JP6020883B2 - Chain transfer agent composition having condensed polycyclic aromatic skeleton, polymer having condensed polycyclic aromatic skeleton, and method for producing polymer - Google Patents

Description

The present invention relates to a chain transfer agent useful for obtaining a low molecular weight polymer and for obtaining a polymer having a condensed polycyclic aromatic skeleton in the molecule. In particular, the present invention relates to a chain transfer agent composition containing a chain transfer agent having a condensed polycyclic aromatic skeleton applicable to a radical polymerizable compound, a polymer produced using the same, and a method for producing the polymer.

Radical polymerizable compounds are organic compounds that are widely used industrially as raw materials for synthetic resins. Examples of such radical polymerizable compounds include acrylic acid, methacrylic acid, esters thereof, and styrene compounds. A wide variety of compounds are known.

In the polymerization process of these radically polymerizable compounds, it is beneficial to adjust the molecular weight of the produced polymer according to the intended use. In particular, when used for applications such as coating agents, adhesives, pressure-sensitive adhesives, paper strength enhancers, binders, resists, etc., molecular weight adjustment is an important technique.

There are various techniques for adjusting the molecular weight in the polymerization reaction of the radical polymerizable compound, but a method of adding a chain transfer agent to the polymerization system is often used. As the chain transfer agent, conventionally, halogenated hydrocarbons typified by carbon tetrachloride, alkyl mercaptan compounds typified by t- or n-dodecyl mercaptan, or sulfide compounds have been used (for example, patent documents). 1-3.)

For example, low molecular weight acrylic polymers have been widely used for applications such as paints, adhesives, and sealing materials. When producing such low molecular weight acrylic polymers, mercaptans as chain transfer agents are used. A compound is used (for example, refer patent documents 4-6).

In the polymerization of styrene, mercaptan chain transfer agents are added to adjust the average molecular weight, molecular weight distribution, melt flow index, and the like (see, for example, Patent Documents 7 and 8).

Also, in the production of polymerized toners used in copiers and printers, t-dodecyl mercaptan, 2-mercaptoethanol, etc. are used to obtain a low molecular weight and sharp molecular weight distribution when polymerizing styrene monomers and acrylic monomers. Mercaptan-based or halogen-based chain transfer agents such as carbon tetrachloride and trichlorobromomethane are used (see, for example, Patent Documents 9, 10, and 11).

Furthermore, since the resist for flat printing and the resist for the printed circuit board require water resistance and film strength of a portion cured by exposure, it is necessary to adjust the polymerization state with a chain transfer agent (see Patent Document 12). ).

On the other hand, chain transfer agents are known not only to adjust the molecular weight as described above, but also to impart their own residues to the polymer ends from the reaction mechanism (see, for example, Non-Patent Documents 1 to 3). .) Utilizing this fact, a technique for imparting a functional group to a polymer terminal by using a chain transfer agent having a functional group has also been proposed (see, for example, Patent Documents 13 and 14, Non-Patent Documents 4 and 5). .)

On the other hand, the compound having a condensed polycyclic aromatic skeleton of the present invention has a quinone skeleton. There are several examples where such a compound having a quinone skeleton is used as a polymerization inhibitor. For example, an example in which benzoquinone is used as a polymerization inhibitor is known (see Patent Document 15). However, this benzoquinone is used as a polymerization inhibitor and is not used as a chain transfer agent. Moreover, there is no suggestion about the effect as a chain transfer agent.

JP 2009-522411 A JP 2008-519137 A JP-A-9-118841 Japanese Patent Publication No.58-455 Japanese Patent Laid-Open No. 55-5950 Japanese Examined Patent Publication No. 46-40693 JP 2002-241413 A JP 2009-197105 A JP-A-7-330912 JP 2004-224840 A JP 2010-197954 A JP 2006-91479 A Japanese Patent Publication No.57-10850 JP 2010-222285 A Special table 2001-514280 gazette

By G. Odian, Principles of Polymerization, 4th edition, 2004, John Wiley & Sons, New York, 238 pages Takatsu Otsu, “Chemistry of Polymer Synthesis” (Chemical Doujin, 1979) p. 93 Edited by Mikiharu Konoike, “Radical Polymerization Handbook” (NTS, 2010), p. 47 Tanaka Seifumi, Nishida Haruo, Endo Go, Macromolecules, 2009, 42, 293-298 Tetsuo Ogawa, paint research (Kansai Paint), No. 137, Oct, 2001, 11 pages.

Conventionally used chain transfer agents such as halogenated hydrocarbons, especially carbon tetrachloride, have environmental problems such as destroying the earth's ozone layer, and alkyl mercaptans and sulfides have strong odors and handling problems. In addition, there is a problem that odor remains in the resin. In addition, these thiol chain transfer agents also have a problem in that the storage stability is inferior because the ene-thiol reaction occurs during storage and thus the viscosity of the polymerizable composition increases and gelation occurs. Furthermore, these thiol chain transfer agents also have a problem of generating a sulfur-containing gas and desorbing from the polymer to corrode the metal.

In addition, when these chain transfer agents are used, naturally, sulfur or the like is taken into the polymerization terminal, which may corrode containers and the like, makes the resin hygroscopic, and may cause environmental problems when the resin is disposed of. It was difficult to use depending on the application. On the other hand, alpha methyl styrene dimer has few environmental problems and is widely used, but still has a problem of having an odor.

In addition, it is known that a chain transfer agent is added to the end of a growing polymer to cause chain transfer, and it has been proposed to produce a polymer having a functional group at the end using this (for example, Patent Document 11). 12, see Non-Patent Documents 4 and 5.). However, all of these chain transfer agents are derivatives of the above-mentioned halogenated hydrocarbons, alkyl mercaptans, and alphamethylstyrene dimers, and it must be said that they have the above-mentioned problems as they are.

Therefore, in view of such circumstances, the present invention provides an entirely new chain transfer agent composition that is environmentally friendly and has a large chain transfer ability. The chain transfer agent composition of the present invention is a molecular weight regulator that produces a polymer having a narrow molecular weight distribution. In particular, the chain transfer agent composition has a number average molecular weight that adversely affects physical properties such as an increase in melt viscosity and a decrease in solubility of the produced polymer. The chain transfer agent composition which can suppress effectively the production | generation of the high molecular weight component exceeding self and self-crosslinking is provided. Furthermore, the objective of this invention is providing the polymer provided with the condensed polycyclic aromatic skeleton which has a functional group at the terminal, and its manufacturing method.

Therefore, in order to solve the above problems, the present inventors have made extensive studies on the chain transfer agent of the radical polymerizable compound, and as a result, the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention and the chain transfer aid described later. The chain transfer agent composition containing a chain transfer agent having a condensed polycyclic aromatic skeleton and a chain transfer aid have an excellent chain transfer effect due to the synergistic effect of the chain transfer agent and the chain transfer of the present invention in the molecule. The present inventors have found that a polymer having a condensed polycyclic aromatic skeleton derived from an agent can be produced.

