing a halogen atom bonded to an atom. For example, the compound (a) in which the central atom is a phosphorus atom or a nitrogen atom includes a compound represented by the following general formula (1).
R ¹ _n M _h X ¹ _m (... Z) _k (1)
In the general formula (1), R ¹ is an alkyl group, an alkyl carboxyl group, a haloalkyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group, an alkylcarbonyl group, an aryl group, or a substituted aryl group, and M is a center An atom which is a phosphorus atom or a nitrogen atom, X ¹ is a halogen atom, Z is an oxygen atom, a nitrogen atom or a sulfur atom, and is bonded to M; n is an integer of 0 to (4 × h), h is an integer of 1 or more, m is an integer of 1 to (5 × h), and k is an integer of 0 to (2 × h). , H is 2 or more, R ¹ , M and X ¹ may be independently bonded to any of the plurality of atoms M, and “...” which is a bond between M and Z is double A bond or a triple bond is shown.

N in the general formula (1) is an integer of 0 to (4 × h). For example, when h is 1, n is 0 to 4, and when h is 2, n is 0 to 8. When n is 2 or more, all R ^{1 s} may be different from each other, may be partially the same, or may all be the same.

M in the general formula (1) is a central atom of the catalyst (p), and is a phosphorus atom or a nitrogen atom.
H in the general formula (1) is an integer of 1 or more, preferably 10 or less, more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, Preferably it is 2 or less, more preferably 1.

When h is an integer of 2 or more, the plurality of atoms M may be the same or different. Preferably all are the same elements.
Moreover, when h is an integer greater than or equal to 2, several atom M is normally couple | bonded by the single bond, the double bond, or the triple bond.
When h is an integer of 2 or more, the substituent R ¹ and the halogen atom X may be independently bonded to any of the plurality of atoms M.

Further, specific examples in the case where h is 2 include a compound having a structure in which two phosphorus atoms described later are bonded (-P = P-). Moreover, when h is 3 or more, a compound having (-P = PP = P-) and the like can be mentioned.
Further, when h is 2, a structure in which two atoms M are bonded can be taken. For example, the structure may be “−M−M−”, “−M = M−”, or “−M≡M−”. Further, when the central atom is phosphorus, as described above, a structure in which two phosphorus atoms are bonded (-P = P-) can be obtained.
When h is 2, the substituent R ¹ and the halogen atom X may be independently bonded to any of the two atoms M.
When h is 3 or more, the h atoms M may be linked in a straight chain or may be linked in a branched chain.

X ¹ in the general formula (1) is a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Of these halogen atoms, a chlorine atom, a bromine atom and an iodine atom are preferable, and an iodine atom is more preferable.

M in the general formula (1) is an integer of 1 to (5 × h), preferably an integer of 2 to (5 × h). For example, when h is 1, m is 1 to 5, and when h is 2, m is 1 to 10.
When m is 2, the two halogen atoms X ¹ may be the same or different. When m is 3 or more, all the halogen atoms X ¹ may be different from each other, may be partially the same, or may all be the same. When m is 2 or more, all the halogen atoms X are preferably the same.

Z in the said General formula (1) is an oxygen atom, a nitrogen atom, or a sulfur atom, Preferably, it is an oxygen atom. The atom Z is bonded to the atom M. The bond between atom Z and atom M is a double bond or a triple bond.
Moreover, k in the said General formula (1) is an integer of 0- (2xh). For example, when h is 1, k is 0 to 2, and when h is 2, k is 0 to 4.

In the general formula (1), all of R ¹ , X, and Z are usually bonded to M. In the general formula (1), n, h, m, and k are selected so that the valence of the chemical formula (1) is balanced.
When M (central atom) is a phosphorus atom or a nitrogen atom, the sum (m + n) of m and n is preferably 3 or 5.

Examples of the compound (a) having a phosphorus atom as a central atom include phosphorus halides, halogenated phosphines, and halogenated phosphorous acid derivatives.
Examples of the phosphorus halide include phosphorus triiodide and phosphorus pentaiodide.
Specific examples of the halogenated phosphine include diphenylphosphine iodide (Ph ₂ PI).
Specific examples of the halogenated phosphite derivative include diethyl iodide phosphite [(C ₂ H ₅ O) ₂ P (O) I] and ethyl phenyl phosphinate [(C ₂ H ₅ O) _2. PhP (O) I], diphenylphosphine oxide [Ph ₂ P (O) I] and the like.

As a compound (a) which makes a nitrogen atom a central atom, in said general formula (1), n becomes like this. Preferably it is 0-3, More preferably, it is 0-2. h is preferably 1, and m is preferably 1 to 3. k is preferably 0. When n is 2 or more, a plurality of R ¹ and M may form a ring structure. In this case, both of R ¹ are preferably alkylcarbonyl, vinylcarbonyl, or phenylcarbonyl. Specific examples of the compound (a) having a nitrogen atom as a central atom include nitrogen halides such as nitrogen triiodide; halogenated amines such as diphenylamine iodide (Ph ₂ NI); succinimide iodide, iodine And halogenated imides such as iodinated maleimide and phthalimide iodide.

  Next, in the case of the compound (a) constituting the catalyst in which the central atom in the catalyst is a carbon atom (hereinafter also referred to as “catalyst (c)”), the central atom composed of carbon is bonded to the central atom. A compound containing a halogen atom. In this case, you may have atoms or groups other than a halogen atom. For example, an arbitrary organic group or inorganic group can be bonded to the central atom.

Examples of the organic group include aryl group, heteroaryl group, substituted aryl group, substituted heteroaryl group, alkenyl group (for example, vinyl group), alkynyl group, alkoxy group (for example, methoxy group, ethoxy group, propoxy group, and butoxy group). Group), ester group (for example, aliphatic carboxylic acid ester), alkylcarbonyl group (for example, methylcarbonyl group), haloalkyl group (for example, trifluoromethyl group) and the like. Among these, an aryl group, a heteroaryl group, a substituted aryl group, a substituted heteroaryl group, an alkenyl group, and an alkynyl group are preferable. Moreover, it is more preferable to use a compound having an aryl group, a heteroaryl group, a substituted aryl group, and a substituted heteroaryl group as a catalyst because the radical activity tends to be higher. That is, as an organic group couple | bonded with a central atom, Preferably, a phenyl group, a C7-C16 alkylphenyl group, a C7-C16 alkyloxyphenyl group, etc. are mentioned.
Examples of the inorganic group include a hydroxyl group, an amino group, and a cyano group.

  The number of the organic group and inorganic group bonded to the central carbon atom is not particularly limited, but is preferably 3 or less, more preferably 1.

Moreover, as the catalyst (c) whose central atom is a carbon atom, a compound in which 1 to 3 substituents for radical stabilization described below are bonded to the central atom is preferable.
Examples of the substituent for radical stabilization include an electron-withdrawing substituent or a substituent that forms a resonance structure together with the central atom (hereinafter also referred to as “substituent that forms a resonance structure”). . When two radical stabilizing substituents are present, the radical stabilizing substituents may be linked to each other to form a ring structure with the central atom and the two radical stabilizing substituents.
Further, when there are three radical stabilizing substituents, two of the three radical stabilizing substituents are connected to each other, and the two connected radical stabilizing substituents and the center A ring structure may be formed with an atom, or three radical stabilizing substituents may be connected to each other to form a ring structure with a central atom and three substituents.

Further, the radical stabilizing substituent may be an electron donating substituent. When two electron donating substituents are present, the electron donating substituents may be linked to each other to form a ring structure with the central atom and the two electron donating substituents.
When three electron-donating substituents are present, two of the three electron-donating substituents are linked to each other, and the two linked electron-donating substituents and the central atom A ring structure may be formed, or three electron-donating substituents may be connected to each other to form a ring structure with the central atom and the three electron-donating substituents.
In the present specification, the electron-withdrawing substituent, the electron-donating substituent, and the substituent that forms a resonance structure together with the central atom are collectively referred to as a “radical stabilizing substituent. "

  The electron-withdrawing substituent is a substituent that is bonded to carbon of the central atom and attracts electrons from the carbon of the central atom. As this electron-withdrawing substituent, a halogen atom is preferable. Specific examples include fluorine, chlorine, bromine, and iodine. The electron-withdrawing substituent other than the halogen atom may be any electron-withdrawing substituent that draws electrons from the central atom carbon to the same extent as the halogen atom. For example, carbonyl oxygen (= O), cyano group , And a nitro group.

  The electron-donating substituent is a substituent that bonds to carbon of the central atom and donates electrons to the carbon of the central atom. Examples of such a substituent include an alkoxy group.

The substituent that forms the resonance structure is a substituent having a double bond or a triple bond, and has a structure in which an atom constituting the double bond or triple bond is bonded to a central atom (carbon). That is, a total of three atoms including a central atom and two atoms constituting a double bond or a triple bond are bonded so as to have a structure represented by the following formula (2a) or (2b). The structure has an atom adjacent to a double bond or triple bond.
“C−M ¹ = M ² ” (2a)
“C−M ³ ≡M ⁴ ” (2b)

In the above formula (2a), M ¹ and M ² are atoms constituting a double bond, and M ¹ is an atom bonded to the central atom. In the above formula (2b), M ³ and M ⁴ are atoms constituting a triple bond, and M ³ is an atom bonded to the central atom. By adopting such a structure, when the central atom becomes a carbon radical, the carbon radical is stabilized by the electron resonance effect of the carbon radical and the double bond or triple bond, and the catalyst has high activity as a catalyst. Show.

M ¹ in the formula (2a) is not particularly limited, and specific examples thereof include a carbon atom, a silicon atom, a phosphorus atom, and a nitrogen atom. Of these, a carbon atom is preferred. Further, when M ¹ is a tetravalent atom, M ¹ further has one monovalent group. Examples of such a group include a hydrogen atom or an alkyl group. When M ¹ is a pentavalent atom, M ¹ further has one divalent group or two monovalent groups. Examples of such a group include a hydrogen atom or an alkyl group.

M ² in the above formula (2a) is not particularly limited, and specific examples include a carbon atom, a silicon atom, a phosphorus atom, a nitrogen atom, and an oxygen atom. Of these, a carbon atom is preferred. When M ² is a trivalent atom, M ² further has one monovalent group. Examples of such a group include a hydrogen atom or an alkyl group. When M ² is a tetravalent atom, M ² further has one divalent group or two monovalent groups. Examples of such a group include a hydrogen atom or an alkyl group. When M ² is a pentavalent atom, M ² further has one trivalent group, or one divalent group and one monovalent group, or three monovalent groups. Examples of such a group include a hydrogen atom or an alkyl group.

M ³ in the above formula (2b) is not particularly limited, and specific examples include a carbon atom, a silicon atom, and a phosphorus atom. Of these, a carbon atom is preferred. Further, when M ³ is a pentavalent atom, M ³ further has one monovalent group. Examples of such a group include a hydrogen atom or an alkyl group.

M ⁴ in the above formula (2b) is not particularly limited, and specific examples thereof include a carbon atom, a silicon atom, a phosphorus atom, and a nitrogen atom. Of these, a carbon atom is preferred. Further, when M ⁴ is a tetravalent atom, M ⁴ further has one monovalent group. Examples of such a group include a hydrogen atom or an alkyl group. When M ⁴ is a pentavalent atom, M ⁴ further has one divalent group or two monovalent groups. Examples of such a group include a hydrogen atom or an alkyl group.

Of the above, preferably, both M ¹ and M ² are carbon atoms. When the central atom has a substituent having a double bond between two carbon atoms, that is, when M ¹ and M ² are carbon atoms, the double bond between the carbon atoms is an aromatic group. It may be a heavy bond or an ethylenic double bond. For example, a structure in which an alkenyl group or an alkynyl group is bonded to the central atom, or a structure in which an aryl group, heteroaryl group, substituted aryl group, or substituted heteroaryl group is bonded to the central atom is preferable. In addition, since the catalyst is preferably not polymerized in the radical reaction (first step), a structure in which an aryl group, heteroaryl group, substituted aryl group, or substituted heteroaryl group is bonded to the central atom is more preferable. In the case of ethylenic double bonds, those having low radical polymerization reactivity are preferred.

Moreover, it is more preferable that the central atom has two or three substituents having the above-described double bond or triple bond. That is, it is more preferable to have a structure in which a central atom is sandwiched between two or three double bonds or triple bonds.
For example, in the case of a structure in which a central atom is sandwiched between two double bonds, the structure is represented by the following formula (2c).
“M ⁶ = M ⁵ −C−M ⁷ = M ⁸ ” (2c)
Here, M ⁵ and M ⁷ in the formula (2c) are the same atoms as M ^1, and M ⁶ and M ⁸ are the same atoms as M ² . In the compound (a) having such a structure, the carbon atom of the central atom becomes a stable carbon radical during living radical polymerization and exhibits high activity as a catalyst.

  In addition, when there are two substituents forming a resonance structure, it is preferable that the two substituents and the central atom constitute one resonance structure as a whole. For example, it is preferable that two substituents and the central atom constitute an aromatic ring structure as a whole. As a more specific example, for example, iodobenzene has a substituent composed of a hydrocarbon at the 2nd, 3rd and 4th positions and a substituent composed of a hydrocarbon at the 5th and 6th positions on the carbon atom at the 1st position. It can be considered that it has a structure in which two substituents are linked between the 4-position carbon and 5-position carbon. The benzene ring constituted as a whole from the two substituents and the central atom constitutes one resonance structure, and the radical at the central atom is stabilized by the resonance structure.

上記一般式（２ｄ）において、Ｘ^２はハロゲン原子を示し、Ｒ^２１、Ｒ^２２及びＲ^２３は二重結合又は三重結合を有する有機基、あるいはハロゲン原子である。Ｒ^２１、Ｒ^２２及びＲ^２３が二重結合又は三重結合を有する有機基である場合、その二重結合又は三重結合を構成する原子のうちの１つが上記式（２ｄ）中の中心原子である炭素原子に結合しており、Ｒ^２１及びＲ^２２が互いに連結されてＲ^２１、Ｒ^２２及び中心原子により環構造を形成してもよく、Ｒ^２１及びＲ^２３が互いに連結されてＲ^２１、Ｒ^２３及び中心原子により環構造を形成してもよく、Ｒ^２２及びＲ^２３が互いに連結されてＲ^２２、Ｒ^２３及び中心原子により環構造を形成してもよく、Ｒ^２１、Ｒ^２２及びＲ^２３が互いに連結されてＲ^２１、Ｒ^２２及びＲ^２３により環構造を形成してもよく、Ｒ^２１及びＲ^２２と中心原子の炭素原子とにより脂肪族不飽和環構造を形成してもよく、Ｒ^２１、Ｒ^２２及びＲ^２３と中心原子の炭素原子とにより芳香族環構造を形成してもよい。Ｒ^２１、Ｒ^２２及びＲ^２３は、互いに同一であっても異なっていてもよい。 As the catalyst (c) whose central atom is a carbon atom, a compound represented by the following general formula (2d) can be used.

In the general formula (2d), X ² represents a halogen atom, and R ²¹ , R ²² and R ²³ are an organic group having a double bond or a triple bond, or a halogen atom. When R ²¹ , R ²² and R ²³ are organic groups having a double bond or a triple bond, one of the atoms constituting the double bond or triple bond is the central atom in the above formula (2d). is attached to a carbon ^{atom, R 21} and ^{R 22} are coupled together, may form a ring structure by ^{R 21, R 22} and the central ^atom, and ^{R 21} and ^{R 23} are connected to each other ^R 21, R ²³ and the central atom may form a ring structure, R ²² and R ²³ may be connected to each other to form a ring structure with R ²² , R ²³ and the central atom, and R ²¹ , R ²² and R ²³ May be connected to each other to form a ring structure with R ²¹ , R ²² and R ²³ , or an aliphatic unsaturated ring structure may be formed with R ²¹ and R ²² and the carbon atom of the central atom, ^{21, R 22} and The carbon atoms of ²³ and the central atom may form an aromatic ring structure. R ²¹ , R ²² and R ²³ may be the same as or different from each other.

Examples of the organic group having a double bond or triple bond in R ²¹ , R ²² and R ²³ include an alkenyl group (for example, vinyl group), an alkynyl group, or an aryl group (for example, phenyl group) and a heteroaryl group. Is mentioned. In the case of an alkenyl group or an alkynyl group, a double bond or a triple bond is present at the terminal, and the carbon atom of the central atom is bonded to the terminal carbon. Such a structure is preferable also in a catalyst precursor, which will be described later, whose central atom is a carbon atom.

Specific examples of the compound (a) having carbon as the central atom include halogenated carbon, halogenated alkyl, and aryl halide.
Examples of the halogenated carbon include carbon tetraiodide (CI ₄ ).
Examples of the alkyl halide and the aryl halide include compounds represented by the following formula (2e).
R ² _n CX ² _m (2e)
However, the above formula (2e), R ² represents an alkyl group or an aryl group, when R ² is more, the R ² may be the same or different. X ² represents a halogen atom. N is an integer of 1 to 3, m is an integer of 1 to 3, and the sum of n and m (n + m) is 4.

Examples of the halogenated alkyl and aryl halide represented by the above formula (2e) include diphenylmethane iodide (Ph ₂ CI ₂ ) and the like.

Next, in the case of the compound (a) constituting the catalyst in which the central atom in the catalyst is an oxygen atom (hereinafter also referred to as “catalyst (o)”), a central atom composed of an oxygen atom and a bond to the central atom The compound is not particularly limited as long as it is a compound containing a halogen atom.
As the catalyst (o), a compound in which a central atom (oxygen atom) is further bonded to a carbon atom, a silicon atom, a nitrogen atom or a phosphorus atom can be used. In addition to the halogen atom, the atom to which the central atom (oxygen atom) is further bonded is preferably a carbon atom.

  Further, the atom to which the central atom (oxygen) is bonded preferably has a double bond or a triple bond with an adjacent atom (for example, a carbon atom). That is, the atom to which the central oxygen atom is bonded is a carbon atom having an unsaturated bond of any one of an alkenyl group (for example, vinyl group), an alkynyl group, or an aryl group (for example, phenyl group). Is preferred. In the case of an alkenyl group or alkynyl group, a double bond or a triple bond is preferably present at the terminal, and a central oxygen atom is more preferably bonded to a carbon atom at the terminal. Such a structure is preferable also in a catalyst precursor described later in the case where the central atom is an oxygen atom.

  When a carbon atom having a double bond or a triple bond is bonded to an oxygen atom which is a central atom, when the oxygen atom becomes an oxygen radical, the oxygen radical becomes stable by resonance stabilization, It is considered that the catalyst exhibits good catalytic activity as a living radical polymerization catalyst.

The oxygen atom which is the central atom of the catalyst (o) may be further bonded to any organic group or inorganic group.
Examples of the organic group include aryl groups (for example, phenyl group), substituted aryl groups, alkenyl groups (for example, vinyl group), alkynyl groups, alkoxy groups (for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.) ), Ester groups (for example, aliphatic carboxylic acid esters), alkylcarbonyl groups (methylcarbonyl groups, etc.), haloalkyl groups (trifluoromethyl groups), and the like. Of these, aryl groups, substituted aryl groups, alkenyl groups, and alkynyl groups are preferred.
Examples of the inorganic group include a hydroxyl group, an amino group, and a cyano group.

  The number of the organic group or inorganic group bonded to the central atom (oxygen) is preferably 3 or less, more preferably 1. Further, when a plurality of the organic groups or inorganic groups are present, they may be the same or different.

As the catalyst when the central atom is an oxygen atom, a compound represented by the following general formula (3a) can be used.
R ³ _n (OX ³ ) _m (3a)
In the general formula (3a), R ³ represents an organic group, X ³ represents a halogen atom, n is an integer of 1 or more, m is an integer of 1 or more, and the oxygen atom (O) is It is bound to both R ³ and X ³ .

The organic group R ³ in the general formula (3a) may be a linear or branched organic group having a chain structure or an organic group having a cyclic structure, and has both a chain structure and a cyclic structure. An organic group may be used.
Specific examples of the organic group R ³ in the general formula (3a) include an alkyl group, an alkenyl group, an alkynyl group, an alkyl carboxyl group, an alkylcarbonyl group, a haloalkyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group, An aryl group and a substituted aryl group are mentioned. Of these, an aryl group, an alkenyl group, and an alkynyl group are preferable.
When R ³ is a substituted aryl group, the substituent is preferably an alkyl group, an alkoxy group, or a cyano group, more preferably an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. And a cyano group.

  N in the general formula (3a) is a positive integer, may be 1, may be 2, or may be an integer of 3 or more. Specifically, 1-10 are preferable, More preferably, it is 1-5, More preferably, it is 1-3, Most preferably, it is 1-2.

In the general formula (3a), X ³ is a halogen atom. m is an integer of 1 or more, may be 1, may be 2, or may be an integer of 3 or more. Specifically, 1-10 are preferable, More preferably, it is 1-5, More preferably, it is 1-3, Most preferably, it is 1-2.

  In general formula (3a), n and m are usually selected so that the entire valence of the chemical formula shown in general formula (3a) is balanced.

As the catalyst (o) having an oxygen atom as a central atom, any known compound corresponding to the above definition can be used, and preferred specific examples thereof include halogenated oxygen (for example, oxygenated iodide), alkoxy halide. Alternatively, carboxyl halide (R ³ OX ³ , for example, iodobenzoic acid (PhCOOI)), a compound in which H (hydrogen atom) of the phenolic hydroxyl group in the phenolic compound is substituted with a halogen (for example, thymol iodide), and the like. It is done.
In addition, as a compound (a) which comprises a catalyst (o), Preferably, it does not have a radical reactive double bond.

Next, the compound (a) constituting the catalyst (hereinafter also referred to as “catalyst (g)”) in which the central atom in the catalyst is a central atom composed of at least one element selected from germanium, tin, or antimony. In this case, the compound includes the above-described central atom and a halogen atom bonded to the central atom.
In the catalyst (g), the central atom may be further bonded to any organic group or inorganic group.

  Examples of the organic group include an aryl group, a substituted aryl group, an alkoxy group (for example, methoxy group), an ester group (for example, aliphatic carboxylic acid ester), and a haloalkyl group (for example, trifluoromethyl group). Among these, a catalyst having an aryl group or a substituted aryl group is preferable because the radical activity tends to be higher.

Examples of the inorganic group include a hydroxyl group, an amino group, and a cyano group.
The number of the organic group and inorganic group is not particularly limited, but is preferably 3 or less, more preferably 1.

  In the case of the catalyst (g), a complex formed by coordination bonding of a ligand can also be used for the polymerization reaction. However, the catalyst of the present invention can usually be used in a polymerization reaction as it is, and it is not necessary to add a ligand to form a complex. In the transition metal complex catalyst in the prior art, the transition metal compound is generally poorly soluble in the reaction solution, and it is necessary to form a complex by adding an appropriate ligand. There is no such need. If a ligand is not used, it is advantageous in terms of material cost, and it is advantageous in that the weight of the catalyst used can be reduced. Further, amine compounds generally used as ligands are usually expensive or require complicated synthesis. Furthermore, considering the properties of the amine, it is considered that the amine complex of the transition metal is likely to be adsorbed on the produced polymer, and therefore it is considered that it takes much more time to remove it.

As the catalyst (g) when the central atom is a germanium atom, a tin atom or an antimony atom, a compound represented by the following general formula (4a) can be used.
R ⁴ _n MX ⁴ _m (4a)
Here, in the general formula (4a), R ⁴ represents an aryl group or a substituted aryl group, M represents a germanium atom, a tin atom, or an antimony atom, X ⁴ represents a halogen atom, and n is 0 to 3. It is an integer, m is an integer of 1-4.

  Most of the catalysts (g) in the case where the central atom is a germanium atom, a tin atom or an antimony atom are known compounds, and commercially available products can be used as they are. Further, these compounds can be synthesized by a known method.

When the catalyst (g) is a compound having a germanium atom as a central atom and an organic group R ⁴ (for example, an aryl group or a substituted aryl group) bonded to the germanium atom, for example, R ⁴ GeI ₃ , R ⁴ GeI ₃ can be synthesized by a method in which germanium iodide is reacted with iodide R ⁴ I of organic group R ⁴ as follows.
R ⁴ −I + GeI ₂ → R ⁴ GeI ₃
Since iodide R ⁴ I is often a liquid, it is possible to carry out the reaction without a solvent in the case of a liquid. Moreover, you may use a solvent (for example, benzene, toluene etc.) as needed. When iodide R ⁴ I is solid, for example, benzene, toluene, etc. can be used as the solvent. Note that this reaction proceeds even if no catalyst is used. Specific examples of such a reaction are described in, for example, the document Journal of Organometallic Chemistry 56, 1-39 (1973), and various organic groups R can be obtained by applying the method described in this document. A compound in which ⁴ is bonded to a germanium atom can be synthesized.

Further, when a compound in which a tin atom is a central atom and an organic group R ⁴ (for example, an aryl group or a substituted aryl group) is bonded to the tin atom is used, for example, (R ⁴ ) ₄ Sn is reacted with SnI ₄ Depending on the method, (R ⁴ ) _n SnI _m (n + m = 4 and n = 1, 2, or 3) can be synthesized. Specific examples of such reactions are described in, for example, the document Angewante Chemie 75, 225-235 (1963), and various organic groups R ⁴ can be obtained by applying the method described in this document. A compound bonded to a tin atom can be synthesized.

When a compound in which an antimony atom is a central atom and an organic group R ⁴ (for example, an aryl group or a substituted aryl group) is bonded to the antimony atom is used, for example, the same as in the case of the germanium atom or tin atom It can be synthesized by the method.

  The alkyl group in the catalyst refers to a monovalent group in which one hydrogen atom is lost from a chain or cyclic aliphatic hydrocarbon. In the case of a chain alkyl group, it may be a linear alkyl group or a branched alkyl group. Moreover, when it is a cyclic | annular alkyl group, you may comprise only from a cyclic structure and the structure which the chain | strand-shaped alkyl group couple | bonded with the cyclic structure may be sufficient. The number of carbon atoms of this alkyl group is preferably 1-30, more preferably 1-20, still more preferably 1-10, still more preferably 1-5, and particularly preferably 1-3. It is. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a pentyl group, and a cyclohexyl group.

  The alkyl carboxyl group in the catalyst means a group in which a hydrogen atom contained in the alkyl group is substituted with a carboxyl group. That is, this alkyl carboxyl group refers to a group represented by RCOO- when the alkyl group is represented by R-. The alkyl group forming this alkyl carboxyl group may be chain-like or cyclic. In the case of a chain alkyl group, it may be a linear alkyl group or a branched alkyl group. Moreover, when it is a cyclic | annular alkyl group, you may comprise only from a cyclic structure and the structure which the chain | strand-shaped alkyl group couple | bonded with the cyclic structure may be sufficient. The number of carbon atoms of the alkyl carboxyl group is preferably 1-30, more preferably 1-20, still more preferably 1-10, still more preferably 1-5, and particularly preferably 1-1. 3. Specific examples include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, benzyloxycarbonyl group and the like.

  The alkylcarbonyl group in the catalyst means a group in which a hydrogen atom contained in the alkyl group is substituted with a carbonyl group. That is, this alkylcarbonyl group refers to a group represented by RCO- when the alkyl group is represented by R-. The alkyl group forming this alkylcarbonyl group may be a chain or a ring. In the case of a chain alkyl group, it may be a linear alkyl group or a branched alkyl group. Moreover, when it is a cyclic | annular alkyl group, you may comprise only from a cyclic structure and the structure which the chain | strand-shaped alkyl group couple | bonded with the cyclic structure may be sufficient. Carbon number of this alkylcarbonyl group becomes like this. Preferably it is 1-30, More preferably, it is 1-20, More preferably, it is 1-10, More preferably, it is 1-5, Especially preferably, it is 1-1. 3. Specifically, an acetyl group, a propionyl group, a butyryl group, etc. are mentioned.

  The haloalkyl group in the catalyst means a group in which a hydrogen atom of the alkyl group is substituted with a halogen atom. In this haloalkyl group, all hydrogen atoms may be substituted with halogen atoms, or only some of the hydrogen atoms may be substituted. Moreover, this haloalkyl group may be a chain or a ring. In the case of a chain haloalkyl group, it may be a linear haloalkyl group or a branched haloalkyl group. Moreover, when it is a cyclic | annular haloalkyl group, you may comprise only from a cyclic structure and the structure which further linked the cyclic | annular alkyl group or the haloalkyl to the cyclic structure may be sufficient. Examples of the halogen atom possessed by the haloalkyl group include fluorine, chlorine, bromine and iodine. The haloalkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 5, and particularly preferably 1 to 3. It is. Specific examples include a trifluoromethyl group.

  The alkoxy group in the catalyst refers to a group in which an oxygen atom is bonded to the alkyl group. That is, this alkoxy group refers to a group represented by RO- when the alkyl group is represented by R-. The alkyl group forming the alkoxy group may be a chain or a ring. In the case of a chain alkyl group, it may be a linear alkyl group or a branched alkyl group. Moreover, when it is a cyclic | annular alkyl group, you may comprise only from a cyclic structure and the structure which the chain | strand-shaped alkyl group couple | bonded with the cyclic structure may be sufficient. Carbon number of this alkoxy group becomes like this. Preferably it is 1-30, More preferably, it is 1-20, More preferably, it is 1-10, More preferably, it is 1-5, Most preferably, it is 1-3. It is. Specific examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, sec-butoxy group, n-pentoxy group, neopentoxy group and the like.

  The aryl group in the catalyst refers to a monovalent group in which one hydrogen atom bonded to the aromatic hydrocarbon ring is lost. The number of aromatic hydrocarbon rings constituting the aryl group is preferably 1 to 3. When there are a plurality of rings of aromatic hydrocarbons in the molecule, the plurality of rings may or may not be condensed. Specific examples include a phenyl group, a naphthyl group, an anthracenyl group, and a biphenyl group.

The substituted aryl group in the catalyst means a group in which a substituent is bonded to the aromatic ring in the aryl. Examples of the substituent bonded to the aromatic ring include an alkyl group, an alkyloxy group, a cyano group, and an amino group. 1-10 are preferable, as for carbon number of this alkyl group, More preferably, it is 1-5, More preferably, it is 1-3. Of these, a particularly preferred alkyl group is a methyl group. Moreover, 1-10 are preferable, as for carbon number of the alkyl group which forms an alkyloxy group, More preferably, it is 1-5, More preferably, it is 1-3. Of these, a particularly preferred alkyl group forming alkyloxy is a methyl group.
The number of substituents in the substituted aryl group is preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.
The position of the substituent in the substituted aryl is arbitrarily selected. When aryl is phenyl (that is, when the substituted aryl group is a substituted phenyl group), the position of the substituent may be any of ortho, meta, and para with respect to the central atom. Preferably, the position is para.

The substituted heteroaryl group in the said catalyst means the group which the substituent couple | bonded with the aromatic ring in heteroaryl. Examples of the substituent to be bonded include an alkyl group, an alkyloxy group, a cyano group, and an amino group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, still more preferably an alkyl group having 1 to 3 carbon atoms, particularly preferably. , A methyl group.
Moreover, as an alkyl group in the said alkyloxy group, a C1-C10 alkyl group is preferable, More preferably, it is a C1-C5 alkyl group, More preferably, it is a C1-C3 alkyl group. And particularly preferably a methyl group.

The number of the substituents in the substituted heteroaryl group is not particularly limited, but is preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.
The position of the substituent in the substituted heteroaryl group is arbitrarily selected.

The alkenyl group in the catalyst refers to a monovalent group generated by losing one hydrogen atom from a chain or cyclic aliphatic hydrocarbon (alkene) having a double bond. In the case of a chain alkenyl group, it may be a linear alkenyl group or a branched alkenyl group. Moreover, when it is a cyclic | annular alkenyl group, it may be comprised only from a cyclic structure and the structure which the chain structure couple | bonded with the cyclic structure may be sufficient. In this case, the double bond may be present in the cyclic structure portion or may be present in the chain structure portion.
In the case of a chain alkene having one double bond, it is generally represented by “C _k H _2k-1 −” (where k is an integer of 2 or more). The number of double bonds is not particularly limited, and may be one or two or more. The structure of the alkenyl group is not particularly limited, but a structure in which double bonds and single bonds are alternately repeated is preferable.
Although carbon number of an alkenyl group is not specifically limited, Preferably it is 2-20, More preferably, it is 2-10, More preferably, it is 2-5, Most preferably, it is 2-3.

The alkenyl group preferably has a double bond at the terminal carbon in the carbon chain, and more preferably has a structure in which the terminal carbon having the double bond is bonded to the central atom. That is, when the central atom is an oxygen atom, it is a structure (“—O—C═C—”) bonded to the oxygen atom.
Moreover, as a preferable alkenyl group structure, “—CR ³¹ ═CR ³² R ³³ ” can be mentioned. R ³¹ , R ³² and R ³³ may be hydrogen or an alkyl group, and other substituents (for example, alkenyl group, alkyl carboxyl group, haloalkyl group, alkylcarbonyl group, amino group, cyano group, alkoxy group, aryl group) And a substituted aryl group). When R ³¹ , R ³² and R ³³ are all hydrogen, this group is a vinyl group.

The alkynyl group in the above catalyst refers to a monovalent group generated by losing one hydrogen atom from a chain or cyclic aliphatic hydrocarbon (alkyne) having a triple bond. In the case of a chain alkynyl group, it may be a linear alkynyl group or a branched alkynyl group. Moreover, when it is a cyclic | annular alkynyl group, it may be comprised only from a cyclic structure and the structure which the chain structure couple | bonded with the cyclic structure may be sufficient. In this case, the triple bond may be present in the cyclic structure portion or may be present in the chain structure portion.
In the case of a chain alkyne having one triple bond, it is generally represented by “C _k H _2k-3- −” (where k is an integer of 2 or more). The number of triple bonds is not particularly limited, and may be one or two or more. The structure of the alkynyl group is not particularly limited, but a structure in which triple bonds and single bonds are alternately repeated is preferable.
Although carbon number of an alkynyl group is not specifically limited, Preferably it is 2-20, More preferably, it is 2-10, More preferably, it is 2-5, Most preferably, it is 2-3.

The alkynyl group preferably has a triple bond at the terminal carbon in the carbon chain, and more preferably has a structure in which the terminal carbon having the triple bond is bonded to the central atom. That is, when the central atom is an oxygen atom, it is a structure (“—O—C≡C—”) bonded to the oxygen atom.
A preferred alkynyl group structure includes “—C≡CR ³⁴ ”. R ³⁴ may be hydrogen or an alkyl group, and other substituents (for example, alkenyl group, alkylcarboxyl group, haloalkyl group, alkylcarbonyl group, amino group, cyano group, alkoxy group, aryl group, substituted aryl group, etc.) It may be.