That is, the first invention in the present invention includes at least a chain transfer agent having a condensed polycyclic aromatic skeleton represented by the following general formula (1), an aliphatic alcohol compound having 1 to 8 carbon atoms, and 2 carbon atoms. -8 aliphatic ketone compounds, ester compounds of fatty acids having 1 to 8 carbon atoms, aliphatic hydrocarbon compounds having 4 to 10 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, fats having 3 to 10 carbon atoms Group ether compound, terpenoid compound, styrene oligomer compound, unsaturated hydrocarbon compound having 4 to 10 carbon atoms, thiol compound having 4 to 14 carbon atoms, aliphatic amine having 2 to 8 carbon atoms, and 8 to 14 carbon atoms It exists in the chain transfer agent composition characterized by including the 1 or 2 or more types of chain transfer adjuvant selected from the group which consists of an aromatic amine compound.

(In the formula (1), n represents an integer of 1 to 4, and when there are a plurality of Rs, each independently represents a hydrogen atom, alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, aryloxy group or halogen. X and Y each independently represent a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an amino group, or a halogen atom, but X and Y are bonded to each other instead of the substituent. A saturated or unsaturated 6-membered ring may be formed, and the 6-membered ring formed by X and Y further has an alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, aryloxy group or halogen atom. May be substituted.)

  The second invention is the chain transfer agent according to the first invention, characterized in that, in general formula (1), n is 4, R is a hydrogen atom, and X and Y are hydrogen atoms. Present in the composition.

  According to a third invention, in the general formula (1), X is a hydroxy group, an alkyl group, an alkoxy group, an amino group, or a halogen atom, and Y is a hydrogen atom. The chain transfer agent composition described.

  A fourth invention is characterized in that, in the general formula (1), n is 4, R is a hydrogen atom, X is a hydroxy group or a methyl group, and Y is a hydrogen atom. The chain transfer agent composition described in the invention.

  A fifth invention is characterized in that, in the general formula (1), n is 4, R is a hydrogen atom, X is a chlorine atom, and Y is a chlorine atom or an amino group. The chain transfer agent composition described in the invention.

  The sixth invention includes at least a chain transfer agent having a condensed polycyclic aromatic skeleton represented by the following general formula (2) or (3), an aliphatic alcohol compound having 1 to 8 carbon atoms, and 2 to 2 carbon atoms. 8 aliphatic ketone compound, ester compound of fatty acid having 1 to 8 carbon atoms, aliphatic hydrocarbon compound having 4 to 10 carbon atoms, aromatic hydrocarbon compound having 6 to 10 carbon atoms, aliphatic having 3 to 10 carbon atoms Ether compounds, terpenoid compounds, styrene oligomer compounds, unsaturated hydrocarbon compounds having 4 to 10 carbon atoms, thiol compounds having 4 to 14 carbon atoms, aliphatic amines having 2 to 8 carbon atoms, and aromas having 8 to 14 carbon atoms It exists in the chain transfer agent composition characterized by containing the 1 or 2 or more types of chain transfer adjuvant selected from the group which consists of a group amine compound.

(In the formula (2), n represents an integer of 1 to 4, and when there are a plurality of R, each independently represents a hydrogen atom, alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, aryloxy group or halogen. Represents an atom, and Q represents a hydrogen atom, an alkyl group or a halogen atom.)

(In the formula (3), n represents an integer of 1 to 4, and when there are a plurality of R, each independently represents a hydrogen atom, alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, aryloxy group or halogen. Represents an atom, and Q represents a hydrogen atom, an alkyl group or a halogen atom.)

In a seventh aspect of the invention, the chain transfer aid is a kind selected from the group consisting of an aliphatic alcohol compound having 1 to 8 carbon atoms, an aliphatic ether compound having 3 to 10 carbon atoms, a terpenoid compound and a styrene oligomer compound. Or it exists in the chain transfer agent composition as described in any one of 1st invention thru | or 6th invention which is 2 or more types.

In an eighth invention, the chain transfer assistant is one or more selected from the group consisting of isopropyl alcohol, isobutanol, tetrahydrofuran, α-methylstyrene dimer and terpinolene. It exists in the chain transfer agent composition as described in any one of this invention.

A ninth invention resides in the chain transfer agent composition according to any one of the first to sixth inventions, wherein the chain transfer assistant is isopropyl alcohol or tetrahydrofuran.

A tenth invention resides in a radical polymerizable composition comprising the chain transfer agent composition described in any one of the first to ninth inventions and a radical polymerizable compound. .

The eleventh invention resides in the radically polymerizable composition according to the tenth invention, wherein the radically polymerizable compound is (meth) acrylic acid, (meth) acrylic acid ester or styrene.

A twelfth invention is a polymer obtained by radical polymerization of the radically polymerizable composition according to the tenth invention or the eleventh invention, wherein the condensation is applied to the terminal of the polymer or a part of the main chain. A polymer having a residue derived from a chain transfer agent having a polycyclic aromatic skeleton.

A thirteenth invention is a polymer terminal characterized by radical polymerizing a radically polymerizable compound in the presence of the chain transfer agent composition described in any one of the first to ninth inventions. Or it exists in the method of manufacturing the polymer which has a residue derived from the chain transfer agent which has a condensed polycyclic aromatic skeleton in a part of main chain.

In the present invention, (meth) acryl represents acryl or methacryl, and (meth) acrylate represents acrylate or methacrylate.

By using a chain transfer agent composition containing a chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention as a radical polymerizable compound, it is possible to effectively adjust the molecular weight of a desired polymer, The occurrence of an unpleasant odor in the polymer can also be suppressed. Furthermore, a polymer having a condensed polycyclic aromatic skeleton at the terminal is synthesized by polymerizing a radical polymerizable compound using a chain transfer agent composition containing a chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention. be able to.

Chromatogram of gel permeation chromatography (manufactured by JASCO). In Example 1 and Comparative Example 2, the gel permeation chromatography (JASCO Corp.) equipped with a GPC column (Showex DPC Shodex GPC KF-806L) by dissolving the polymerization product after performing the polymerization reaction for 5 hours in tetrahydrofuran. The result of measuring the molecular weight distribution is shown. The horizontal axis represents the retention time in the column. The shorter the retention time, the larger the molecule.

[Chain transfer agent composition]
The chain transfer agent composition of the present invention contains at least a chain transfer agent having a condensed polycyclic aromatic skeleton represented by the following general formula (1) and a chain transfer aid described later.

(In the formula (1), n represents an integer of 1 to 4, and when there are a plurality of Rs, each independently represents a hydrogen atom, alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, aryloxy group or halogen. X and Y each independently represent a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an amino group, or a halogen atom, but X and Y are bonded to each other instead of the substituent. A saturated or unsaturated 6-membered ring may be formed, and the 6-membered ring formed by X and Y further has an alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, aryloxy group or halogen atom. May be substituted.)

[Chain transfer agent having a condensed polycyclic aromatic skeleton]
The chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention is represented by general formulas (1) to (3).

(In the formula (1), n represents an integer of 1 to 4, and when there are a plurality of Rs, each independently represents a hydrogen atom, alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, aryloxy group or halogen. X and Y each independently represent a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an amino group, or a halogen atom, but X and Y are bonded to each other instead of the substituent. A saturated or unsaturated 6-membered ring may be formed, and the 6-membered ring formed by X and Y further has an alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, aryloxy group or halogen atom. May be substituted.)

(In the formula (2), n represents an integer of 1 to 4, and when there are a plurality of R, each independently represents a hydrogen atom, alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, aryloxy group or halogen. Represents an atom, and Q represents a hydrogen atom, an alkyl group or a halogen atom.)

(In the formula (3), n represents an integer of 1 to 4, and when there are a plurality of R, each independently represents a hydrogen atom, alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, aryloxy group or halogen. Represents an atom, and Q represents a hydrogen atom, an alkyl group or a halogen atom.)

In general formula (1) thru | or (3), as an alkyl group represented by R, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, tert-butyl Group, n-pentyl group, n-hexyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group and the like. As the aryl group, phenyl group, p-tolyl group, o-tolyl group, naphthyl Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, and i. -A propoxy group etc. are mentioned, A phenoxy group, a triloxy group etc. are mentioned as an aryloxy group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

In the general formulas (2) and (3), examples of the alkyl group represented by Q include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and tert-butyl. Group, n-pentyl group, n-hexyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group, and the like. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

Examples of the alkyl group represented by X and Y in the general formula (1) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a pentyl group, 2- Examples include an ethylhexyl group, a 4-methylpentyl group, a 4-methyl-3-pentenyl group, and the alkoxy group includes a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and the like. Includes fluorine, chlorine, bromine and iodine.

In the general formula (1), as an example in which X and Y are bonded to each other, X and Y are CH ₂ CH ₂ groups, and X and Y are bonded by a single bond (this compound is Represented by the formula (3)), X and Y are CH ₂ CH groups, and X and Y are bonded by a double bond (this compound is represented by the general formula (2)). ), X and Y are CH═CH groups, and X and Y are bonded by a single bond to form an aromatic ring. The 6-membered ring formed by X and Y may be further substituted with an alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, aryloxy group or halogen atom. Furthermore, examples of the substituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a tert-butyl group, and the aryl group includes a phenyl group. Group, p-tolyl group, o-tolyl group, naphthyl group, and the like. Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, naphthylethyl group, and the like. Methoxy group, ethoxy group, n-propoxy group, i-propoxy group and the like. Examples of the aryloxy group include a phenoxy group and a triloxy group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Next, specific examples of the compound represented by the general formula (1) will be given. First, in the general formula (1), examples of the compound in which X and Y are hydrogen atoms include the following compounds. For example, 1,4-naphthoquinone, 5-methyl-1,4-naphthoquinone, 6-methyl-1,4-naphthoquinone, 6,7-dimethyl-1,4-naphthoquinone, 5-butyl-1,4-naphthoquinone, 6-butyl-1,4-naphthoquinone, 6,7-dibutyl-1,4-naphthoquinone, 5-pentyl-1,4-naphthoquinone, 6-pentyl-1,4-naphthoquinone, 5-chloro-1,4- Naphthoquinone, 6-chloro-1,4-naphthoquinone, 6,7-dichloro-1,4-naphthoquinone, 5-hydroxy-1,4-naphthoquinone, 6-hydroxy-1,4-naphthoquinone, 5,8-dihydroxy- 1,4-naphthoquinone, 5,6,8-trihydroxy-1,4-naphthoquinone, 5-methoxy-1,4-naphthoquinone, 6-methoxy-1,4-naphthoquinone 5,8-dimethoxy-1,4-naphthoquinone and the like.

Among these compounds, 1,4-naphthoquinone is easily available as a reagent. The compounds having substituents at the 5th to 8th positions are the corresponding naphthalenes as described in the 5th edition, Experimental Chemistry Lecture 15, Synthesis of Organic Compounds III Aldehyde, Ketone, and Quinone (edited by the Chemical Society of Japan), page 379. Oxidation treatment of compounds, as well as 5th edition Experimental Chemistry Course 15 Synthesis of Organic Compounds III Aldehyde / Ketone / Quinone (Edited by Chemical Society of Japan), page 393 Cycloadducts can be synthesized by Alder reaction, then isomerized and oxidized.

Among these compounds, 1,4-naphthoquinone is particularly preferable because it is easy to produce and highly active.