As described above, as the catalyst used in the production of the first polymer in the first step, the above-mentioned compound (a) can be used as it is (that is, the catalyst is polymerized together with the vinyl monomer). The first polymer can be obtained by putting in a container). Moreover, you may use the 1 type, or 2 or more types of compound (henceforth a "catalyst precursor") which forms a compound (a), without using the said compound (a).
Here, the catalyst precursor is a material that can form the catalyst before or during the polymerization reaction when the catalyst precursor is present in the reaction system. That is, the catalyst precursor does not correspond to the catalyst in a state before being charged into the reaction vessel (polymerizing the first polymer), but in the reaction vessel (during polymerization), due to a chemical change (chemical reaction), The catalyst can be formed. Even when this catalyst precursor is used, the first polymer can be formed efficiently.

  A compound that can generate an activated radical similar to the activated radical generated from the catalyst during the polymerization reaction in which the vinyl monomer is living radically polymerized to obtain the first polymer corresponds to the catalyst precursor. To do. For example, phosphorus hydride corresponds to the precursor. That is, if hydrogen of the hydride of phosphorus is extracted by peroxide or the like, activated radicals of the phosphorus compound are generated, and living radical polymerization can be performed. Hydrogenation of nitrogen or the like also corresponds to the catalyst precursor.

As the catalyst precursor, a catalyst precursor composed of a compound having a central atom and a catalyst precursor composed of a compound having a halogen atom or halogen (halogen alone) can be used in combination. From these catalyst precursors, a catalyst is formed.
Therefore, in the production of the first polymer, the catalyst may be used as it is, or a catalyst precursor that forms the catalyst may be used. In this case, it is preferable to chemically change the catalyst precursor before the step of performing the polymerization reaction to obtain the first polymer. This chemical change of the catalyst precursor may be performed in a container or the like for performing the polymerization reaction of the first polymer, or may be performed in a container or the like different from the container or the like for performing the polymerization reaction.

Examples of the compound that becomes a precursor of a catalyst having a phosphorus atom as a central atom include compounds having the structure [R ¹ ₂ PH (═O)] shown below. Specifically, (CH ₃ CH ₂ ) ₂ PH (═O), (CH ₃ CH ₃ CH ₂ ) ₂ PH (═O), (CH ₃ CH ₂ ) PhPH (═O), and the like can be given.
Moreover, diethyl phosphite etc. can also be used.
The phosphite may be a phosphonic acid monoester or a diester.

As a compound used as the catalyst precursor centering on a nitrogen atom, an amine compound and an imide compound are mentioned, for example. Specifically, examples of the amine compound include diphenylamine (Ph ₂ NH).
Examples of the imide compound include succinimide [(CH ₂ ) ₂ (C═O) ₂ NH].

  Next, a compound (hereinafter, also referred to as “compound (c)”) that is a precursor of the catalyst (c) having a carbon atom as a central atom is a central atom in the compound (a) that is the catalyst. A compound in which a halogen atom bonded to a carbon atom is replaced with a hydrogen atom can be used. Except for replacing the halogen atom with a hydrogen atom, the above description of the catalyst (c) basically applies to the catalyst precursor (compound (c)) as it is.

  Therefore, for example, as the compound (c), a compound in which one or two hydrogen atoms and two or three substituents for radical stabilization are bonded to a carbon atom serving as a central atom can be preferably used. Here, the substituent for radical stabilization is preferably a substituent that forms a resonance structure together with the central atom. The carbon atom of the central atom may be bonded with one substituent other than the hydrogen atom and the stabilizing radical stabilizing substituent, but the substituent other than the hydrogen atom and the stabilizing radical stabilizing substituent is It is preferably not bonded to the carbon atom of the central atom.

  However, for the catalyst (c), a compound in which a halogen atom is directly bonded to an aromatic ring can be used, but a compound in which a halogen atom of the compound is substituted with a hydrogen atom (that is, an aromatic cyclic carbonization such as benzene). Hydrogen compound) is not preferable as a catalyst precursor of the catalyst (c) because its activity as a catalyst is very low.

  As for the catalyst (c), a methane tetrahalide can be used, but a compound in which all halogen atoms of the compound are substituted with hydrogen atoms (for example, methane) is a gas. Since it is difficult to use as a catalyst precursor of c) and its activity is low, it is not preferred.

  Examples of the compound (c) in which the halogen atom bonded to the carbon atom which is the central atom of the catalyst (c) is substituted with a hydrogen atom include a C—H group bonded to a carbon atom, a silicon atom, a nitrogen atom or a phosphorus atom. And a compound having the above structure.

  The catalyst precursor of the catalyst (c) is preferably a compound having a structure in which two aromatic rings are bonded to methylene.

  The atom (hereinafter referred to as “1-position atom” for convenience), to which the carbon atom serving as the central atom of the catalyst precursor (compound (c)) is bonded, is preferably a carbon atom, a nitrogen atom or a phosphorus atom. Preferably it is a carbon atom. In addition to the hydroxyl group, it is preferable that only an atom selected from a carbon atom and a hydrogen atom is bonded to the 1-position atom. The atom adjacent to the 1-position atom (hereinafter referred to as “2-position atom” for convenience) is preferably a carbon atom. It is preferable that only an atom selected from a carbon atom, an oxygen atom and a hydrogen atom is bonded to the 2-position atom. Moreover, it is preferable that a double bond exists between the 1-position atom and the 2-position atom. Preferably, a compound in which two 2-position atoms are present and a double bond is present between one 2-position atom and the 1-position atom can be used as the catalyst precursor. For example, a catalyst precursor is a compound in which the first atom is a carbon atom, two carbon atoms exist as the second atom, and a double bond exists between one carbon atom and the first carbon atom. Can be used as a body. Further, it is preferable that two or more 2-position atoms are present, and a double bond between one 2-position atom and the 1-position atom and between another 2-position carbon atom and the 1-position carbon atom. The single bond is preferably a part of the conjugated system. For example, the first atom is a carbon atom, two carbon atoms are present as the second atom, a double bond between one second atom and the first atom, another second atom and the first position It is preferable that the single bond between the atoms is a part of the conjugated system.

  Accordingly, the catalyst precursor of the catalyst (c) is preferably a hydrocarbon compound having a structure in which a hydrocarbon group is bonded to an aromatic ring, such as an aryl group, a heteroaryl group, a substituted aryl group, or a substituted heteroaryl group. A compound in which a hydrocarbon group is bonded to is preferable. For example, a compound in which two aromatic substituents are bonded to a methylene group is preferable. Here, the aryl group is preferably a phenyl group or a biphenyl group. Here, the substituent in the substituted aryl group or the substituted heteroaryl group is preferably an alkyl group, an alkoxyl group, a cyano group or the like. As the alkyl group and the alkoxyl group, an alkyl group having 10 or less carbon atoms and an alkoxyl group are more preferable.

  The catalyst precursor in which the carbon atom is the central atom is preferably a compound having no radical reactive double bond. That is, the catalyst precursor of the catalyst (c) may have a double bond having low reactivity with a radical, such as an aromatic double bond (for example, a double bond of a benzene ring). Moreover, even if it is an aliphatic double bond, the double bond with low reactivity with a radical can be used as a catalyst precursor.

  On the other hand, a compound having a double bond or a triple bond only at a position away from a hydrocarbon group (that is, a carbon having a 1-position carbon atom having no double bond or a triple bond and having a 2-position carbon atom or more apart) A compound in which an atom has a double bond or a triple bond) has a tendency that the performance of the catalyst (c) as a catalyst precursor is not relatively high. Therefore, it is preferable to select a compound other than a compound having a double bond or a triple bond only at a position away from the hydrocarbon group as the catalyst precursor of the catalyst (c).

  Preferably, the catalyst precursor having a carbon atom as a central atom is a compound having a hydrocarbon group (that is, Si—CH, N—CH, P—CH) bonded to a silicon atom, a nitrogen atom, or a phosphorus atom. Can also be used.

As the catalyst precursor in which the carbon atom is the central atom, the structure of a preferable compound is exemplified below.
(2-1) A compound in which a hydrogen atom is bonded to a carbon atom adjacent to an aliphatic double bond can be used. In particular, a compound in which a hydrogen atom is bonded to a carbon atom sandwiched between two aliphatic double bonds can be used. For example, a compound having methylene sandwiched between two aliphatic double bonds can be used. For example, a compound (1,4-cyclohexadiene) having a structure represented by the following formula (5) can be used.

In addition, as a compound having a structure similar to 1,4-cyclohexadiene, there is 1,3-cyclohexadiene. In 1,3-cyclohexadiene, one methylene is present between the double bond and the double bond. Since the structure is not sandwiched between groups, the effect of stabilizing the carbon radical of the methylene group is low, and it is not suitable as a catalyst.
(2-2) A compound in which a hydrogen atom is bonded to a carbon atom adjacent to an aromatic ring can be used. In particular, a compound in which a hydrogen atom is bonded to a carbon atom sandwiched between two or more aromatic rings can be used. For example, a compound having methylene sandwiched between two aromatic rings. For example, compounds having structures represented by the following formulas (6) to (14) can be used.

(2-3) A compound in which a hydrogen atom is bonded to a carbon atom adjacent to a double bond such as an ester bond can be used. In particular, a compound in which a hydrogen atom is bonded to a carbon atom sandwiched between two double bonds can be used. For example, a compound having methylene sandwiched between two double bonds can be used. For example, a compound having a structure represented by the following formula (15) can be used.

  Next, as a compound (hereinafter also referred to as “compound (o)”) as a precursor of the catalyst (o) having an oxygen atom as a central atom, the central atom in the compound (a) as the catalyst (o) is used. A compound in which a halogen atom bonded to an oxygen atom is substituted with a hydrogen atom can be used. That is, a compound having a structure in which a hydroxyl group is bonded to a carbon atom, a silicon atom, a nitrogen atom, or a phosphorus atom can be used.

  The compound (o) preferably has a phenolic compound having a structure in which —OH (hydroxyl group) is bonded to an aromatic ring, or a structure in which —OH (hydroxyl group) is bonded to carbon of an aliphatic group. It is an aliphatic alcohol compound.

In the compound (o), an atom to which a hydroxyl group is bonded (hereinafter referred to as “position 1 atom” for convenience) is preferably a carbon atom, a silicon atom, a nitrogen atom, or a phosphorus atom, and among these, more preferably, It is a carbon atom. In addition to the hydroxyl group, it is preferable that only an atom selected from a carbon atom and a hydrogen atom is bonded to the 1-position atom. The atom adjacent to the 1-position atom (hereinafter referred to as “2-position atom” for convenience) is preferably a carbon atom. It is preferable that only an atom selected from a carbon atom, an oxygen atom and a hydrogen atom is bonded to the 2-position atom. Moreover, it is more preferable to have a structure in which a double bond exists between the 1-position atom and the 2-position atom. Preferably, a compound in which two 2-position atoms are present and a double bond is present between one 2-position atom and the 1-position atom can be used as the catalyst precursor of the catalyst (o). .
For example, a compound in which the first atom is a carbon atom, two carbon atoms are present as the second atom, and a double bond exists between one carbon atom and the first carbon atom is catalyzed. It can be used as the catalyst precursor of (o).
It is preferable that two or more 2-position atoms are present, and a double bond between one 2-position atom and the 1-position atom and a single bond between another 2-position carbon and the 1-position carbon. Are preferably part of the conjugated system.
For example, the first atom is a carbon atom, two carbon atoms are present as the second atom, a double bond between one second atom and the first atom, another two atom and 1 It is preferable that the single bond between the coordinate atoms is part of the conjugated system.

  Accordingly, the catalyst precursor of the catalyst (o) is preferably a compound having a structure in which a hydroxyl group is bonded to an aromatic ring. For example, the compound which consists of an aryl group or a substituted aryl group, and a hydroxyl group is mentioned. Preference is given to phenolic compounds. Here, the aryl group is preferably a phenyl group, a biphenyl group, or the like. Moreover, as a substituent of a substituted aryl group, an alkyl group, an alkoxyl group, a cyano group, etc. are preferable. An alkyl group and an alkoxyl group having 10 or less carbon atoms are more preferable.

The catalyst precursor in which oxygen is the central atom is preferably a compound having no radical reactive double bond. That is, the catalyst precursor of the catalyst (o) may have a double bond having low reactivity with a radical, such as an aromatic double bond (for example, a double bond of a benzene ring). . Moreover, even if it is an aliphatic double bond, the double bond with low reactivity with a radical like the double bond in vitamin C can be used as a catalyst precursor of a catalyst (o). Therefore, vitamin C and the like can be used as a catalyst precursor of the catalyst (o). In general, a double bond by a carbon atom having a hydroxyl group is not reactive with a radical. For example, vinyl alcohol _(CH 2 = CH-OH) is not a radical polymerizable monomer. Triple bonds with carbon atoms having hydroxyl groups are likewise not radically reactive and such compounds are not radically polymerizable monomers and can be used as catalyst precursors where oxygen is the central atom.

  On the other hand, a compound having a double bond or a triple bond only at a position away from the hydroxyl group (that is, the carbon atom at the 1-position atom does not have a double or triple bond, or the carbon atom at the 2-position atom or higher) Compounds having carbon atoms separated by a double bond or triple bond) tend not to have a relatively high performance as a catalyst precursor. Therefore, it is preferable to select a compound other than a compound having a double bond or a triple bond only at a position away from the hydroxyl group as the catalyst precursor of the catalyst (o).

  Moreover, it is preferable to use the hydroxyl group containing compound which has the performance as antioxidants, such as vitamin E, as a catalyst precursor of the catalyst (o) whose oxygen is a central atom. However, regarding antioxidants, it is generally considered that a large substituent is present in the vicinity of the hydroxyl group. However, the catalyst precursor in the present invention is not limited to this, and hydroxyl groups are not limited. Large substituents need not be present near the group. For example, even a compound having no substituent other than a hydroxyl group, such as phenol, can be suitably used as a catalyst precursor in the present invention.

  Further, as a catalyst precursor in which oxygen is a central atom, a compound having a hydroxyl group bonded to silicon, nitrogen, or phosphorus (that is, Si—OH, N—OH, P—OH) can also be used.

  The halogen compound serving as the catalyst precursor is not particularly limited as long as it is a compound having a halogen atom. For example, an organic halogen compound, an inorganic halogen compound, etc. are mentioned. Of these, organic halogen compounds are preferred. Examples of the organic halogen compound include an initiator composed of an organic halogen compound described later. That is, an initiator composed of an organic halogen compound can also be used as a catalyst precursor (halogen compound). In this case, a 1st polymer is obtained by using the catalyst precursor which has a central atom, and the initiator which consists of an organic halogen compound.

In the first polymerization step, when a catalyst precursor is used, a radical generator can be used. By using a radical generator, a catalyst can be efficiently obtained from the catalyst precursor.
The radical generator is not particularly limited. Examples of the radical generator include a peroxide-based radical generator and an azo-based radical generator.

  The peroxide radical generator is preferably an organic peroxide. Specifically, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, t-butyl peroxyisopropyl monocarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate , Di (2-ethylhexyl) peroxydicarbonate, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, and dicumyl peroxide. These can be used alone or in combination of two or more.

  Specific examples of the azo radical generator 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'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (methylisobutyrate) and the like. These can be used alone or in combination of two or more.

For example, the correspondence of forming a catalyst using a catalyst precursor, a halogen compound and a radical generator is exemplified below.
When diethyl phosphite (catalyst precursor having a central atom) and diiodoxylene (halogen compound) are used as the catalyst precursor and benzoyl peroxide is used as the radical generator, the catalyst is formed as follows. The
A radical is generated from benzoyl peroxide, the radical derived from benzoyl peroxide extracts hydrogen of diethyl phosphite, and the radical derived from benzoyl peroxide becomes carboxylic acid. In addition, diethyl phosphite from which hydrogen has been extracted becomes a phosphorus radical, and this phosphorus radical extracts iodine from diiodoxylene, or iodine at the end of the polymer during polymerization. Accordingly, diethyl iodine phosphate as a catalyst is formed.
Moreover, the said radical generator has a role which advances superposition | polymerization similarly to a normal radical initiator, when it is used for the synthesis | combination of a 1st polymer.

The initiator used in the first step is an organic halogen compound, and is a compound having at least one carbon atom and a halogen atom bond (hereinafter also referred to as “carbon-halogen bond”).
When the organic halogen compound is used as an initiator, a halogen atom derived from the organic halogen compound (hereinafter referred to as “halogen atom (b)”) is formed by polymerization of a vinyl monomer by the action of the catalyst. It will be located at the end of the growing chain of the first polymer. In the first step, the halogen atom (b) at the end of the growing chain is exchanged with the halogen atom (a) of the catalyst, and the halogen atom (a) or (b) moves through the polymer end in the polymerization process. And it becomes a protecting group for protecting the growing chain during the reaction in the living radical polymerization.

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.