Next, in the general formula (1), examples of the compound in which X is a hydroxy group, an alkyl group, an alkoxy group, an amino group, or a halogen atom, and Y is a hydrogen atom include the following compounds. For example, 2-methyl-1,4-naphthoquinone, 2-ethyl-1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, 2-methoxy-1,4-naphthoquinone, 2-chloro-1,4- Naphthoquinone, 2-amino-1,4-naphthoquinone, 2,5-dimethyl-1,4-naphthoquinone, 2,6-dimethyl-1,4-naphthoquinone, 2,6,7-trimethyl-1,4-naphthoquinone, 2-methyl-5-butyl-1,4-naphthoquinone, 2-methyl-6-butyl-1,4-naphthoquinone, 2-methyl-6,7-dibutyl-1,4-naphthoquinone, 2-methyl-5 Pentyl-1,4-naphthoquinone, 2-methyl-6-pentyl-1,4-naphthoquinone, 2-methyl-5-chloro-1,4-naphthoquinone, 2-methyl-6-chloro-1,4-naphth Quinone, 2-methyl-6,7-dichloro-1,4-naphthoquinone, 2-methyl-5-hydroxy-1,4-naphthoquinone, 2-methyl-6-hydroxy-1,4-naphthoquinone, 2-methyl- 5,8-dihydroxy-1,4-naphthoquinone, 2-methyl-5,6,8-trihydroxy-1,4-naphthoquinone, 2-methyl-5-methoxy-1,4-naphthoquinone, 2-methyl-6 -Methoxy-1,4-naphthoquinone, 2-methyl-5,8-dimethoxy-1,4-naphthoquinone, 2-hydroxy-5-methyl-1,4-naphthoquinone, 2-ethyl-5-methyl-1,4 -Naphthoquinone, 2-ethyl-6-methyl-1,4-naphthoquinone, 2-ethyl-6,7-dimethyl-1,4-naphthoquinone, 2-ethyl-5-butyl-1,4-naphthoquino 2-ethyl-6-butyl-1,4-naphthoquinone, 2-ethyl-6,7-dibutyl-1,4-naphthoquinone, 2-ethyl-5-pentyl-1,4-naphthoquinone, 2-ethyl-6 -Pentyl-1,4-naphthoquinone, 2-ethyl-5-chloro-1,4-naphthoquinone, 2-ethyl-6-chloro-1,4-naphthoquinone, 2-ethyl-6,7-dichloro-1,4 -Naphthoquinone, 2-ethyl-5-hydroxy-1,4-naphthoquinone, 2-ethyl-6-hydroxy-1,4-naphthoquinone, 2-ethyl-5,8-dihydroxy-1,4-naphthoquinone, 2-ethyl -5,6,8-trihydroxy-1,4-naphthoquinone, 2-ethyl-5-methoxy-1,4-naphthoquinone, 2-ethyl-6-methoxy-1,4-naphthoquinone, 2-ethyl- 5,8-dimethoxy-1,4-naphthoquinone, 2-hydroxy-6-methyl-1,4-naphthoquinone, 2-hydroxy-6,7-dimethyl-1,4-naphthoquinone, 2-hydroxy-5-butyl- 1,4-naphthoquinone, 2-hydroxy-6-butyl-1,4-naphthoquinone, 2-hydroxy-6,7-dibutyl-1,4-naphthoquinone, 2-hydroxy-5-pentyl-1,4-naphthoquinone, 2-hydroxy-6-pentyl-1,4-naphthoquinone, 2-hydroxy-5-chloro-1,4-naphthoquinone, 2-hydroxy-6-chloro-1,4-naphthoquinone, 2-hydroxy-6,7- Dichloro-1,4-naphthoquinone, 2,5-dihydroxy-1,4-naphthoquinone, 2,6-dihydroxy-1,4-naphthoquinone, 2,5,8-toe Hydroxy-1,4-naphthoquinone, 2,5,6,8-tetrahydroxy-1,4-naphthoquinone, 2-hydroxy-5-methoxy-1,4-naphthoquinone, 2-hydroxy-6-methoxy-1,4 -Naphthoquinone, 2-hydroxy-5,8-dimethoxy-1,4-naphthoquinone, 2-methoxy-5-methyl-1,4-naphthoquinone, 2-methoxy-6-methyl-1,4-naphthoquinone, 2-methoxy -6,7-dimethyl-1,4-naphthoquinone, 2-methoxy-5-butyl-1,4-naphthoquinone, 2-methoxy-6-butyl-1,4-naphthoquinone, 2-methoxy-6,7-dibutyl -1,4-naphthoquinone, 2-methoxy-5-pentyl-1,4-naphthoquinone, 2-methoxy-6-pentyl-1,4-naphthoquinone, 2-methoxy 5-chloro-1,4-naphthoquinone, 2-methoxy-6-chloro-1,4-naphthoquinone, 2-methoxy-6,7-dichloro-1,4-naphthoquinone, 2-methoxy-5-hydroxy-1, 4-naphthoquinone, 2-methoxy-6-hydroxy-1,4-naphthoquinone, 2-methoxy-5,8-dihydroxy-1,4-naphthoquinone, 2-methoxy-5,6,8-trihydroxy-1,4 -Naphthoquinone, 2,5-dimethoxy-1,4-naphthoquinone, 2,6-dimethoxy-1,4-naphthoquinone, 2,5,8-trimethoxy-1,4-naphthoquinone, 2-chloro-5-methyl-1 , 4-naphthoquinone, 2-chloro-6-methyl-1,4-naphthoquinone, 2-chloro-6,7-dimethyl-1,4-naphthoquinone, 2-chloro-5-butyl-1, 4-naphthoquinone, 2-chloro-6-butyl-1,4-naphthoquinone, 2-chloro-6,7-dibutyl-1,4-naphthoquinone, 2-chloro-5-pentyl-1,4-naphthoquinone, 2- Chloro-6-pentyl-1,4-naphthoquinone, 2,5-dichloro-1,4-naphthoquinone, 2,6-dichloro-1,4-naphthoquinone, 2,6,7-trichloro-1,4-naphthoquinone, 2-chloro-5-hydroxy-1,4-naphthoquinone, 2-chloro-6-hydroxy-1,4-naphthoquinone, 2-chloro-5,8-dihydroxy-1,4-naphthoquinone, 2-chloro-5, 6,8-trihydroxy-1,4-naphthoquinone, 2-chloro-5-methoxy-1,4-naphthoquinone, 2-chloro-6-methoxy-1,4-naphthoquinone, 2-chloro-5 8-dimethoxy-1,4-naphthoquinone, 2-amino-5-methyl-1,4-naphthoquinone, 2-amino-6-methyl-1,4-naphthoquinone, 2-amino-6,7-dimethyl-1, 4-naphthoquinone, 2-amino-5-butyl-1,4-naphthoquinone, 2-amino-6-butyl-1,4-naphthoquinone, 2-amino-6,7-dibutyl-1,4-naphthoquinone, 2- Amino-5-pentyl-1,4-naphthoquinone, 2-amino-6-pentyl-1,4-naphthoquinone, 2-amino-5-chloro-1,4-naphthoquinone, 2-amino-6-chloro-1, 4-naphthoquinone, 2-amino-6,7-dichloro-1,4-naphthoquinone, 2-amino-5-hydroxy-1,4-naphthoquinone, 2-amino-6-hydroxy-1,4-naphthoquinone 2-amino-5,8-dihydroxy-1,4-naphthoquinone, 2-amino-5,6,8-trihydroxy-1,4-naphthoquinone, 2-amino-5-methoxy-1,4-naphthoquinone, 2 -Amino-6-methoxy-1,4-naphthoquinone, 2-amino-5,8-dimethoxy-1,4-naphthoquinone and the like.

Although many of these naphthoquinone compounds having a substituent at the 2-position are available as reagents, a hydroquinone compound substituted at the 2-position by reaction of a 1,4-naphthoquinone compound with the corresponding nucleophile is used. Thereafter, it can be obtained by oxidation treatment. For example, Fifth Edition Experimental Chemistry Lecture 15 Synthesis of Organic Compounds III Aldehyde / Ketone / Quinone (Edited by Chemical Society of Japan) pages 369 and 384 can be synthesized.

In general, a compound having a substituent at the 2-position of the naphthoquinone skeleton is easy to produce and is preferable. Among these compounds, 2-methyl-1,4-naphthoquinone and 2-hydroxy-1,4-naphthoquinone are: It is preferable because it is easy to produce and highly active.

Furthermore, in the general formula (1), examples of the compound in which X and Y are a hydroxy group, an alkyl group, an alkoxy group, an amino group, or a halogen atom include the following compounds. For example, 2,3-dimethyl-1,4-naphthoquinone, 2,3-diethyl-1,4-naphthoquinone, 2-methyl-3-hydroxy-1,4-naphthoquinone, 2-methyl-3-methoxy-1, 4-naphthoquinone, 2,3-dihydroxy-1,4-naphthoquinone, 2,3-dimethoxy-1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, 2-amino-3-chloro-1, 4-naphthoquinone, 2,3,6-trimethyl-1,4-naphthoquinone, 2,3,6,7-tetramethyl-1,4-naphthoquinone, 2,3-dimethyl-5-butyl-1,4-naphthoquinone 2,3-dimethyl-6-butyl-1,4-naphthoquinone, 2,3-dimethyl-6,7-dibutyl-1,4-naphthoquinone, 2,3-dimethyl-5-pentyl-1,4-naphthoquinone 2,3-dimethyl-6-pentyl-1,4-naphthoquinone, 2,3-dimethyl-5-chloro-1,4-naphthoquinone, 2,3-dimethyl-6-chloro-1,4-naphthoquinone, 2,3-dimethyl-6,7-dichloro-1,4-naphthoquinone, 2,3-dimethyl-5-hydroxy-1,4-naphthoquinone, 2,3-dimethyl-6-hydroxy-1,4-naphthoquinone, 2,3-dimethyl-5,8-dihydroxy-1,4-naphthoquinone, 2,3-dimethyl-5,6,8-trihydroxy-1,4-naphthoquinone, 2,3-dimethyl-5-methoxy-1 , 4-naphthoquinone, 2,3-dimethyl-6-methoxy-1,4-naphthoquinone, 2,3-dimethyl-5,8-dimethoxy-1,4-naphthoquinone, 2,6-dimethyl-3-hydroxy- , 4-naphthoquinone, 2,6,7-trimethyl-3-hydroxy-1,4-naphthoquinone, 2-methyl-3-hydroxy-5-butyl-1,4-naphthoquinone, 2-methyl-3-hydroxy-6 -Butyl-1,4-naphthoquinone, 2-methyl-3-hydroxy-6,7-dibutyl-1,4-naphthoquinone, 2-methyl-3-hydroxy-5-pentyl-1,4-naphthoquinone, 2-methyl -3-hydroxy-6-pentyl-1,4-naphthoquinone, 2-methyl-3-hydroxy-5-chloro-1,4-naphthoquinone, 2-methyl-3-hydroxy-6-chloro-1,4-naphthoquinone 2-methyl-3-hydroxy-6,7-dichloro-1,4-naphthoquinone, 2-methyl-3,5-dihydroxy-1,4-naphthoquinone, 2-methyl-3, 6-dihydroxy-1,4-naphthoquinone, 2-methyl-3,5,8-trihydroxy-1,4-naphthoquinone, 2-methyl-3,5,6,8-tetrahydroxy-1,4-naphthoquinone, 2-methyl-3-hydroxy-5-methoxy-1,4-naphthoquinone, 2-methyl-3-hydroxy-6-methoxy-1,4-naphthoquinone, 2-methyl-3-hydroxy-5,8-dimethoxy- 1,4-naphthoquinone, 2,3-dichloro-6-methyl-1,4-naphthoquinone, 2,3-dichloro-6,7-dimethyl-1,4-naphthoquinone, 2,3-dichloro-5-butyl- 1,4-naphthoquinone, 2,3-dichloro-6-butyl-1,4-naphthoquinone, 2,3-dichloro-6,7-dibutyl-1,4-naphthoquinone, 2,3-dichloro-5-pen 1,4-naphthoquinone, 2,3-dichloro-6-pentyl-1,4-naphthoquinone, 2,3,5-trichloro-1,4-naphthoquinone, 2,3,6-trichloro-1,4- Naphthoquinone, 2,3,6,7-tetrachloro-1,4-naphthoquinone, 2,3-dichloro-5-hydroxy-1,4-naphthoquinone, 2,3-dichloro-6-hydroxy-1,4-naphthoquinone 2,3-dichloro-5,8-dihydroxy-1,4-naphthoquinone, 2,3-dichloro-5,6,8-trihydroxy-1,4-naphthoquinone, 2,3-dichloro-5-methoxy- 1,4-naphthoquinone, 2,3-dichloro-6-methoxy-1,4-naphthoquinone, 2,3-dichloro-5,8-dimethoxy-1,4-naphthoquinone, 2-amino-3-chloro-6 Me 1,4-naphthoquinone, 2-amino-3-chloro-6,7-dimethyl-1,4-naphthoquinone, 2-amino-3-chloro-5-butyl-1,4-naphthoquinone, 2-amino- 3-chloro-6-butyl-1,4-naphthoquinone, 2-amino-3-chloro-6,7-dibutyl-1,4-naphthoquinone, 2-amino-3-chloro-5-pentyl-1,4- Naphthoquinone, 2-amino-3-chloro-6-pentyl-1,4-naphthoquinone, 2-amino-3-chloro-5-chloro-1,4-naphthoquinone, 2-amino-3,6-dichloro-1, 4-naphthoquinone, 2-amino-3,6,7-trichloro-1,4-naphthoquinone, 2-amino-3-chloro-5-hydroxy-1,4-naphthoquinone, 2-amino-3-chloro-6 Hydroxy-1,4 -Naphthoquinone, 2-amino-3-chloro-5,8-dihydroxy-1,4-naphthoquinone, 2-amino-3-chloro-5,6,8-trihydroxy-1,4-naphthoquinone, 2-amino- 3-chloro-5-methoxy-1,4-naphthoquinone, 2-amino-3-chloro-6-methoxy-1,4-naphthoquinone, 2-amino-3-chloro-5,8-dimethoxy-1,4- And naphthoquinone.

Many of these naphthoquinone compounds having a substituent at the 2-position are available as reagents, but are obtained by repeating the oxidation treatment after the reaction between the 1,4-naphthoquinone compound and the corresponding nucleophile. be able to. For example, it can be synthesized by the method described in page 386 of Fifth Edition Experimental Chemistry Lecture 15 Synthesis of Organic Compounds III Aldehyde / Ketone / Quinone (Edited by Chemical Society of Japan).

Among these compounds, 2,3-dichloro-1,4-naphthoquinone and 2-amino-3-chloro-1,4-naphthoquinone are preferable because they are easy to produce and highly active.