As said halogen atom (b), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Of these halogen atoms, chlorine, bromine and iodine are preferable, and iodine is more preferable.
Further, the halogen atom (b) of the organic halogen compound may be the same as or different from the halogen atom (a) of the catalyst. Even if the halogen atom (b) and the halogen atom (a) are different types of halogen atoms, the halogen atoms can be exchanged between the organic halogen compound and the catalyst. However, if the halogen atom (b) and the halogen atom (a) are the same, it is preferable because the exchange of the halogen atom between the organic halogen compound and the catalyst is carried out satisfactorily. These organic halogen compounds can be used alone or in combination of two or more.

The carbon-halogen bond of the initiator functions 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.
Further, in the production of the first polymer, when the initiator used is a monofunctional initiator, the obtained first polymer 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.
When a bifunctional initiator is used, the first polymer obtained has halogen atoms at both ends.

  The bifunctional initiator 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. Examples thereof include compounds represented by the following general formulas (16) to (25). These compounds can be used alone or in combination of two or more.

上記一般式（１６）において、Ｒ^５１及びＲ^５２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^５１及びＲ^５２は同一であっても、異なっていてもよい。
また、上記一般式（１６）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 (16), R ⁵¹ and R ⁵² 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 ⁵¹ and R ⁵² may be the same or different.
In the general formula (16), 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（１７）において、Ｒ^５３及びＲ^５４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^５３及びＲ^５４は同一であっても、異なっていてもよい。
また、上記一般式（１７）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 (17), R ⁵³ and R ⁵⁴ 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 ⁵³ and R ⁵⁴ may be the same or different.
In the general formula (17), 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（１８）において、Ｒ^５６及びＲ^５７は、水素又は炭素数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^５６及びＲ^５７は同一であっても、異なっていてもよい。
また、上記一般式（１８）において、Ｒ^５５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（１８）において、Ｒ^５８及びＲ^５９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^５８及びＲ^５９は同一であっても、異なっていてもよい。
また、上記一般式（１８）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 (18), R ⁵⁶ and R ⁵⁷ are hydrogen 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 ⁵⁶ and R ⁵⁷ may be the same or different.
In the general formula (18), R ⁵⁵ is a divalent alkylene group having 1 to 20 carbon atoms, and may be branched or linear.
In the general formula (18), R ⁵⁸ and R ⁵⁹ are each an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group. It doesn't matter. R ⁵⁸ and R ⁵⁹ may be the same or different.
In the general formula (18), 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（１９）において、Ｒ^６１及びＲ^６２は、水素又は炭素数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^６１及びＲ^６２は同一であっても、異なっていてもよい。
また、上記一般式（１９）において、Ｒ^６０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（１９）において、Ｒ^６３及びＲ^６４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^６３及びＲ^６４は同一であっても、異なっていてもよい。
また、上記一般式（１９）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 (19), R ⁶¹ and R ⁶² are hydrogen 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 ⁶¹ and R ⁶² may be the same or different.
In the general formula (19), R ⁶⁰ is a divalent alkylene group having 1 to 20 carbon atoms, and may be branched or linear.
In the general formula (19), R ⁶³ and R ⁶⁴ are each an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group. It does n’t matter. R ⁶³ and R ⁶⁴ may be the same or different.
In the general formula (19), 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（２０）において、Ｒ^６５、Ｒ^６６、Ｒ^６７、及びＲ^６８は、水素又は炭素数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^６５、Ｒ^６６、Ｒ^６７、及びＲ^６８は同一であっても、異なっていてもよい。
また、上記一般式（２０）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 (20), R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , and R ⁶⁸ are hydrogen or an alkyl group having 1 to 5 carbon atoms, and this alkyl group may be branched or linear. It doesn't matter. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , and R ⁶⁸ may be the same or different.
In the general formula (20), 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（２１）において、Ｒ^７０、Ｒ^７１、Ｒ^７２、及びＲ^７３は、水素又は炭素数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^７０、Ｒ^７１、Ｒ^７２、及びＲ^７３は同一であっても、異なっていてもよい。
また、上記一般式（２１）において、Ｒ^６９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（２１）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 (21), R ⁷⁰ , R ⁷¹ , R ⁷² , and R ⁷³ are hydrogen or an alkyl group having 1 to 5 carbon atoms, and the alkyl group may be branched or linear. It doesn't matter. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. R ⁷⁰ , R ⁷¹ , R ⁷² , and R ⁷³ may be the same or different.
In the general formula (21), R ⁶⁹ is a divalent alkylene group having 1 to 20 carbon atoms, and may be branched or linear.
In the general formula (21), 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（２２）において、Ｒ^７６、Ｒ^７７、Ｒ^７８、及びＲ^７９は、水素又は炭素数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^７６、Ｒ^７７、Ｒ^７８、及びＲ^７９は同一であっても、異なっていてもよい。
また、上記一般式（２２）において、Ｒ^７５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（２２）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 (22), R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , and R ⁷⁹ are hydrogen or an alkyl group having 1 to 5 carbon atoms, and the alkyl group may be branched or linear. It doesn't matter. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , and R ⁷⁹ may be the same or different.
In the general formula (22), R ⁷⁵ is a divalent alkylene group having 1 to 20 carbon atoms, and may be branched or linear.
In the general formula (22), 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（２３）において、Ｒ^８０、Ｒ^８１、Ｒ^８２、及びＲ^８３は、水素又は炭素数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^８０、Ｒ^８１、Ｒ^８２、及びＲ^８３は同一であっても、異なっていてもよい。
また、上記一般式（２３）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 (23), R ⁸⁰ , R ⁸¹ , R ⁸² , and R ⁸³ are hydrogen or an alkyl group having 1 to 5 carbon atoms, and the alkyl group may be branched or linear. It doesn't matter. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. R ⁸⁰ , R ⁸¹ , R ⁸² , and R ⁸³ may be the same or different.
In the general formula (23), 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（２４）において、Ｒ^８４、Ｒ^８５、Ｒ^８６、及びＲ^８７は、水素又は炭素数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^８４、Ｒ^８５、Ｒ^８６、及びＲ^８７は同一であっても、異なっていてもよい。
また、上記一般式（２４）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 above general formula (24), R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , and R ⁸⁷ are hydrogen or an alkyl group having 1 to 5 carbon atoms, and this alkyl group may be branched or linear. It doesn't matter. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , and R ⁸⁷ may be the same or different.
In the general formula (24), 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（２５）において、Ｒ^８９、Ｒ^９０、Ｒ^９１、及びＲ^９２は、水素又は炭素数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^８９、Ｒ^９０、Ｒ^９１、及びＲ^９２は同一であっても、異なっていてもよい。
また、上記一般式（２５）において、Ｒ^８８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（２５）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 (25), R ⁸⁹ , R ⁹⁰ , R ⁹¹ , and R ⁹² are hydrogen or an alkyl group having 1 to 5 carbon atoms, and the alkyl group may be branched or linear. It doesn't matter. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group. R ⁸⁹ , R ⁹⁰ , R ⁹¹ , and R ⁹² may be the same or different.
In the general formula (25), R ⁸⁸ is a divalent alkylene group having 1 to 20 carbon atoms, and may be branched or linear.
In the general formula (25), 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, dibromoxylene, dichloroxylene, diethyl-2,5-diiododipate, diethyl-2,5-dibromoadipate, diethyl-2,5-dichloro. Examples include adipate.

〔但し、上記一般式（２６）において、Ｒ^９１は、水素原子、又は炭素数１〜５のアルキル基を示し、Ｒ^９２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。〕

〔但し、上記一般式（２７）において、Ｒ^９３は、水素原子、又は炭素数１〜５のアルキル基を示し、Ｒ^９４は、炭素数１〜５のアルキレン基を示し、Ｒ^９５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 (26), C (CH ₃ ) ₂ (CN) I represented by the following general formula (27), and the following formula (30c) And the like.

[However, in the said General formula (26), ^R91 shows a hydrogen atom or a C1-C5 alkyl group, ^R92 shows a hydrogen atom or a C1-C5 alkyl group, X Represents a halogen atom selected from a chlorine atom, a bromine atom and an iodine atom. ]

[In the general formula (27), R ⁹³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁹⁴ represents an alkylene group having 1 to 5 carbon atoms, and R ⁹⁵ represents hydrogen. An atom, a hydroxyl group, a carboxyl group or an amino group is shown, and X represents a halogen atom selected from a chlorine atom, a bromine atom and an iodine atom. ]

  Specific examples of the initiator composed of an organic halogen compound include methyl chloride, methylene chloride, chloroform, chloroethane, dichloroethane, trichloroethane, bromomethyl, dibromomethane, bromoform, bromoethane, dibromoethane, tribromoethane, and tetrabromoethane. , Bromotrichloromethane, dichlorodibromomethane, chlorotribromomethane, iodotrichloromethane, dichlorodiiodomethane, iodotribromomethane, dibromodiiodomethane, bromotriiodomethane, iodoform, diiodomethane, methyl iodide, isopropyl chloride, chloride t-butyl, isopropyl bromide, t-butyl bromide, triiodoethane, ethyl iodide, diiodopropane, isopropyl iodide, t-butyl iodide, bromodichloro Tan, chlorodibromoethane, bromochloroethane, iododichloroethane, chlorodiiodoethane, diiodopropane, chloroiodopropane, iododibromoethane, bromoiodopropane, 2-iodo-2-polyethyleneglycosylpropane, 2-iodo-2-amidino Propane, 2-iodo-2-cyanobutane, 2-iodo-2 monocyano-4-methylpentane, 2-iodo-2-cyano-4-methyl-4-methoxypentane, 4-iodo-4-cyano-pentanoic acid, Methyl-2-iodoisobutyrate, 2-iodo-2-methylpropanamide, 2-iodo-2,4-dimethylpentane, 2-iodo-2-cyanobutanol, 4-methylpentane, cyano-4-methylpentane 2-iodo-2-methyl-N- (2-hydroxyethyl) Propionamide 4-methylpentane, 2-iodo-2-methyl-N- (1,1-bis (hydroxymethyl) -2-hydroxyethyl) propionamide 4-methylpentane, 2-iodo-2- (2-imidazoline -2-yl) propane, 2-iodo-2- (2- (5-methyl-2-imidazolin-2-yl) propane, etc. These halides may be used alone or in combination of two or more. Can be used.

  In the production of the first polymer, the organic halogen compound can be used as it is as the initiator. Moreover, you may use the 1 type, or 2 or more types of compound (henceforth an "initiator precursor") which forms said organic halogen compound, without using the said initiator. 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 an organic halogen compound. For example, an initiator precursor composed of an organic compound such as an azo compound (hereinafter referred to as “initiator precursor (a)”) and an initiator precursor composed of a single halogen (hereinafter referred to as “initiator precursor (b)”. Can be used in combination. Specifically, as shown in the following formula (30), 4,4-azobis-4-cyanovaleric acid (30a) of an azo compound as an initiator precursor (a), and an initiator precursor (b) ) To form an initiator (30c) from an initiator precursor of iodine (30b). This initiator (30c) is a monofunctional initiator included in the general formula (27).

Examples of the initiator precursor (a) include azo compounds and organic peroxides. These can be used alone or in combination of two or more.
Examples of the azo compound include 4,4-azobis-4-cyanovaleric acid, 2,2′-azobis- {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propion. Amide} and 2,2′-azobis {2-methyl-N- [2- (1-hydroxybutyl)] propionamide} and the like.
Moreover, as said organic peroxide, Disuccinic acid peroxide (For example, (brand name) "Perroyl SA", the product made from NOF Corporation) etc. are mentioned.
Examples of the initiator precursor (b) include fluorine, chlorine, bromine and iodine alone. Of these halogen simple substances, chlorine, bromine and iodine are preferable, and iodine is more preferable. These can be used alone or in combination of two or more.

The vinyl monomer forming the first polymer is not particularly limited as long as it is a vinyl unsaturated compound having radical polymerizability. Examples of vinyl unsaturated compounds include (meth) acrylic compounds, aromatic vinyl compounds, conjugated diene compounds, maleimide compounds, vinyl ester compounds, vinyl ether compounds, alkene compounds, which are unsaturated compounds having a (meth) acryloyl group , Unsaturated acid anhydrides, monoalkyl esters of unsaturated dicarboxylic acids, dialkyl esters of unsaturated dicarboxylic acids, and the like. These compounds can be used alone or in combination of two or more.
The (meth) acrylic compound includes an unsaturated carboxylic acid compound, a (meth) acrylic acid ester compound, a hydroxyl group-containing unsaturated compound, an amino group-containing unsaturated compound, an amide group-containing unsaturated compound, and an alkoxyl group-containing unsaturated compound. Examples thereof include saturated compounds, cyano group-containing unsaturated compounds, and nitrile group-containing unsaturated compounds. Although a compound is illustrated below, the unsaturated compound which does not have a (meth) acryloyl group is also included.

  Examples of the unsaturated carboxylic acid compound include (meth) acrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, α-chloroacrylic acid, cinnamic acid, α-chloroacrylic acid and the like. It is done. These compounds can be used alone or in combination of two or more.

  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 hydroxyl group-containing unsaturated compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Mono (meth) acrylic acid ester of polyalkylene glycol such as 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol, polypropylene glycol, p-hydroxystyrene, m-hydroxystyrene, o-Hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol and the like. These may 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.

Preferred examples of use of the vinyl monomer are shown below.
The vinyl monomer is preferably a (meth) acrylic compound, more preferably a (meth) acrylic acid ester compound, and still more preferably a methacrylic acid ester compound.
The proportion of the (meth) acrylic compound used is preferably 40 to 100% by mass, more preferably 60% by mass or more, when the total amount of the vinyl monomer forming the first polymer is 100% by mass. 80% by mass or more is more preferable.
Moreover, when the total amount of the (meth) acrylic compound used for the vinyl monomer forming the first polymer is 100% by mass, the usage ratio of the (meth) acrylic acid ester compound is 40 to 100% by mass. % Is preferable, 60% by mass or more is more preferable, and 80% by mass or more is further preferable.
Further, when the vinyl monomer forming the first polymer contains a (meth) acrylic acid ester compound (methacrylic acid ester compound and acrylic acid ester compound), use of the methacrylic acid ester compound and the acrylic acid ester compound The proportion of the amount is preferably 50 to 100% by mass and 0 to 50% by mass, more preferably 70 to 100% by mass and 0 to 30% by mass, respectively, when the total of both is 100% by mass. More preferred are mass% and 0-10 mass%. When the ratio of the compound used is in the above range, a cured product having excellent strength and elasticity can be obtained.

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

  In the first step, when the initiator and the initiator precursor used are a bifunctional initiator or an initiator precursor that forms a bifunctional initiator, the first polymer obtained is Have a halogen atom. 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 catalyst used is preferably 0.001 to 2 mol, more preferably 0.005 to 1 mol, and still more preferably 0.01 to 0.5 mol, relative to 100 mol of the total amount of vinyl monomers. Is a mole. When the amount of the catalyst used is within the above range, a first polymer having a low degree of dispersion can be efficiently obtained.

  Moreover, the usage-amount in the case of using a catalyst precursor as a catalyst is as follows. The amount of the catalyst precursor having a central atom is preferably 0.001 to 2 mol, more preferably 0.01 to 1 mol, still more preferably 0.02 to 100 mol of the total amount of vinyl monomers. 0.5 mole. The amount of the halogen-containing catalyst precursor or halogen alone is preferably 0.01 to 10 mol, more preferably 0.05 to 5 mol, and still more preferably with respect to 100 mol of the total amount of vinyl monomers. 0.1 to 3 mol. When the usage-amount of a catalyst precursor exists in the said range, the 1st polymer with a small dispersion degree is obtained efficiently.

  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, the 1st polymer with a 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, the 1st polymer with small dispersion degree is obtained efficiently.

  Furthermore, when a radical generator is used, the amount of radical generator 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. Preferably it is 0.1-3 mol. When the amount of the radical generator used is within the above range, a first polymer having a low degree of dispersion can be efficiently obtained.

  The living radical polymerization in the first step 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 living radical polymerization is based on solution polymerization using a polymerization solvent, the polymerization solvent includes cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene and xylene, and esters such as ethyl acetate and butyl acetate. And ketones such as acetone, methyl ethyl ketone and cyclohexanone, and alcohols such as methyl orthoformate, 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 caused by the polymerization solvent occurs, and it may be difficult to control the polymerization such as molecular weight control, molecular weight distribution (dispersion degree) control, and terminal living property.

  The polymerization temperature in the first step is preferably 30 ° C to 130 ° C, more preferably 40 ° C to 110 ° C, 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 curable composition that gives a cured product having excellent strength and elasticity when the finally obtained vinyl polymer is used 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 the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is in the above range, the resulting cured polymer has excellent strength and elasticity when using the finally obtained vinyl polymer. It can be set as the curable composition which gives a thing.

  The first polymer includes a halogen atom derived from the catalyst or the initiator 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 end of the first polymer is modified by terminal modification described later, and the (meth) acryloyl group, hydroxyl group, carboxyl group, and amino group are used. This is a step of making a vinyl polymer having at least one selected functional group at the molecular end.

〔但し、一般式（４１）において、Ｒ^１は水素原子又はメチル基であり、Ｍ^＋はアルカリ金属イオン、又は４級アンモニウムイオンである。〕
（２）末端ハロゲンの置換の直接置換による、水酸化ナトリウム等の水酸化化合物を用いた、ヒドロキシル基等の導入。
（３）ハロゲン−アミノ置換反応による、アミノエタノール、グリシン、（アミノイソシアネート）、エチレンジアミン及びカダベリン等のアミン化合物を用いた、ヒドロキシル基、カルボン酸基、イソシアネート基及びアミノ基等の導入。
（４）ハロゲン−メルカプト置換反応による、メルカプトエタノール、メルカプトプロピオン酸、メルカプトイソシアネート及びメルカプトアミン等のメルカプト化合物を用いた、ヒドロキシル基、カルボン酸基、イソシアネート基及びアミノ基等の導入。
（５）末端ハロゲンをクロロスルホン酸で置換後、加水分解を行う等による、カルボキシル基等の導入。
（６）ハロゲン−カルボン酸塩置換反応による、コハク酸モノナトリウム塩等を用いた、カルボキシル基等の導入。 As the terminal modification method of the first polymer in the second step, a general chemical reaction can be used. Moreover, the compound (molecular terminal modifier) used when introducing a functional group into the terminal of the vinyl polymer is not particularly limited, and a general compound can be used.
In the second step, for example, the following modes (methods) can be mentioned. According to these methods, the first polymer can be efficiently end-modified without deteriorating.
(1) Introduction of a (meth) acryloyl group using a compound represented by the following general formula (41).

[However, in the general formula (41), R ¹ is a hydrogen atom or a methyl group, M ⁺ is an alkali metal ion, or a quaternary ammonium ion. ]
(2) Introduction of a hydroxyl group or the like using a hydroxide compound such as sodium hydroxide by direct substitution of the terminal halogen.
(3) Introduction of a hydroxyl group, a carboxylic acid group, an isocyanate group, an amino group, and the like using an amine compound such as aminoethanol, glycine, (aminoisocyanate), ethylenediamine, and cadaverine by a halogen-amino substitution reaction.
(4) Introduction of a hydroxyl group, a carboxylic acid group, an isocyanate group, an amino group, and the like using a mercapto compound such as mercaptoethanol, mercaptopropionic acid, mercaptoisocyanate, and mercaptoamine by a halogen-mercapto substitution reaction.
(5) Introduction of a carboxyl group or the like by hydrolyzing after replacing the terminal halogen with chlorosulfonic acid.
(6) Introduction of a carboxyl group or the like using succinic acid monosodium salt or the like by a halogen-carboxylate substitution reaction.

The method (1) will be described. In the compound represented by the general formula (41), M ⁺ is a counter cation of an oxyanion. Examples of M ⁺ include alkali metal ions, specifically lithium ions, sodium ions, potassium ions, and quaternary ammonium ions. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, and dimethylpiperidinium ion. Among these, sodium is preferable. Ions and potassium ions. Among these, preferable compounds include potassium (meth) acrylate, sodium (meth) acrylate, and the like. These can be used alone or in combination of two or more.

In the method (1), the first polymer is reacted with the compound represented by the general formula (41). Then, by the substitution reaction between the halogen atom at the molecular end of the first polymer and the compound represented by the general formula (41), the elimination of the terminal halogen atom in the first polymer results in the general formula (41). A vinyl polymer in which a (meth) acryloyl group derived from a compound represented by
The usage-amount of the compound represented by the said General formula (41) becomes like this. Preferably it is 1-10 equivalent with respect to a terminal halogen atom, More preferably, it is 1-5 equivalent.
In addition, the reaction may be performed in a solvent. In this case, the solvent to be used is not particularly limited. However, since this reaction is a nucleophilic substitution reaction, it is preferable to use a polar solvent. Examples of the polar solvent include tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric triamide, and acetonitrile.
Moreover, 0-80 degreeC is preferable normally in this reaction, and 25 degreeC-70 degreeC is more preferable.

In the method (2), 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.
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 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.
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 (4), 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.
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 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.
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.
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 (6), 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, 0-80 degreeC is preferable normally and 25 degreeC-70 degreeC is more preferable.

  In addition, the vinyl polymer which has the functional group chosen from a hydroxyl group, a carboxyl group, an isocyanate group, and an amino group at the terminal by the method of said (2)-(6) as mentioned above is obtained. By using a vinyl polymer having these functional groups, a vinyl polymer having a (meth) acryloyl group at the terminal can be obtained. That is, a vinyl polymer having a functional group such as a hydroxyl group, a carboxyl group, an isocyanate group and an amino group at the terminal, and a vinyl unsaturated compound having a functional group capable of reacting with the functional group (hereinafter referred to as “unsaturated”). (Also referred to as compound (a) ”), a vinyl polymer having a (meth) acryloyl group at the terminal can be obtained. The unsaturated compound (a) having a functional group capable of reacting with these functional groups is not particularly limited. Specifically, a vinyl unsaturated compound having a carboxyl group, a glycidyl group, a hydroxyl group, or an isocyanate group may be used. Can be mentioned.

〔但し、一般式（４２）において、Ｒ^６は水素原子又はメチル基であり、Ｒ^７はあってもなくてもよく、Ｒ^７を有する場合は、−Ｃ（Ｏ）−Ｏ−、−ＯＣ（Ｏ）−、−ＮＨ−、又は−Ｃ_６Ｈ_４−であり、Ｒ^８は、−Ｒ^９−Ｏ−（Ｒ^９は炭素数２〜４のアルキレン基）、−Ｒ^１０−Ｃ（Ｏ）−Ｏ−（Ｒ^１０は炭素数１〜８のアルキレン基）、−Ｒ^１１−Ｏ−Ｃ（Ｏ）−Ｒ^１２−（Ｒ^１１は炭素数１〜８のアルキレン基、Ｒ^１２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。〕
上記一般式（４２）に示されるカルボキシル基を有する不飽和化合物（ａ）としては、具体的には、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、マレイン酸、フマル酸、及び４−カルボキシルスチレン等が挙げられる。 As unsaturated compound (a) which has said carboxyl group, the compound shown by following General formula (42) is mentioned, for example. These compounds can be used alone or in combination of two or more.

[However, in General Formula (42), R ⁶ is a hydrogen atom or a methyl group, R ⁷ may or may not be present, and when R ⁷ is present, —C (O) —O—, —OC (O) —, —NH—, or —C ₆ H ₄ —, wherein R ⁸ is —R ⁹ —O— (R ⁹ is an alkylene group having 2 to 4 carbon atoms), —R ¹⁰ —C (O ) —O— (R ¹⁰ is an alkylene group having 1 to 8 carbon atoms), —R ¹¹ —O—C (O) —R ¹² — (R ¹¹ is an alkylene group having 1 to 8 carbon atoms, and R ¹² is carbon number) 1 to 8 alkylene groups), —C ₆ H ₄ —, or —CH ₂ ═CH ₂ —, and n is 0 to 4. ]
Specific examples of the unsaturated compound (a) having a carboxyl group represented by the general formula (42) include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, and 4 -Carboxylstyrene etc. are mentioned.

〔但し、一般式（４３）において、Ｒ^１３は水素原子又はメチル基であり、Ｒ^１４はあってもなくてもよく、Ｒ^１４を有する場合は、−Ｃ（Ｏ）−Ｏ−、−ＯＣ（Ｏ）−、−ＮＨ−、又は−Ｃ_６Ｈ_４−であり、Ｒ^１５は−Ｒ^１６−Ｏ−（Ｒ^１６は炭素数２〜４のアルキレン基）、−Ｒ^１７−Ｃ（Ｏ）−Ｏ−（Ｒ^１７は炭素数１〜８のアルキレン基）、−Ｒ^１８−Ｏ−Ｃ（Ｏ）−Ｒ^１９−（Ｒ^１８は炭素数１〜８のアルキレン基、Ｒ^１９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。〕
上記一般式（４３）に示されるグリシジル基を有する不飽和化合物（ａ）としては、具体的には、グリシジル（メタ）アクリレート、３，４−エポキシシクロヘキシルメチルメタクリレート等が挙げられる。 Examples of the unsaturated compound (a) having the glycidyl group include a compound represented by the following general formula (43). These compounds can be used alone or in combination of two or more.

[However, in General Formula (43), R ¹³ is a hydrogen atom or a methyl group, R ¹⁴ may or may not be present, and when R ¹⁴ is present, —C (O) —O—, —OC (O) —, —NH—, or —C ₆ H ₄ —, wherein R ¹⁵ is —R ¹⁶ —O— (R ¹⁶ is an alkylene group having 2 to 4 carbon atoms), —R ¹⁷ —C (O). —O— (R ¹⁷ is an alkylene group having 1 to 8 carbon atoms), —R ¹⁸ —O—C (O) —R ¹⁹ — (R ¹⁸ is an alkylene group having 1 to 8 carbon atoms, R ¹⁹ is 1 carbon atom) 8 alkylene _{group), - C 6 H 4 -} , or _{-CH 2} = CH 2 - a and, n represents 0-4. ]
Specific examples of the unsaturated compound (a) having a glycidyl group represented by the general formula (43) include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl methacrylate.

〔但し、一般式（４４）において、Ｒ^２０は水素原子又はメチル基であり、Ｒ^２１はあってもなくてもよく、Ｒ^２１を有する場合は、−Ｃ（Ｏ）−Ｏ−、−ＯＣ（Ｏ）−、−ＮＨ−、又は−Ｃ_６Ｈ_４−であり、Ｒ^２２は−Ｒ^２３−Ｏ−（Ｒ^２３は炭素数２〜４のアルキレン基）、−Ｒ^２４−Ｃ（Ｏ）−Ｏ−（Ｒ^２４は炭素数１〜８のアルキレン基）、−Ｒ^２５−Ｏ−Ｃ（Ｏ）−Ｒ^２６−（Ｒ^２５は炭素数１〜８のアルキレン基、Ｒ^２６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。〕
上記一般式（４４）に示されるヒドロキシル基を有する不飽和化合物（ａ）としては、具体的には、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、ヒドロキシペンチル（メタ）アクリレート、ヒドロキシヘキシル（メタ）アクリレート、ヒドロキシオクチル（メタ）アクリレート、ペンタエリスリトールトリ、ジ又はモノ（メタ）アクリレート及びトリメチロールプロパンジ又はモノ（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート等が挙げられる。 As unsaturated compound (a) which has said hydroxyl group, the compound shown by following General formula (44) is mentioned, for example. These compounds can be used alone or in combination of two or more.

[However, in General Formula (44), R ²⁰ is a hydrogen atom or a methyl group, R ²¹ may or may not be present, and when R ²¹ is present, —C (O) —O—, —OC (O) —, —NH—, or —C ₆ H ₄ —, wherein R ²² is —R ²³ —O— (R ²³ is an alkylene group having 2 to 4 carbon atoms), —R ²⁴ —C (O). —O— (R ²⁴ is an alkylene group having 1 to 8 carbon atoms), —R ²⁵ —O—C (O) —R ²⁶ — (R ²⁵ is an alkylene group having 1 to 8 carbon atoms, and R ²⁶ is 1 carbon atom) 8 alkylene group), _- C 6 _{H 4 -} or _{-CH 2} = CH 2 - a and, n represents 0-4. ]
Specific examples of the unsaturated compound (a) having a hydroxyl group represented by the general formula (44) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth). Hydroxyalkyl (such as acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, pentaerythritol tri, di or mono (meth) acrylate and trimethylolpropane di or mono (meth) acrylate ( And (meth) acrylate.

〔但し、一般式（４５）において、Ｒ^２７は水素原子又はメチル基であり、Ｒ^２８はあってもなくてもよく、Ｒ^２８を有する場合は、−Ｃ（Ｏ）−Ｏ−、−ＯＣ（Ｏ）−、−ＮＨ−、又は−Ｃ_６Ｈ_４−であり、Ｒ^２９は−Ｒ^３０−Ｏ−（Ｒ^３０は炭素数２〜４のアルキレン基）、−Ｒ^３１−Ｃ（Ｏ）−Ｏ−（Ｒ^３１は炭素数１〜８のアルキレン基）、−Ｒ^３２−Ｏ−Ｃ（Ｏ）−Ｒ^３３−（Ｒ^３２は炭素数１〜８のアルキレン基、Ｒ^３３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。〕
上記一般式（４５）に示されるイソシアネート基を有する不飽和化合物（ａ）としては、具体的には、２−エチルイソシアネート（メタ）アクリレート、イソシアネート（メタ）アクリレート等が挙げられる。 As unsaturated compound (a) which has said isocyanate group, the compound shown by following General formula (45) is mentioned. These compounds can be used alone or in combination of two or more.

[However, in the general formula (45), R ²⁷ is a hydrogen atom or a methyl group, R ²⁸ may or may not be present, and when R ²⁸ is present, —C (O) —O—, —OC (O) —, —NH—, or —C ₆ H ₄ —, wherein R ²⁹ is —R ³⁰ —O— (R ³⁰ is an alkylene group having 2 to 4 carbon atoms), —R ³¹ —C (O). —O— (R ³¹ is an alkylene group having 1 to 8 carbon atoms), —R ³² —O—C (O) —R ³³ — (R ³² is an alkylene group having 1 to 8 carbon atoms, and R ³³ is 1 carbon atom) 8 alkylene _{group), - C 6 H 4 -} , or _{-CH 2} = CH 2 - a and, n represents 0-4. ]
Specific examples of the unsaturated compound (a) having an isocyanate group represented by the general formula (45) include 2-ethyl isocyanate (meth) acrylate and isocyanate (meth) acrylate.

  A vinyl polymer having a (meth) acryloyl group at its end by reacting a vinyl polymer having a terminal functional group selected from a hydroxyl group, a carboxyl group, an isocyanate group and an amino group with the unsaturated compound (a). When used as a polymer, the amount of the unsaturated compound (a) used is usually 0.8 to 4 mol with respect to 1 mol of the vinyl polymer having the functional group at its terminal. Moreover, it is 1-2 equivalent normally with respect to the said functional group terminal 1 equivalent. When the amount of the unsaturated compound (a) is less than 0.8 mol, there is a vinyl polymer having no (meth) acryloyl group introduced at the terminal, which may cause poor curing. When the amount is more than 4 mol, a large amount of the compound having a (meth) acryloyl group remains, and the storage stability may be deteriorated.

The compatibility between the type of the functional group in the vinyl polymer having a functional group selected from a hydroxyl group, a carboxyl group, an isocyanate group and an amino group and the type of the unsaturated compound (a) is not particularly limited. For example, it can be set as the following combinations, and the reaction is smoothly performed with these combinations.
(1) When the functional group of the vinyl polymer is a hydroxyl group, the unsaturated compound (a) to be used is preferably an unsaturated compound having an isocyanate group.
(2) When the functional group of the vinyl polymer is a carboxyl group, an unsaturated compound having a glycidyl group, a carboxyl group, or an amino group is preferable.
(3) When the functional group of the vinyl polymer is an isocyanate group, an unsaturated compound having a hydroxyl group is preferable.
(4) When the functional group which the said vinyl polymer has is an amino group, the unsaturated compound which has a glycidyl group, a carboxyl group, or an isocyanate group is preferable.

Moreover, in the said 1st process, when the used initiator and initiator precursor are initiator precursors which form a monofunctional initiator or a monofunctional initiator, the 1st polymer obtained is a piece. It has a halogen atom only at the terminal. In this case, the other terminal not having a halogen atom has a structure derived from an initiator.
In this case, when the terminal of the first polymer is an initiator-derived hydroxyl group, carboxyl group, isocyanate group, or amino group, the terminal having a structure derived from the initiator is a (meth) acryloyl group as described above. Can be modified to the terminal end.

In addition to the first step and the second step, the method for producing the vinyl polymer having the functional group according to the present invention further includes a desolubilization step (third step) for removing residual volatiles after the second step. Step).
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 polymer has at the terminal will not dissociate from a vinyl polymer, and decomposition | disassembly of a vinyl polymer will not arise easily. On the other hand, when it exceeds 250 ° C., the functional group possessed by the vinyl polymer at its terminal may be dissociated, and the vinyl polymer may be partially decomposed to produce a low molecular weight product. Coloring may also occur.

  When a (meth) acrylic compound is used as the vinyl monomer, the vinyl polymer obtained according to the present invention is a polymer containing a unit derived from this (meth) acrylic compound in the main chain ((meta ) Acrylic polymer). In the present invention, this (meth) acrylic polymer is preferred.

  The molecular weight of the vinyl polymer in the present invention is a number average molecular weight (Mn) in terms of polystyrene by gel permeation chromatography (GPC), preferably 3000 to 50000, more preferably 6000 to 25000, and 8000 to 15000. Is more preferable. When Mn is lower than 3000, the crosslink density of the cured product becomes too high, and the elongation of the cured product may be remarkably reduced. On the other hand, if Mn is higher than 50000, the viscosity becomes very high, and workability may be remarkably deteriorated.

  Further, the degree of dispersion of the vinyl polymer is less than 2.0 (usually 1.05 or more), preferably 1.3 to 1.8, more preferably less than 1.6. When the degree of dispersion is in the above range, a cured product having excellent strength and elasticity can be obtained.

The vinyl polymer in the present invention has at least one functional group selected from a (meth) acryloyl group, a hydroxyl group, a carboxyl group, and an amino group at the molecular end. This vinyl polymer has the above functional group at at least one of its molecular ends, and preferably has the above functional group at both ends.