In the general formula (1), examples in which X and Y are bonded to each other include the following compounds. First, X and Y are CH ₂ CH groups, and those in which X and Y are bonded by a double bond are compounds represented by the general formula (2). Specific examples thereof include 1, 4-dihydro-9,10-anthraquinone, 2-methyl-1,4-dihydro-9,10-anthraquinone, 2-chloro-1,4-dihydro-9,10-anthraquinone, 6-methyl-1,4- Dihydro-9,10-anthraquinone, 2,6-dimethyl-1,4-dihydro-9,10-anthraquinone, 2-chloro-6-methyl-1,4-dihydro-9,10-anthraquinone, 2,6- Examples include dichloro-1,4-dihydro-9,10-anthraquinone. A compound in which X and Y are CH ₂ CH ₂ groups and X and Y are bonded by a single bond is a compound represented by the general formula (3). , 3,4-tetrahydro-9,10-anthraquinone, 2-methyl-1,2,3,4-tetrahydro-9,10-anthraquinone, 2-chloro-1,2,3,4-tetrahydro-9,10 -Anthraquinone, 6-methyl-1,2,3,4-tetrahydro-9,10-anthraquinone, 2,6-dimethyl-1,2,3,4-tetrahydro-9,10-anthraquinone, 2-chloro-6 -Methyl-1,2,3,4-tetrahydro-9,10-anthraquinone, 2,6-dichloro-1,2,3,4-tetrahydro-9,10-anthraquinone and the like. Furthermore, examples of the compound other than the compound represented by the general formula (2) or (3) in which X and Y are bonded to each other in the general formula (1) include 9,10-anthraquinone, 2- Methyl-9,10-anthraquinone, 2-chloro-9,10-anthraquinone, 6-methyl-9,10-anthraquinone, 2,6-dimethyl-9,10-anthraquinone, 2-chloro-6-methyl-9, Examples include 10-anthraquinone and 2,6-dichloro-9,10-anthraquinone.

These compounds synthesize cycloaddition products by Diels-Alder reaction of 1,4-naphthoquinone compounds and the corresponding butadiene compounds, then isomerize and then oxidize, and further catalytically reduce this oxidant with hydrogen. Can be synthesized.

Among these compounds, 1,4-dihydro-9,10-anthraquinone, 1,2,3,4-tetrahydro-9,10-anthraquinone, 2-methyl-1,4-dihydro-9,10-anthraquinone 2-methyl-1,2,3,4-tetrahydro-9,10-anthraquinone, 2-chloro-1,4-dihydro-9,10-anthraquinone, 2-chloro-1,2,3,4-tetrahydro -9,10-anthraquinone is preferred because it is easy to produce and highly active.

[Chain transfer aid]
The chain transfer aid of the present invention includes an aliphatic alcohol compound having 1 to 8 carbon atoms, an aliphatic ketone compound having 2 to 8 carbon atoms, an ester compound of a fatty acid having 1 to 8 carbon atoms, and a fat having 4 to 10 carbon atoms. Group hydrocarbon compound, aromatic hydrocarbon compound having 6 to 10 carbon atoms, aliphatic ether compound having 3 to 10 carbon atoms, terpenoid compound, styrene oligomer compound, unsaturated hydrocarbon compound having 4 to 10 carbon atoms, carbon One or two or more compounds selected from the group consisting of a thiol compound having 4 to 14 carbon atoms, an aliphatic amine having 2 to 8 carbon atoms and an aromatic amine compound having 8 to 14 carbon atoms are used.

The aliphatic alcohol compound is preferably an aliphatic alcohol compound having 1 to 8 carbon atoms, and may be a monohydric alcohol having one hydroxyl group in a molecule or a polyhydric alcohol having two or more hydroxyl groups. Class 3 or 3 can be used. Examples of the monohydric alcohol include methanol, ethanol, propanol, isopropyl alcohol, butanol, isobutanol, t-butanol, pentanol, hexanol, heptanol, octanol and the like. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, glycerin, trimethylolpropane and the like.

As the aliphatic ketone compound, an aliphatic ketone compound having 2 to 8 carbon atoms is preferable, and examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone.

The fatty acid ester compound is preferably a fatty acid ester compound having 1 to 8 carbon atoms, and examples thereof include ethyl acetate, n-butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, and butyl carbitol acetate.

As an aliphatic hydrocarbon compound, a C4-C10 aliphatic hydrocarbon compound is preferable, and an alicyclic compound may be sufficient. For example, n-butane, n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane, cyclobutane, decalin and the like can be mentioned. Some of these compounds may be substituted with a halogen atom.

As an aromatic hydrocarbon compound, a C6-C10 aromatic hydrocarbon compound is preferable, and toluene, xylene, ethylbenzene, isopropylbenzene, etc. are mentioned.

As an aliphatic ether compound, a C3-C10 aliphatic ether compound is preferable, and a C4-C10 alicyclic ether compound may be sufficient. For example, n-butyl ether, dioxane, tetrahydrofuran and the like can be mentioned. Glycol ethers can also be used. For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 3-methoxy Examples include butanol.

Examples of the styrene oligomer compound include α-methylstyrene dimer and styrene dimer.

Examples of terpenoid compounds include limonene, myrcene, α-terpinene, β-terpinene, γ-terpinene, terpinolene, β-pinene, α-pinene, and dipentene.

Examples of the unsaturated hydrocarbon compound include 1,4-cyclohexadiene, 2-methyl-1,4-cyclohexadiene, 1,2-dihydronaphthalene, 9,10- which are unsaturated hydrocarbon compounds having 4 to 10 carbon atoms. Examples include dihydrophenanthrene, octahydrophenanthrene, 9,10-dihydroanthracene, octahydroanthracene, tetralin, indene and the like.

The thiol compound may be a thiol compound having 4 to 14 carbon atoms having one or more mercapto groups, such as n-butyl mercaptan, t-butyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan. , T-dodecyl mercaptan, mercaptoethanol, mercaptoethylamine, mercaptopropionic acid, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2- Examples include mercapto-2,5-dimethylaminopyridine.

As an amine compound, one or more of amino groups may be substituted with an alkyl group or a substituted alkyl group, and a carboxyl group, alkoxycarbonyl group, substituted alkoxycarbonyl group, phenoxycarbonyl group, substituted It may be substituted with a phenoxycarbonyl group, a nitrile group or the like. For example, C2-C8 aliphatic amines such as triethanolamine and methyldiethanolamine, 2-dimethylaminoethylbenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid Examples thereof include aromatic amines having 8 to 14 carbon atoms such as isobutyl, 4,4-dimethylaminobenzophenone and N, N-dimethylaniline.

These chain transfer aids may be used alone or in combination of two or more.

Among these, an aliphatic alcohol compound having 1 to 8 carbon atoms, an aliphatic ether compound having 3 to 10 carbon atoms including an alicyclic ether compound having 4 to 10 carbon atoms, a terpenoid compound, and a styrene dimer compound are preferable. In particular, secondary alcohols such as isopropyl alcohol, isobutanol, alicyclic ethers of tetrahydrofuran, styrene oligomeric compounds of α-methylstyrene dimer, and terpenoids of terpinolene are preferable, and isopropyl alcohol and tetrahydrofuran are more preferable. preferable.