Moreover, in the formation of the first polymer, when a vinyl monomer having no functional group such as a (meth) acrylic acid ester compound is used, the obtained first polymer is a polymer having no functional group. It is. In this case, the average number (number f) of functional groups of the vinyl polymer after terminal modification is preferably 1 to 2, more preferably 1.4 or more, and still more preferably 1.5 or more. Yes, particularly preferably 1.8 or more.
Further, in the formation of the first polymer, when the vinyl monomer having the functional group described above (hydroxyl group-containing unsaturated compound, amino group-containing unsaturated compound, etc.) is used, the obtained first polymer is A polymer having a functional group derived from a vinyl monomer in the molecular chain. Further, when the first polymer is terminal-modified, it becomes a polymer having a functional group at the molecular end. In this case, when the types of functional groups in the molecular chain are the same as the functional groups at the molecular ends, the average number of functional groups in the vinyl polymer after terminal modification is preferably 1.0 to 10.0. More preferably, it is 1.4-4.0, More preferably, it is 1.8-3.5. The average number of functional groups (number f) is calculated as follows.
Average number (number f) = concentration of the functional group in the vinyl polymer [mol / kg] / (1000 / number average molecular weight)
When the average number (number f) is less than 1.0, the cured product has a low crosslink density and may have a low breaking strength. On the other hand, when the number is more than 10.0, the crosslink density becomes high, and the cured product may be brittle and not stretched.

  The curable composition of the present invention contains a vinyl polymer having the functional group at the molecular end. The curable composition may be the total amount of the above-mentioned vinyl polymer, or may be partially contained. The content of the vinyl polymer in the curable composition is preferably 10 to 100% by mass, more preferably 20 to 90% by mass, even more preferably when the total amount of the curable composition is 100% by mass. Is 30 to 80% by mass. If content of a vinyl type polymer is this range, it can be set as the curable composition which gives the hardened | cured material which is excellent in intensity | strength and elasticity.

  The curable composition of the present invention can further contain a polymerizable monomer and / or oligomer in addition to the vinyl polymer as long as the object of the present invention is achieved. As the polymerizable monomer and / or oligomer, a monomer and / or oligomer having a radical polymerizable group or a single monomer having an anion polymerizable group from the viewpoint of obtaining rapid curability. Body and / or oligomers.

  Examples of the radical polymerizable group include (meth) acryloyl groups such as (meth) acrylic groups, styrene groups, acrylonitrile groups, vinyl ester groups, N-vinylpyrrolidone groups, acrylamide groups, conjugated diene groups, vinyl ketone groups, and chlorides. A vinyl group etc. are mentioned. Among these, those having a (meth) acryloyl group similar to the vinyl polymer used in the present invention are preferable. These can be used alone or in combination of two or more.

  Examples of the anionic polymerizable group include (meth) acryloyl groups such as (meth) acrylic groups, styrene groups, acrylonitrile groups, N-vinylpyrrolidone groups, acrylamide groups, conjugated diene groups, and vinyl ketone groups. Among these, those having a (meth) acryloyl group similar to the vinyl polymer used in the present invention are preferable. These can be used alone or in combination of two or more.

  Examples of the polymerizable monomer include (meth) acrylate compounds, cyclic acrylates, styrene compounds, acrylonitrile, vinyl ester compounds, N-vinyl pyrrolidone, acrylamide compounds, conjugated diene compounds, vinyl ketone compounds. , Vinyl halide / vinylidene halide compounds, polyfunctional compounds and the like. These can be used alone or in combination of two or more.

  Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate , N-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) Dodecyl acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, (meth Benzyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate , Glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, (Meth) acrylic acid 2-trifluoromethylethyl, (meth) acrylic acid 2-perfluoroethylethyl, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutylethyl, (meth) acrylic acid 2-per Fluoroethyl, perfluoromethyl (meth) acrylate , (Meth) acrylic acid diperfluoromethyl methyl, (meth) acrylic acid 2-perfluoromethyl-2-perfluoroethyl ethyl, (meth) acrylic acid 2-perfluorohexyl ethyl, (meth) acrylic acid 2-par Fluorodecyl ethyl, (meth) acrylic acid 2-perfluorohexadecyl ethyl, isobornyl acrylate and the like can be mentioned. These can be used alone or in combination of two or more.

  Examples of the styrenic compound include styrene and α-methylstyrene. Examples of the vinyl ester compound include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of acrylamide compounds include acrylamide and N, N-dimethylacrylamide. Examples of the conjugated diene compound include butadiene and isoprene. Examples of the vinyl ketone compound include methyl vinyl ketone. Examples of the vinyl halide / vinylidene halide compound include vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, and vinylidene bromide. These can be used alone or in combination of two or more.

  Examples of the polyfunctional compound include trimethylolpropane triacrylate, neopentyl glycol polypropoxydiacrylate, trimethylolpropane polyethoxytriacrylate, bisphenol F polyethoxydiacrylate, bisphenol A polyethoxydiacrylate, and dipentaerythritol polyhexa. Nolide hexaacrylate, tris (hydroxyethyl) isocyanurate polyhexanolide triacrylate, tricyclodecane dimethylol diacrylate 2- (2-acryloyloxy-1,1-dimethyl) -5-ethyl-5-acryloyloxy Methyl-1,3-dioxane, tetrabromobisphenol A diethoxydiacrylate, 4,4-dimercaptodiphenyl sulfide dimethacrylate, Li tetraethylene glycol diacrylate, 1,9-nonanediol diacrylate, and ditrimethylolpropane tetraacrylate. These can be used alone or in combination of two or more.

  Examples of the oligomer include epoxy acrylate resins such as bisphenol A type epoxy acrylate resins, phenol novolac type epoxy acrylate resins, cresol novolac type epoxy acrylate resins, carboxyl group-modified epoxy acrylate resins; polyols (polytetramethylene glycol, ethylene Polyester diol of glycol and adipic acid, ε-caprolactone modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl group-terminated hydrogenated polyisoprene, hydroxyl group-terminated polybutadiene, hydroxyl group-terminated polyisobutylene, etc.) and organic isocyanate (tolylene diene) Isocyanate, isophorone diisocyanate, diphenylmethane Urethane resin obtained from isocyanate, hexamethylene diisocyanate, xylylene diisocyanate, etc.) is converted into hydroxyl group-containing (meth) acrylate {hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol Urethane acrylate resin obtained by reacting with triacrylate, etc .; a resin in which a (meth) acryl group is introduced into the polyol via an ester bond; a polyester acrylate resin, a poly (meth) acryl acrylate resin (polymerizable) (Poly (meth) acrylic acid ester resin having a reactive group) and the like. These can be used alone or in combination of two or more.

Of these polymerizable monomers and / or oligomers, monomers and / or oligomers having a (meth) acryloyl group are more preferred.
The number average molecular weight of the oligomer is preferably 5000 or less.
Further, when a polymerizable monomer is used in order to improve the surface curability and reduce the viscosity for improving workability, the molecular weight is preferably 1000 or less. If the molecular weight is 1000 or less, the compatibility with the vinyl polymer is good.

  When the polymerizable monomer and / or oligomer is blended, the amount used is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the vinyl polymer. The amount is preferably 10 to 50 parts by mass. If the usage-amount is in the said range, the viscosity of a curable composition will become low and it will be excellent in workability | operativity. Furthermore, it can be set as the curable composition which gives the hardened | cured material which is excellent in intensity | strength and elasticity.

The curable composition of the present invention can further contain other components as long as the object of the present invention is achieved. Other components include inorganic machine fillers (reinforcing agents, fillers), plasticizers, adhesion promoters, solvents, curability modifiers, physical property modifiers, storage stability modifiers, radical inhibitors, metal deactivators. Agents, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents and the like. These may use only 1 type and may use 2 or more types together.
In addition, since the vinyl polymer in the present invention is a polymer having excellent durability, an anti-aging agent is not always necessary, but general antioxidants, ultraviolet absorbers, light stabilizers and the like are appropriately used. be able to.

The inorganic filler is used as a reinforcing agent or a filler. Although this inorganic filler is not specifically limited, For example, reinforcing fillers such as fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay And fillers such as talc, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white and shirasu balloon; and fibrous fillers such as asbestos, glass fibers and filaments. These can be used alone or in combination of two or more.
When it is desired to obtain a cured product having high strength by using an inorganic filler, fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay and Use of activated zinc or the like is preferred. In this case, the amount of the inorganic filler used is preferably 0.1 to 250 parts by mass, more preferably 80 to 180 parts by mass with respect to 100 parts by mass of the vinyl polymer.
In addition, when it is desired to obtain a cured product having low strength and large elongation, it is mainly preferable to use titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like. In this case, the amount of the inorganic filler used is preferably from 0.1 to 200 parts by weight, more preferably from 80 to 150 parts by weight, based on 100 parts by weight of the vinyl polymer. These inorganic fillers may be used alone or in combination of two or more.

  The plasticizer is not particularly limited. For example, phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate, and butyl benzyl phthalate; non-aromatic such as dioctyl adipate and dioctyl sebacate Dibasic acid esters; esters of polyalkylene glycols such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; phosphate esters such as tricresyl phosphate and tributyl phosphate; polyerylene glycol, polypropylene glycol or hydroxyls thereof Group-modified polyethers; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; weight average molecular weight (Mw) 1000 to 70 0 of Tg-10 ° C. or less of the poly (meth) acrylate. These can be used alone or in combination of two or more. The amount of plasticizer used is preferably 0.1 to 400 parts by weight, more preferably 0.1 to 200 parts by weight, and 0.1 to 100 parts by weight with respect to 100 parts by weight of the vinyl polymer. Part is particularly preferred.

  Examples of the adhesion-imparting agent include silane compounds such as amino silane, epoxy silane, vinyl silane, and methyl silanes. These can be used alone or in combination of two or more. Moreover, 0.1-100 mass parts is preferable with respect to 100 mass parts of vinyl polymers, and, as for the usage-amount in the case of using an adhesive provision agent, 0.1-50 mass parts is more preferable, 30 parts by mass is particularly preferred.

  Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone. Can be mentioned. These can be used alone or in combination of two or more. Moreover, you may use a solvent at the time of manufacture of a polymer. The amount of solvent used is preferably 0.1 to 400 parts by weight, more preferably 0.1 to 200 parts by weight, and 0.1 to 100 parts by weight with respect to 100 parts by weight of the vinyl polymer. Is particularly preferred.

  Moreover, the curable composition of this invention can be made into the composition containing a hardening | curing agent further. And this curable composition can be made into hardened | cured material by using for a hardening process (active energy irradiation, heating, etc.). The said hardening | curing agent fulfill | performs the effect which expresses sclerosis | hardenability to a curable composition, when a hardening process is given. The curing agent is appropriately selected depending on the curing method (curing treatment) and the type of functional group at the end of the vinyl polymer.

  When the vinyl polymer contained in the curable composition of the present invention is a vinyl copolymer having a (meth) acryloyl group at the terminal or the like, usually active energy rays such as ultraviolet rays, visible rays, and electron beams. It is preferable to cure by irradiation or heat. Accordingly, as the curing agent used (blended) in the curable composition, an appropriate compound is selected depending on each curing method.

  For example, when it is set as the curable composition hardened | cured with an active energy ray, it is preferable to contain a photoinitiator as a hardening | curing agent. The photopolymerization initiator is not particularly limited, but a photo radical initiator and a photo anion initiator are preferable, and a photo radical initiator is particularly preferable. Specifically, benzoin such as benzoin, benzoin methyl ether and benzoin propyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2 -Hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one and N , Acetophenone such as N-dimethylaminoacetophenone; anthraquinone such as 2-methylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxa And thioxanthones such as 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzylmethyl ketal; benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, Michler's ketone and 4-benzoyl Benzophenones such as -4'-methyldiphenyl sulfide; and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4'-trimethylpentylphosphine oxide, camphorquinone, etc. Can be mentioned. These photopolymerization initiators may be used alone or in combination of two or more. Furthermore, it can also be combined with a sensitizer such as amines.

  As for the addition amount of said photoinitiator, 0.01-50 mass parts is preferable with respect to 100 mass parts of vinyl polymers. More preferably, it is 0.1-30 mass parts, More preferably, it is 0.5-10 mass parts.

  When curing a curable composition containing a photopolymerization initiator, the active energy ray source is not particularly limited. Examples thereof include light and electron beams from a high pressure mercury lamp, a low pressure mercury lamp, an electron beam irradiation device, a halogen lamp, a light emitting diode, a semiconductor laser, and the like. Among these, it can select suitably according to the property etc. of the photoinitiator contained in a curable composition.

  Moreover, when making it harden | cure with a heat | fever, it is preferable to contain a thermal-polymerization initiator. The thermal polymerization initiator is not particularly limited. Examples include azo initiators, peroxides, persulfates, redox initiators, and the like. These can be used alone or in combination of two or more.

  Examples of the azo initiator 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'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (methylisobutyrate), and the like. These can be used alone or in combination of two or more.

Examples of the peroxide include benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, t-butylperoxyisopropyl monocarbonate, and di (4-t-butylcyclohexyl). Examples include peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate, t-butylperoxy-2-ethylhexanoate, and dicumyl peroxide. These can be used alone or in combination of two or more.
Examples of the persulfate include potassium persulfate, sodium persulfate, and ammonium persulfate.

  In addition, as a redox (oxidation-reduction) initiator, a combination of the above-mentioned persulfate initiator and a reducing agent such as sodium metabisulfite and sodium bisulfite; a combination of a system based on an organic peroxide and a tertiary amine For example, systems based on benzoyl peroxide and dimethylaniline; combinations of organic hydroperoxides and systems based on transition metals, such as systems based on cumene hydroperoxide and cobalt naphthate. These can be used alone or in combination of two or more.

  Examples of other thermal polymerization initiators include pinacol such as tetraphenyl 1,1,2,2-ethanediol. As these thermal polymerization initiators, azo initiators and peroxide initiators are preferable. These photopolymerization initiators may be used alone or in combination of two or more.

  The addition amount of the thermal polymerization initiator is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the vinyl polymer. More preferably, it is 0.1-20 mass parts, More preferably, it is 0.5-10 mass parts.

  In the case of curing a curable composition containing a thermal polymerization initiator, the thermosetting conditions for curing with heat are not particularly limited. The temperature is selected depending on the type of thermal polymerization initiator, polymer, compound to be added, etc., but is preferably 50 ° C to 250 ° C, more preferably 70 ° C to 200 ° C. The curing time is selected depending on the thermal polymerization initiator, monomer, solvent, reaction temperature, etc. to be used, but is usually 1 minute to 24 hours.

  When the vinyl polymer contained in the curable composition of the present invention is a vinyl copolymer having a hydroxyl group at the terminal or the like, a compound having two or more functional groups capable of reacting with a hydroxyl group is used as a curing agent. Can be used as Examples of such a curing agent include polyisocyanate compounds having two or more isocyanate groups in one molecule, aminoplast resins such as methylolated melamine and its alkyl etherified product or low-condensed product, and polyfunctional carboxylic acid. And halides thereof. By using these curing agents, the curable composition can be uniformly cured. Moreover, when preparing hardened | cured material using these hardening | curing agents, the suitable hardening catalyst according to each hardening | curing agent can be used.

  When the vinyl polymer contained in the curable composition of the present invention is a vinyl copolymer having an amino group at the terminal, a compound having two or more functional groups capable of reacting with an amino group is used as a curing agent. Can be used. Specific examples of the curing agent include, for example, a polyvalent isocyanate compound having two or more isocyanate groups in one molecule. 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.

  When the vinyl polymer contained in the curable composition of the present invention is a vinyl copolymer having a hydroxyl group or an amino group at the terminal or the like, conditions such as thermosetting are not particularly limited. For example, although temperature changes with kinds, such as a hardening | curing agent (polymerization initiator) to be used, a polymer, and the compound added, 50 to 250 degreeC is preferable normally and 70 to 200 degreeC is more preferable. The curing time varies depending on the curing agent, monomer, solvent, reaction temperature, etc. used, but is usually 1 minute to 24 hours.

Further, since the curable composition of the present invention is excellent in storage stability even at a relatively high temperature, the curable composition can be handled with a lower viscosity, and is suitably used for liquid injection molding at a high temperature. be able to. Moreover, when making the curable composition of this invention flow, it is preferable to carry out at the temperature of 30 to 80 degreeC, and it is more preferable to make it flow at the temperature of 40 to 70 degreeC.
In addition, the curable composition of this invention can be made to flow at the temperature of 30 to 80 degreeC. Furthermore, the curing reaction can be performed while flowing at 30 ° C. or higher. That is, the curable composition of the present invention can also be used as a resin composition for injection molding (RIM, LIM, etc.).

  When forming into a molded object using the curable composition of this invention, it does not specifically limit as the shaping | molding method, The various shaping | molding methods generally used can be used. For example, cast molding, compression molding, transfer molding, injection molding, extrusion molding, rotational molding, hollow molding, thermoforming, and the like can be given. In particular, from the viewpoint of being able to be automated and continuous and being excellent in productivity, the one by injection molding is preferable.

  The manufacturing method of the curable composition of this invention is not specifically limited. Specifically, the above-mentioned vinyl polymer and other additives (polymerizable monomers and / or oligomers, other components, curing agents) used as necessary are mixed with a stirrer and a planetary stirrer. It can manufacture by mixing suitably using an apparatus etc.

  The use of the curable composition of the present invention is not particularly limited. For example, it can be used as an adhesive, a sealing material, a coating material, a potting material, and the like. Specifically, electrical and electronic component materials such as solar cell backside sealing materials, electrical insulation materials such as insulation coating materials for electric wires and cables, foams, potting materials for electrical and electronic materials, films, gaskets, casting materials, artificial materials It can be used for various applications such as marble, various molding materials, meshed glass, and sealing material for rust prevention and waterproofing of the end face (cut portion) of laminated glass. Furthermore, the molded product showing rubber elasticity obtained from the curable composition of the present invention can be widely used mainly for gaskets and packings. For example, in the automobile field, it can be used as a body part as a sealing material for maintaining airtightness, an anti-vibration material for glass, an anti-vibration material for vehicle body parts, particularly a wind seal gasket and a door glass gasket. As chassis parts, it can be used for vibration-proof and sound-proof engines and suspension rubbers, especially engine mount rubbers. As engine parts, they can be used for hoses for cooling, fuel supply, exhaust control, etc., sealing materials for engine oil, and the like. It can also be used for exhaust gas cleaning device parts and brake parts. In the home appliance field, it can be used for packing, O-rings, belts and the like. Specifically, decorations for lighting fixtures, waterproof packings, anti-vibration rubbers, insect-proof packings, anti-vibration / sound absorption and air sealing materials for cleaners, drip-proof covers for electric water heaters, waterproof packings, heater parts Packing, electrode packing, safety valve diaphragm, hose for sake cans, waterproof packing, solenoid valve, waterproof packing for steam microwave oven and jar rice cooker, water tank packing, water absorption valve, water receiving packing, connection hose, belt, heat insulation Oil packing for combustion equipment such as heater packing, steam outlet seal, O-ring, drain packing, pressure tube, blower tube, feed / intake packing, anti-vibration rubber, oil filler packing, oil meter packing, oil feed tube, Speaker gaskets, speaker edges, turntables for acoustic equipment such as diaphragm valves and air pipes Seat, belts, pulleys, and the like. In the construction field, it can be used for structural gaskets (zipper gaskets), air membrane roof materials, waterproof materials, fixed sealing materials, vibration-proof materials, sound-proof materials, setting blocks, sliding materials, and the like. In the sports field, it can be used for all-weather pavement materials and gymnasium floors as sports floors, shoe sole materials and midsole materials as sports shoes, and golf balls as ball for ball games. In the field of anti-vibration rubber, it can be used as anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, anti-vibration materials, and the like. In the marine and civil engineering fields, structural materials include rubber expansion joints, bearings, waterstops, waterproof sheets, rubber dams, elastic pavements, anti-vibration pads, protective bodies, etc., rubber molds, rubber packers, rubber skirts as construction secondary materials , Sponge mats, mortar hoses, mortar strainers, etc., rubber sheets, air hoses, etc. as construction auxiliary materials, rubber buoys, wave-absorbing materials, etc. as safety measures products, oil fences, silt fences, antifouling materials, marine hoses, etc. Can be used for draging hoses, oil skimmers, etc. In addition, it can be used for sheet rubber, mats, foam boards and the like.

  The sealing material composition of the present invention is a composition containing the curable composition of the present invention. The sealing material composition may be the total amount of the curable composition or may be partially contained. The content of the curable composition in the sealing material composition is preferably 1 to 100% by mass when the total amount of the sealing material composition is 100% by mass.

  Moreover, the sealing material composition of this invention can mix | blend another additive as needed further in addition to a curable composition.

  The manufacturing method of this sealing material composition is not specifically limited, For example, it obtains by mix | blending and mixing a curable composition, its additive agent, etc. In addition, the mixing | blending order of each component is not specifically limited.

  The adhesive composition of the present invention is a composition containing the curable composition of the present invention. This adhesive composition may be the total amount of the curable composition, or may be partially contained. The content of the curable composition in the adhesive composition is preferably 1 to 100% by mass when the total amount of the adhesive composition is 100% by mass.

  Moreover, the adhesive composition of this invention can mix | blend another additive as needed further in addition to a curable composition.

  The method for producing the adhesive composition is not particularly limited, and can be obtained, for example, by blending and mixing the curable composition and its additive. In addition, the mixing | blending order of each component is not specifically limited.

  The pressure-sensitive adhesive composition of the present invention is a composition containing the curable composition of the present invention. The pressure-sensitive adhesive composition may be the whole amount of the curable composition or may be partially contained. The content of the curable composition in the pressure-sensitive adhesive composition is preferably 1 to 100% by mass when the total amount of the pressure-sensitive adhesive composition is 100% by mass.

  In addition to the curable composition, the pressure-sensitive adhesive composition of the present invention may further contain other additives as necessary.

  The manufacturing method of this adhesive composition is not specifically limited, For example, it can obtain by mix | blending and mixing a curable composition, its additive agent, etc. In addition, the mixing | blending order of each component is not specifically limited.

Examples of the present invention will be described below together with comparative examples, but it goes without saying that the scope of the present invention is not limited to these examples. In the following, “part” is based on mass unless otherwise specified.
In the synthesis examples, examples and comparative examples, “Mn” means the number average molecular weight, “Mw” means the weight average molecular weight, and Mw / Mn means the degree of dispersion. “Mn” and “Mw” are values calculated in terms of standard polystyrene by gel permeation chromatography (GPC) measurement.
Moreover, the number of functional groups, such as the number of acryloyl groups, the number of hydroxyl groups, and the number of amino groups in the polymer in an Example and a comparative example, is the average number computed by the following formula from the integrated value measured by < ¹ > H-NMR spectrum.
Number of functional groups (average number) = (integral value derived from functional group) / [(integral value derived from monomer) / (degree of polymerization)]

1. Production of First Polymer Synthesis Example 1 [Synthesis of First Polymer A]
In a 1 liter pressurized stirred tank reactor equipped with an oil jacket (1 liter brown separable flask), 306 parts of lauryl methacrylate (hereinafter also referred to as “LMA”) as a vinyl monomer and acrylic. 1. 51 parts of butyl acid (hereinafter also referred to as “BA”), 7.2 parts of diiodoxylene, 0.35 part of diethyl phosphite, and benzoyl peroxide (hereinafter also referred to as “BPO”) 4 parts and 132 parts of anisole as a solvent were charged. Thereafter, the inside of the reactor was sufficiently deaerated by bubbling using nitrogen gas. Next, the internal temperature was set to 70 ° C., and polymerization was started while stirring the reaction system. At that time, the jacket temperature was adjusted so that the temperature of the reaction system was maintained at 70 ° C. Three hours after the start of the polymerization, the LMA polymerization rate was measured to be 70%, and the BA polymerization rate was measured to be 80%. Subsequently, after cooling the reaction system, the obtained reaction liquid was extracted. Then, the reaction solution was dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours to obtain a first polymer A. When the GPC measurement of the obtained 1st polymer A was performed, they were Mw18630, Mn13500, and Mw / Mn1.38. Also, the vinyl monomer, initiator (initiator precursor), catalyst (catalyst precursor) used for the synthesis of the first polymer A, and Mw, Mn, and Mw / Mn of the first polymer A are shown. It is shown in 1.
Diiodoxylene was used as a catalyst precursor and an initiator. Diethyl phosphite was used as the catalyst precursor.
The benzoyl peroxide was used as a radical generator. This radical derived from benzoyl peroxide pulls out a hydrogen atom of diethyl phosphite, and diethyl phosphite from which the hydrogen atom has been pulled out becomes a phosphorus radical. And this phosphorus radical pulls out the iodine atom of the molecular terminal in polymerization and diiodoxylene. Then, a catalyst composed of diethyl iodine phosphate is formed.

Synthesis Example 2 [Synthesis of first polymer B]
In a 1 liter pressurized stirred tank reactor equipped with an oil jacket, 306 parts of LMA and 46 parts of BA as vinyl monomers, 10.8 parts of diiodoxylene, 0.52 parts of diethyl phosphite, 3.6 parts of BPO as a radical generator and 132 parts of anisole as a solvent were charged. Thereafter, the inside of the reactor was sufficiently deaerated by bubbling using nitrogen gas. Next, the internal temperature was set to 70 ° C., and polymerization was started while stirring the reaction system. At that time, the jacket temperature was adjusted so that the temperature of the reaction solution was maintained at 70 ° C. Three hours after the start of polymerization, the LMA polymerization rate was measured to be 72%, and the BA polymerization rate was measured to be 85%. Subsequently, after cooling the reaction system, the obtained reaction liquid was extracted. Then, the reaction solution was dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours to obtain a first polymer B. When the GPC measurement of the obtained 1st polymer B was performed, they were Mw12600, Mn9000, and Mw / Mn1.40. Also, the vinyl monomer, initiator (initiator precursor), catalyst (catalyst precursor) used for the synthesis of the first polymer B, and Mw, Mn, and Mw / Mn of the first polymer B are shown. It is written together with 1.
Diiodoxylene was used as a catalyst precursor and an initiator. Diethyl phosphite was used as the catalyst precursor.

但し、上記式（１１）において、Ｒは、−Ｃ_４Ｈ_９、又は−Ｃ_１２Ｈ_２５を示す。 Synthesis Example 3 [Synthesis of first polymer C]
In a 1-liter pressurized stirred tank reactor equipped with an oil jacket, 306 parts of LMA and 51 parts of BA, 2.6 parts of iodine, 4,4-azobis-4-cyanovaleric acid (hereinafter referred to as “vinyl monomer”) , And also referred to as “ACVA”.) 5.6 parts and 0.34 part of diethyl phosphite, and 134 parts of anisole as a solvent were charged. Thereafter, the inside of the reactor was sufficiently deaerated by bubbling using nitrogen gas. Next, the internal temperature was set to 80 ° C., and polymerization was started while stirring the reaction system. At that time, the jacket temperature was adjusted so that the temperature of the reaction solution was maintained at 80 ° C. Six hours after the start of polymerization, the LMA polymerization rate was measured to be 72%, and the BA polymerization rate was measured to be 85%. Subsequently, after cooling the reaction system, the obtained reaction liquid was extracted. Then, the reaction solution was dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours to obtain a first polymer C. When the GPC measurement of the obtained 1st polymer C was performed, they were Mw21130, Mn15200, and Mw / Mn1.39. Also, the vinyl monomer, initiator (initiator precursor), catalyst (catalyst precursor) used for the synthesis of the first polymer C, and Mw, Mn, and Mw / Mn of the first polymer C are shown. It is written together with 1.
In addition, iodine was used as a catalyst precursor and an initiator precursor. ACVA was used as the initiator precursor. Diethyl phosphite was used as the catalyst precursor.
Moreover, the obtained first polymer C has a halogen atom at one end and a structure derived from an initiator (carboxyl group) at the other end, as shown in the following formula (50).

However, in the above formula (11), R represents a _-C 4 _{H 9,} or _-C 12 _{H 25.}

Synthesis Example 4 [Synthesis of first polymer D]
In a 1 liter pressurized stirred tank reactor equipped with an oil jacket, 311 parts of LMA and 43 parts of BA as vinyl monomers and 0.314 parts of N-iodosuccinimide (hereinafter also referred to as “NIS”). And 2.8 parts of iodine, 6.2 parts of ACVA, and 149 parts of anisole as a solvent. Thereafter, the inside of the reactor was sufficiently deaerated by bubbling using nitrogen gas. Next, the internal temperature was set to 80 ° C., and polymerization was started while stirring the reaction system. At that time, the jacket temperature was adjusted so that the temperature of the reaction solution was maintained at 80 ° C. Five hours after the start of polymerization, the polymerization rate of LMA was measured to be 76%, and the polymerization rate of BA was measured to be 80%. Subsequently, after cooling the reaction system, the obtained reaction liquid was extracted. The reaction solution was dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours to obtain a first polymer D. When the GPC measurement of the obtained 1st polymer D was performed, they were Mw20300, Mn14000, and Mw / Mn1.45. Also, the vinyl monomer, initiator (initiator precursor), catalyst (catalyst precursor) used for the synthesis of the first polymer D, and Mw, Mn, and Mw / Mn of the first polymer D are shown. It is written together with 1.
Note that NIS was used as a catalyst. ACVA was used as the initiator precursor. Iodine was used as the initiator precursor.
Moreover, the obtained 1st polymer D is shown by the said Formula (50).

Synthesis Example 5 [Synthesis of first polymer E]
In a 1 liter pressurized stirred tank reactor equipped with an oil jacket, LMA 305 parts and BA 51 parts, diiodoxylene 7.2 parts, vitamin E 2.2 parts, radical generator As BPO 2.4 parts and as solvent anisole 132 parts. Thereafter, the inside of the reactor was sufficiently deaerated by bubbling using nitrogen gas. Next, the internal temperature was set to 70 ° C., and polymerization was started while stirring the reaction system. At that time, the jacket temperature was adjusted so that the temperature of the reaction solution was maintained at 70 ° C. Three hours after the start of polymerization, the polymerization rate of LMA was measured to be 71%, and the polymerization rate of BA was measured to be 81%. Subsequently, after cooling the reaction system, the obtained reaction liquid was extracted. The reaction solution was dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours to obtain a first polymer E. It was Mw20660, Mn13800, and Mw / Mn1.49 when the GPC measurement of the obtained 1st polymer E was performed. Also, the vinyl monomer, initiator (initiator precursor), catalyst (catalyst precursor) used for the synthesis of the first polymer E, and Mw, Mn, and Mw / Mn of the first polymer E are shown. It is written together with 1.
Diiodoxylene was used as a catalyst precursor and an initiator. Vitamin E was used as the catalyst precursor.

Synthesis Example 6 [Synthesis of first polymer F]
In a 1 liter pressurized stirred tank reactor equipped with an oil jacket, 306 parts of LMA and 51 parts of BA as a vinyl monomer, 7.2 parts of diiodylene and 0.08 part of 1,4-cyclohexadiene Then, 2.4 parts of BPO as a radical generator and 132 parts of anisole as a solvent were charged. Thereafter, the inside of the reactor was sufficiently deaerated by bubbling using nitrogen gas. Next, the internal temperature was set to 70 ° C., and polymerization was started while stirring the reaction system. At that time, the jacket temperature was adjusted so that the temperature of the reaction solution was maintained at 70 ° C. Three hours after the start of polymerization, the polymerization rate of LMA was measured to be 72%, and the polymerization rate of BA was measured to be 75%. Subsequently, after cooling the reaction system, the obtained reaction liquid was extracted. Then, the reaction solution was dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours to obtain a first polymer F. It was Mw21300, Mn14200, and Mw / Mn1.50 when the GPC measurement of the obtained 1st polymer F was performed. The vinyl monomers, initiator (initiator precursor), catalyst (catalyst precursor) used for the synthesis of the first polymer F, and Mw, Mn, and Mw / Mn of the first polymer F are also shown. It is written together with 1.
Diiodoxylene was used as a catalyst precursor and an initiator. 1,4-cyclohexadiene was used as the catalyst precursor.

2. Production of vinyl polymer Synthesis Example 7 [Synthesis of vinyl polymer G having an acryloyl group at the molecular end]
In a 1 liter pressurized stirred tank reactor equipped with an oil jacket, 50 parts of the first polymer A obtained in Synthesis Example 1 was dissolved in 50 parts of N, N-dimethylacetamide. 3.2 parts of potassium acrylate was added. Thereafter, the internal temperature was set to 70 ° C., and the reaction was performed for 3 hours while stirring the reaction system. In that case, it adjusted so that the temperature of a reaction liquid might be maintained at 70 degreeC. After completion of the reaction, the reaction solution was dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours to distill off N, N-dimethylacetamide. Subsequently, toluene was added to the residue obtained by drying under reduced pressure, and the insoluble matter was removed by filtration. The obtained filtrate was again dried under reduced pressure in an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours, and toluene was distilled off to obtain a vinyl polymer G. When the number of acryloyl groups of the obtained vinyl polymer G was measured, the average number was 1.8. Moreover, when the GPC measurement of the vinyl-type polymer G was performed, they were Mw18630, Mn13500, and Mw / Mn1.38. In addition, the first polymer used for the synthesis of the vinyl polymer G, the molecular terminal modifier (molecular terminal modification method), and the functional group type, the number of functional groups, Mw, Mn, and Mw / Mn of the vinyl polymer G It shows in Table 2.

Synthesis Example 8 [Synthesis of vinyl polymer H having a hydroxyl group at the molecular end]
In a 1 liter pressurized stirred tank reactor equipped with an oil jacket, 50 parts of the first polymer A obtained in Synthesis Example 1 was dissolved in 50 parts of ethyl acetate. 8 parts were added. Thereafter, the internal temperature was set to 70 ° C., and the reaction was performed for 3 hours while stirring the reaction system. In that case, it adjusted so that the temperature of a reaction liquid might be maintained at 70 degreeC. After completion of the reaction, unreacted aminoethanol was removed. Next, the reaction product was dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours to obtain a vinyl polymer H. When the number of hydroxyl groups of the obtained vinyl polymer H was measured, the average number was 1.9. Moreover, when the GPC measurement of the vinyl polymer H was performed, they were Mw18630, Mn13500, and Mw / Mn1.38. In addition, the first polymer used for the synthesis of the vinyl polymer H, the molecular terminal modifier (molecular terminal modification method), and the functional group type, the number of functional groups, Mw, Mn, Mw / Mn of the vinyl polymer H This is also shown in Table 2.