The serial transfer agent composition of the present invention is a composition containing at least a chain transfer agent having a condensed polycyclic aromatic skeleton and the above chain transfer aid. The optimum addition ratio of the chain transfer aid to the chain transfer agent having a condensed polycyclic aromatic skeleton in the chain transfer agent composition of the present invention varies depending on the chain transfer aid used.

The chain transfer aid of the present invention exhibits some chain transfer effect alone in the polymerization reaction. The chain transfer assistant (Cs) having a chain transfer constant (Cs) of 0.1 or less in the polymerization system to be used is a mass ratio of 0. 0 to the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention. It is preferable to add 01 times or more and less than 50 times, and more preferably 0.1 times or more and less than 30 times. If it is less than 0.01 times, the effect of the chain transfer aid to be added is small, and even if it is added 50 times or more, no more effect can be expected. Examples of such chain transfer aids having a chain transfer constant (Cs) of 0.1 or less include aliphatic alcohol compounds, aliphatic ether compounds, aliphatic hydrocarbons, aromatic hydrocarbons, and other compounds that are generally used as solvents. It is.

In addition, the chain transfer aid (Cs) in the polymerization system used has a chain transfer constant (Cs) of 0.1 or more, in a mass ratio of 0 to the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention. It is preferable to add 0.01 times or more and less than 2 times. If the amount is less than 0.01 times, the effect of the chain transfer aid to be added is small, and if added twice or more, the effect is that a polymer having a condensed polycyclic aromatic skeleton derived from the chain transfer agent of the present invention is generated in the molecule. This is not preferable because it is not sufficient. Examples of such chain transfer aids having a chain transfer constant (Cs) of 0.1 or more include thiol compounds.

[Radical polymerization]
By using the chain transfer agent composition of the present invention, the degree of polymerization of the radical polymerizable compound can be adjusted in the polymerization reaction of the radical polymerizable compound.

As the polymerization method, various polymerization methods such as solution polymerization, emulsion polymerization and suspension polymerization can be employed.

In the aqueous solution polymerization method, water is used as a solvent, for example, a water-soluble ethylenically unsaturated monomer such as acrylic acid or a sodium salt thereof is mixed and dissolved with a radical polymerization initiator, and the aqueous solution is heated to polymerize. In that case, the polymerization degree etc. of a radically polymerizable compound can be adjusted by adding the chain transfer agent composition of this invention.

In the emulsion polymerization method, usually, water is used as a medium, and a hydrophobic monomer that is hardly soluble in water such as vinyl acetate, styrene, or methyl methacrylate and a radical polymerization initiator are mixed in the presence of a surfactant. Stir and polymerize in the emulsified state (O / W emulsion). In that case, the polymerization degree etc. of a radically polymerizable compound can be adjusted by adding the chain transfer agent composition of this invention.

In the emulsion polymerization method, a method (W / O type emulsion) in which a hydrophilic monomer that is hardly soluble in an organic solvent is polymerized in the presence of a radical polymerization initiator using an organic solvent as a medium can also be used. By adding the chain transfer agent composition of the invention, the degree of polymerization of the radically polymerizable compound can be adjusted.

In the suspension polymerization method, for example, a hydrophobic monomer that is hardly soluble in water, such as vinyl acetate, styrene, and methyl methacrylate, and a radical polymerization initiator in water using a dispersion stabilizer, the mixture is stirred and suspended. Polymerize in the state. In that case, the polymerization degree etc. of a radically polymerizable compound can be adjusted by adding the chain transfer agent composition of this invention.

Further, an aqueous solution of a water-soluble ethylenically unsaturated monomer such as acrylic acid and its alkali metal salt, methacrylic acid and its alkali metal salt, acrylamide, methacrylamide and N, N-dimethylacrylamide is used as a surfactant, radical There is also a reverse phase suspension polymerization method in which a polymerization initiator, a crosslinking agent and an organic solvent are mixed, heated with stirring, and polymerized in a water-in-oil system. Also in that case, the degree of polymerization of the radical polymerizable compound can be adjusted by adding the chain transfer agent composition of the present invention.

[Radically polymerizable composition]
The chain transfer agent composition of the present invention can be used as a radically polymerizable composition by adding it to a radically polymerizable compound. In the chain transfer agent composition of the present invention, a chain transfer agent having a condensed polycyclic aromatic skeleton and a chain transfer aid can be separately added to the polymerization reactor. A radically polymerizable composition will be formed.

If necessary, a radical polymerization initiator that initiates a radical reaction is added to the radical polymerizable composition containing the chain transfer agent composition of the present invention as an essential component. A polymer having a molecular weight adjusted can be produced by applying initiation energy such as heat and light necessary for initiating the polymerization and initiating the polymerization.

The blending amount of the chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention is usually preferably 0.01 to 5% by weight based on the radical polymerizable compound from the viewpoint of sufficient chain transfer effect and economy. 0.05 to 3% by weight is more preferable.

The number average molecular weight of the polymer can be adjusted by the blending amount of the radically polymerizable compound generally used, the blending amount of the chain transfer agent composition of the present invention, and the blending amount of the radical polymerization initiator. The number average molecular weight increases as the blending amount of the radical polymerizable compound increases, and conversely decreases as the blending amount of the chain transfer agent composition increases. In consideration of this, the number average molecular weight can be adjusted by appropriately changing the amount within the range of the amount of the chain transfer agent composition of the present invention.

As a method for adding the chain transfer agent composition of the present invention to the radical polymerizable compound, known addition methods such as batch addition, batch addition, continuous addition, or a combination thereof are used. For example, a chain transfer agent is added batchwise in each step, a monomer mixture and a chain transfer agent are continuously added in each step, a chain transfer agent is added in combination with batch addition and continuous addition in each step, etc. There is an addition method. Alternatively, the chain transfer agent may be added directly as a solid or powder, or the chain transfer agent may be dissolved in an appropriate organic solvent and added.

In addition, a chain transfer agent having a condensed polycyclic aromatic skeleton and a chain transfer aid may be mixed in advance and used as a chain transfer agent composition, but may be added separately to the polymerization reaction system. Moreover, after adding one in a radically polymerizable compound previously, you may dispense the other. Various combinations of addition methods such as batch and dispensing of a chain transfer agent having a condensed polycyclic aromatic skeleton, a chain transfer aid and a radical polymerization initiator can also be taken. Further, from the viewpoint of controlling the molecular weight, a method of supplying the chain transfer agent, the chain transfer auxiliary agent, and the radical polymerizable compound while keeping the ratio thereof in-situ while keeping the concentration constant is also preferable.