Synthesis Example 9 [Synthesis of vinyl polymer I having acryloyl group at molecular end]
In a 1 liter pressurized stirred tank reactor equipped with an oil jacket, 5 parts of the vinyl polymer H obtained in Synthesis 8 was dissolved in 5 parts of ethyl acetate, and ethyl acrylate isocyanate ( 0.13 parts by mass) (hereinafter also referred to as “AOI”) and 0.1 part by mass of triethylamine were added. Thereafter, the internal temperature was set to 70 ° C., and the reaction was performed for 3 hours while stirring the reaction system. In that case, it adjusted so that the temperature of a reaction liquid might be maintained at 70 degreeC. After the reaction was completed, unreacted AOI was removed. Next, the reaction product was dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours to obtain a vinyl polymer I. When the number of acryloyl groups of the obtained vinyl polymer I was measured, the average number was 1.8. Moreover, it was Mw18630, Mn13500, Mw / Mn1.38 when the GPC measurement of the vinyl-type polymer I was performed. Further, the first polymer used for the synthesis of the vinyl polymer I, the molecular terminal modifier (molecular terminal modification method), and the functional group type, the number of functional groups, Mw, Mn, Mw / Mn of the vinyl polymer I This is also shown in Table 2.

Synthesis Example 10 [Synthesis of vinyl polymer J having a hydroxyl group at the molecular end]
In a 1 liter pressurized stirred tank reactor equipped with an oil jacket, 50 parts of the first polymer A obtained in Synthesis Example 1 was dissolved in 50 parts of ethyl acetate, and ethylenediamine 4.4 was added to the resulting solution. Part was added. Thereafter, the internal temperature was set to 70 ° C., and the reaction was performed for 3 hours while stirring the reaction system. In that case, it adjusted so that the temperature of a reaction liquid might be maintained at 70 degreeC. After completion of the reaction, unreacted ethylenediamine was removed. Subsequently, the reaction product was dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours, to obtain a vinyl polymer J. When the number of amino groups of the obtained polymer H was measured, the average number was 1.6. Moreover, when the GPC measurement of the vinyl-type polymer J was performed, they were Mw18630, Mn13500, and Mw / Mn1.38. In addition, the first polymer used for the synthesis of the vinyl polymer J, the molecular terminal modifier (molecular terminal modification method), and the functional group type, the number of functional groups, Mw, Mn, Mw / Mn of the vinyl polymer J This is also shown in Table 2.

Synthesis Example 11 [Synthesis of vinyl polymer K having acryloyl group at molecular end]
In a 1 liter pressurized stirred tank reactor equipped with an oil jacket, 50 parts of the first polymer B obtained in Synthesis Example 2 was dissolved in 50 parts of N, N-dimethylacetamide. 4.9 parts of potassium acrylate was added. Thereafter, the internal temperature was set to 70 ° C., and the reaction was performed for 3 hours while stirring the reaction system. In that case, it adjusted so that the temperature of a reaction liquid might be maintained at 70 degreeC. After completion of the reaction, the reaction solution was dried under reduced pressure in an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours to distill off N, N-dimethylacetamide. Subsequently, toluene was added to the residue obtained by drying under reduced pressure, and the insoluble matter was removed by filtration. The obtained filtrate was again dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours, and toluene was distilled off to obtain a vinyl polymer K. When the number of acryloyl groups of the obtained vinyl polymer K was measured, the average number was 1.9. Moreover, when the GPC measurement of the vinyl polymer K was performed, they were Mw12600, Mn9000, and Mw / Mn1.40. In addition, the first polymer used for the synthesis of the vinyl polymer K, the molecular terminal modifier (molecular terminal modification method), and the functional group type, the number of functional groups, Mw, Mn, and Mw / Mn of the vinyl polymer K This is also shown in Table 2.

Synthesis Example 12 [Synthesis of vinyl polymer L having an acryloyl group at the molecular end]
In a 1 liter pressurized stirred tank reactor equipped with an oil jacket, 50 parts of the polymer C obtained in Synthesis Example 3 above was dissolved in 50 parts of N, N-dimethylacetamide, and acrylic acid was added to the resulting solution. 0.8 parts of -4-hydroxybutyl glycidyl ether (hereinafter also referred to as “4HBAGE”), 1.5 parts of tetrabutylammonium bromide (hereinafter also referred to as “TBAB”), and 1.4 parts of potassium acrylate were added. Thereafter, the internal temperature was set to 70 ° C., and the reaction was performed for 3 hours while stirring the reaction system. In that case, it adjusted so that the temperature of a reaction liquid might be maintained at 70 degreeC. After completion of the reaction, the reaction solution was dried under reduced pressure in an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours to distill off N, N-dimethylacetamide. Subsequently, toluene was added to the residue obtained by drying under reduced pressure, and the insoluble matter was removed by filtration. The obtained filtrate was again dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours, and toluene was distilled off to obtain a vinyl polymer L. When the number of acryloyl groups of the obtained vinyl polymer L was measured, the average number was 1.7. Moreover, when the GPC measurement of the vinyl polymer L was performed, they were Mw21130, Mn15200, and Mw / Mn1.39. In addition, the first polymer used for the synthesis of the vinyl polymer L, the molecular terminal modifier (molecular terminal modification method), and the functional group type, the number of functional groups, Mw, Mn, and Mw / Mn of the vinyl polymer L This is also shown in Table 2.
In addition, in the synthesis | combination of the vinyl polymer L, the 1st polymer C has the carboxyl group derived from ACVA used for the manufacture in the start terminal ((alpha) terminal). Therefore, the carboxyl group was reacted with the glycidyl group of the above 4HBAGE, and the terminal was an acryloyl group. The TBAB was used as a catalyst for reacting a carboxyl group and a glycidyl group. The other terminal having an iodine atom (ω terminal) was reacted with potassium acrylate to form an acryloyl group.

Synthesis Example 13 [Synthesis of vinyl polymer M having acryloyl group at molecular end]
In a 1 liter pressurized stirred tank reactor equipped with an oil jacket, 50 parts of the polymer D obtained in Synthesis Example 4 was dissolved in 50 parts of N, N-dimethylacetamide, and 4HBAGE0. 9 parts, 1.5 parts of TBAB and 1.6 parts of potassium acrylate were added. Thereafter, the internal temperature was set to 70 ° C., and the reaction was performed for 3 hours while stirring the reaction system. In that case, it adjusted so that the temperature of a reaction liquid might be maintained at 70 degreeC. After completion of the reaction, the reaction solution was dried under reduced pressure in an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours to distill off N, N-dimethylacetamide. Subsequently, toluene was added to the residue obtained by drying under reduced pressure, and the insoluble matter was removed by filtration. The obtained filtrate was again dried under reduced pressure by an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours, and toluene was distilled off to obtain a vinyl polymer M. When the number of acryloyl groups of the obtained vinyl polymer M was measured, the average number was 1.7. Moreover, when the GPC measurement of the vinyl polymer M was performed, they were Mw20300, Mn14000, and Mw / Mn1.45. In addition, the first polymer used for the synthesis of the vinyl polymer M, the molecular terminal modifier (molecular terminal modification method), and the functional group type, the number of functional groups, Mw, Mn, and Mw / Mn of the vinyl polymer M This is also shown in Table 2.
In addition, in the synthesis | combination of the vinyl polymer M, the 1st polymer D has the carboxyl group derived from ACVA used for the manufacture at the start terminal (alpha terminal). Therefore, the carboxyl group was reacted with the glycidyl group of the above 4HBAGE, and the terminal was an acryloyl group. The TBAB was used as a catalyst for reacting a carboxyl group and a glycidyl group. The other terminal having an iodine atom (ω terminal) was reacted with potassium acrylate to form an acryloyl group.

Synthesis Example 14 [Synthesis of vinyl polymer N having acryloyl group at molecular end]
In a 1 liter pressurized stirred tank reactor equipped with an oil jacket, 50 parts of the polymer E obtained in Synthesis Example 5 was dissolved in 50 parts of N, N-dimethylacetamide, and acrylic acid was added to the resulting solution. 3.2 parts of potassium was added. Thereafter, the internal temperature was set to 70 ° C., and the reaction was performed for 3 hours while stirring the reaction system. In that case, it adjusted so that the temperature of a reaction liquid might be maintained at 70 degreeC. After completion of the reaction, the reaction solution was dried under reduced pressure in an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours to distill off N, N-dimethylacetamide. Subsequently, toluene was added to the residue obtained by drying under reduced pressure, and the insoluble matter was removed by filtration. The obtained filtrate was again dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours, and toluene was distilled off to obtain a vinyl polymer N. When the number of acryloyl groups of the obtained vinyl polymer N was measured, the average number was 1.9. Moreover, when the GPC measurement of the vinyl polymer N was performed, they were Mw20660, Mn13800, and Mw / Mn1.49. In addition, the first polymer used for the synthesis of the vinyl polymer N, the molecular terminal modifier (molecular terminal modification method), and the functional group type, the number of functional groups, Mw, Mn, Mw / Mn of the vinyl polymer N This is also shown in Table 2.

Synthesis Example 15 [Synthesis of vinyl polymer O having acryloyl group at molecular end]
In a 1 liter pressurized stirred tank reactor equipped with an oil jacket, 50 parts of the polymer F obtained in Synthesis Example 6 above was dissolved in 50 parts of N, N-dimethylacetamide, and acrylic acid was added to the resulting solution. A mixed solution containing 3.1 parts of potassium was charged. Thereafter, the internal temperature was set to 70 ° C., and the reaction was performed for 3 hours while stirring the reaction system. In that case, it adjusted so that the temperature of a reaction liquid might be maintained at 70 degreeC. After completion of the reaction, the reaction solution was dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours to distill off N, N-dimethylacetamide. Subsequently, toluene was added to the residue obtained by drying under reduced pressure, and the insoluble matter was removed by filtration. The obtained filtrate was again dried under reduced pressure in an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours, and toluene was distilled off to obtain a vinyl polymer O. When the number of acryloyl groups of the obtained vinyl polymer O was measured, the average number was 1.9. Moreover, when the GPC measurement of the vinyl polymer O was performed, they were Mw21300, Mn14200, and Mw / Mn1.50. In addition, the first polymer used for the synthesis of the vinyl polymer O, the molecular terminal modifier (molecular terminal modification method), and the functional group type, the number of functional groups, Mw, Mn, and Mw / Mn of the vinyl polymer O This is also shown in Table 2.

Synthesis Example 16 [Synthesis of vinyl polymer P having acryloyl group]
In a pressure-resistant stirred tank type glass reactor equipped with an oil jacket, 341 parts of butyl acrylate (hereinafter also referred to as “BA”) as a vinyl monomer and a living radical polymerization initiator represented by the following formula (51) 17.0 parts and 341 parts of butyl acetate as a solvent were charged. Thereafter, the inside of the reactor was sufficiently deaerated by bubbling using nitrogen gas. Next, the internal temperature was set to 112 ° C., and polymerization was started while stirring the reaction system. At that time, the jacket temperature was adjusted so that the temperature of the reaction solution was maintained at 112 ° C. Two hours after the initiation of polymerization, the polymerization rate of BA was measured and found to be 70%. Subsequently, after cooling the reaction system, the obtained reaction liquid was extracted. The reaction solution was dried under reduced pressure by an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours to obtain a polymer PBA (polybutyl acrylate). When the GPC measurement of the obtained polymer PBA was performed, they were Mw8600, Mn6230, and Mw / Mn1.38.
Next, in a pressure-resistant stirring tank type glass reactor equipped with an oil jacket, 215 parts of the polymer PBA obtained above, 6 parts of methacrylic acid (hereinafter also referred to as “MAA”), and 221 parts of butyl acetate were charged. Thereafter, the inside of the reactor was sufficiently deaerated by bubbling using nitrogen gas. Next, the internal temperature was 112 ° C., the polymerization was started while stirring the reaction system, and the jacket temperature was adjusted so that the temperature of the reaction solution was maintained at 112 ° C. Six hours after the start of polymerization, the BA polymerization rate was measured to be 96%, and the MAA polymerization rate was measured to be 98%. Subsequently, after cooling the reaction liquid temperature to 85 ° C., the obtained reaction liquid was mixed with 23 parts of 4-hydroxybutyl acrylate glycidyl ether (hereinafter also referred to as “4HBAGE”) and tetrabutylammonium bromide (hereinafter also referred to as “TBAB”). .) 9 parts were added and reacted at 85 ° C. for 8 hours. After the reaction, the reaction rate of 4HBAGE was measured and found to be 97%. Subsequently, after cooling the reaction system, the obtained reaction liquid was extracted and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and a temperature of 80 ° C. for 5 hours to obtain a polymer P. When the number of acryloyl groups of the obtained polymer P was measured, the average number was 2.6. Moreover, when the GPC measurement of the obtained polymer P was performed, they were Mw13150, Mn7460, and Mw / Mn1.76. In addition, the first polymer used for the synthesis of the vinyl polymer P, the molecular terminal modifier (molecular terminal modification method), and the functional group type, the number of functional groups, Mw, Mn, and Mw / Mn of the vinyl polymer P This is also shown in Table 2.

3. Manufacture and evaluation of curable composition (1) Manufacture of curable composition and hardened | cured material Using vinyl-type polymer GP obtained by the above, and the following hardening | curing agent (a)-(d), A curable composition was prepared according to the formulation shown in Table 3. Moreover, each compounding quantity of the polymers G-P was 100 parts, respectively.
Then, the mold was filled with the curable composition and cured by leaving it in the atmosphere at a temperature of 150 ° C. for 5 minutes to obtain a rubber-like cured product having a thickness of 2 mm.
The curing agents used in the curable composition are as follows.
Curing agent (a): Isobornyl acrylate Curing agent (b): Benzoyl peroxide (trade name “Nyper BW”, manufactured by NOF Corporation)
Curing agent (c): Trifunctional isocyanate compound (trade name “B-45”, manufactured by Yushi Co., Ltd.)
Curing agent (d): Dibutyltin diacetylacetonate (trade name “U-220”, manufactured by Nitto Kasei Co., Ltd.)

(2) Evaluation of hardened | cured material (2-1) Gel fraction About the hardened | cured material obtained by the above, the gel fraction was measured. The gel fraction (%) is obtained by immersing the cured product in toluene (25 ° C., 3 days), extracting the uncured portion of the cured product, and the mass before and after the immersion, before extracting the uncured portion of the cured product. The mass and the mass of the cured product after extraction of the uncured part of the cured product were measured, and the mass ratio was calculated by the following formula.
Gel fraction (%) = [(mass of cured product after extraction of uncured part of cured product) / (mass before extraction of uncured part of cured product)] × 100

(2-2) Breaking strength and elongation About each hardened | cured material obtained by the above, based on JISK7113, the tension test was done on the following conditions, and the breaking strength (MPa) and elongation (%) of each hardened | cured material were measured. .
Equipment: Shimadzu (Autograph, model “AGS-J”)
Test piece: No. 2 dumbbell shape (length 70 mm, width 10 mm, thickness 2 mm)
Distance between grips: 40mm
Tensile speed: 200 mm / min Temperature: 23 ° C.
Relative humidity; 55%

From the results in Table 3, the curable compositions of Examples 1 to 9 containing a polymer obtained by living radical polymerization using a predetermined catalyst have a breaking strength of the obtained cured product of 1.10 MPa or more. It can be seen that the curable composition gives a cured product having excellent strength. Moreover, it turns out that the curable composition of Examples 1-9 is a curable composition which gives the hardened | cured material which the elongation of the hardened | cured material obtained is 260% or more, and is excellent also in elongation.
On the other hand, the curable composition of Comparative Example 1 containing a polymer obtained by ordinary radical polymerization has a low breaking strength of 0.81 MPa of the obtained cured product, and the resulting cured product has a breaking strength of 0.81 MPa. It turns out that it is inferior compared with Examples 1-9. Furthermore, the elongation of the obtained cured product is as low as 170%, and it can be seen that the obtained cured product is inferior in breaking strength.

Claims (8)

A curable composition containing a vinyl polymer having at least one functional group selected from a (meth) acryloyl group, a hydroxyl group, a carboxyl group, and an amino group at the molecular end,
The vinyl polymer includes a catalyst comprising a compound including a central atom composed of at least one element selected from phosphorus, nitrogen, carbon, oxygen, germanium, tin, and antimony, and a halogen atom bonded to the central atom. The first polymer having a terminal halogen atom derived from the catalyst or the initiator was obtained by living radical polymerization of the vinyl monomer in the presence of an initiator composed of an organic halogen compound. Thereafter, the first polymer is terminal-modified, and the halogen atom contained in the first polymer is substituted with the functional group,
A curable composition, wherein a ratio (Mw / Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) of the vinyl polymer is less than 2.0.   The curable composition according to claim 1, wherein the vinyl polymer is a (meth) acrylic polymer.   The curable composition according to claim 1 or 2, wherein the vinyl polymer has a number average molecular weight of 3000 to 50000.   The vinyl monomer forming the first polymer includes a methacrylic acid ester compound and an acrylic acid ester compound, and the ratio of the amount of the methacrylic acid ester compound and the acrylic acid ester compound used is the sum of both. The curable composition according to any one of claims 1 to 3, wherein the content is 50 to 100% by mass and 0 to 50% by mass, respectively.   Furthermore, the curable composition in any one of Claims 1 thru | or 4 containing a hardening | curing agent.   A sealing material composition comprising the curable composition according to claim 1.   An adhesive composition comprising the curable composition according to any one of claims 1 to 5.   A pressure-sensitive adhesive composition comprising the curable composition according to claim 1.