In general, the chain transfer aid having a condensed polycyclic aromatic skeleton of the present invention is simple to use as a serial transfer agent composition in combination with a chain transfer aid as described above. A chain transfer agent having a condensed polycyclic aromatic skeleton and a chain transfer assistant are separately added to form a radical polymerizable composition, or a chain transfer having a condensed polycyclic aromatic skeleton in the polymerization process of a radical polymerizable compound. The radical polymerization operation may be performed by adding an agent and a chain transfer aid in an arbitrary order and number of times.

[Radically polymerizable compound]
The radically polymerizable compound in the present invention is not particularly limited as long as it is a compound having a polymerizable double bond in the molecule. Examples of such radically polymerizable compounds include α, β-unsaturated carboxylic acid compounds such as acrylic acid and methacrylic acid; methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, Α-, β-unsaturated carboxylic acid ester compounds such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methyl methacrylate, butyl methacrylate; vinyl ester compounds such as vinyl acetate; acrylonitrile, acrylamide, etc. Acrylic compounds; aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene and divinylbenzene; substituted ethylene compounds such as vinyl chloride and vinylidene chloride; ethylene, propylene, butene, butadiene, isoprene, cyclopentadiene, and pinet And unsaturated organic silane compounds such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and vinyltrimethoxysilane.

Among the radical polymerizable compounds, α, β-unsaturated carboxylic acid compounds, α, β-unsaturated carboxylic acid ester compounds, aromatic vinyl compounds, vinyl ester compounds, or combinations thereof are preferable.

Among these compounds, (meth) acrylic acid which is an α, β-unsaturated carboxylic acid compound, (meth) acrylic ester which is an α, β-unsaturated carboxylic acid ester, styrene which is an aromatic vinyl compound, or A combination thereof is preferred. In particular, styrene, α-methylstyrene, vinyltoluene, and divinylbenzene, which are aromatic vinyl compounds, are preferable from the viewpoint that the effect of the chain transfer agent composition of the present invention is remarkable.

The form and content of the radical polymerizable compound contained in the radical polymerizable composition are not particularly limited. For example, a radical polymerizable compound itself or a solution of a radical polymerizable compound can be used.

[Radical polymerization initiator]
The radical polymerization initiator is not particularly limited as long as it gives energy and generates an active radical for the radical polymerizable compound. Generally, so-called radical polymerization initiators that are commercially available can be used. For convenience, what is used with thermal energy applied is called a thermal radical polymerization initiator, and what gives light energy is called a photo radical polymerization initiator. In the present invention, both a thermal radical polymerization initiator and a photo radical polymerization initiator can be used.

It does not specifically limit as a thermal radical polymerization initiator, A well-known compound can be used. For example, a peroxide, a hydroperoxide, and an azo compound are mentioned. Specifically, benzoyl peroxide, di-t-amyl peroxide, t-butyl peroxybenzoate, 2,5-dimethyl-2,5 di- (t-butylperoxy) hexane, 2,5-dimethyl-2,5- Di- (t-butylperoxy) hexyne-3, and peroxides such as di-cumyl peroxide, hydroperoxides such as t-amyl hydroperoxide, t-butyl hydroperoxide, and hydrogen peroxide, (2,2′-azobis (2,4-dimethylpentanenitrile)), (2,2′-azobis (2-methylpropanenitrile)), (2,2′-azobis (2-methylbutanenitrile)), (2,2′-azobis) (Cyclohexanecarbonitrile)) and the like.

In addition, in order to use a thermal radical polymerization initiator at a relatively low temperature, a so-called redox initiator system is used in which a reducing agent such as a transition metal or an amine is combined with an oxidizing initiator such as peroxide, hydroperoxide, or ascorbic acid. You can also

It does not specifically limit as radical photopolymerization initiator, A well-known compound can be used. For example, benzoin compounds, acetophenones, benzophenones, thioxanthones, α-acyloxime esters, phenylglyoxylates, benzyls, azo compounds, diphenyl sulfide compounds, acylphosphine oxide compounds, organic dye compounds , Iron-phthalocyanine series, benzoins, benzoin ethers, anthraquinones. Specifically, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy- Acetophenones such as 2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; Anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone; 2,4-diethylthioxanthone, 2-isopropylthioxanthate Thioxanthones such as 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylaminobenzophenone; 2 , 4,6-trimethylbenzoyldiphenylphosphine oxide, phosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. Photo radical polymerization initiators introduced in known literature such as Journal of Synthetic Organic Chemistry 66, 458 (2008) can also be used.

Further, as a photo radical polymerization initiator available from the market, 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba Specialty Chemicals, Inc., Irgacure is a registered trademark of Ciba Specialty Chemicals), (2-methyl-1- ( Acylphosphines such as 4- (methylthio) phenyl) -2- (4-morpholinyl) -1-propanone) (Irgacure 907) and bis (2,4,6-trimethylbenzoyl) -diphenyl-phosphine oxide (Irgacure 819) Oxide compounds; titanocenes such as bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (Irgacure 784) Compound; 6,12-bis (trimethylsilane And naphthacenequinone compounds such as ryloxy) -1,11-naphthacenequinone.

These radical polymerization initiators may be used alone or in combination of two or more. The amount of radical polymerization initiator added depends on the radical polymerizable compound and chain transfer agent composition used, but is in the range of 0.0001 parts by mass to 10 parts by mass with respect to 100 parts by mass of the total amount of radical polymerizable compounds. Is preferably within.

[Starting energy]
The starting energy may be any energy that can generate radicals from the added radical initiator. In general, thermal energy and ionization wave energy are appropriately selected. Specific examples of the energy source include heat, light, electron beam (EB), microwave, radiation and other electromagnetic rays. Depending on the energy source used, thermal polymerization, electromagnetic ray polymerization (photopolymerization, electron beam polymerization, Microwave polymerization, radiation polymerization) and the like.

In the case of thermal polymerization, although it depends on the polymerizable compound used and its mode, the temperature range used for the polymerization is usually -20 to 200 ° C, preferably 0 to 150 ° C, more preferably 10 to 120 ° C.

Furthermore, redox polymerization using a redox (redox) initiator (described later) is one type of thermal polymerization. Under the present circumstances, the temperature range used is lower than normal thermal polymerization, is -40-100 degreeC, Preferably it is -20-80 degreeC, More preferably, it is 0-60 degreeC.

In photopolymerization, ultraviolet light, visible light, infrared light, or the like can be used as light to be irradiated. A radical photopolymerization initiator or a sensitizer can also be used. In the case of ultraviolet rays and visible rays, specifically, for example, rays in the wavelength range of 300 to 800 nm. As the light source, an LED (light emitting diode) or a lamp that can irradiate light having a wavelength in the range of 300 to 800 nm is used. Examples of the LED include a UV-LED, a blue LED, and a white LED. Examples of the lamp include a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, and a metal halide lamp.

Electron beam polymerization is performed by electron beam irradiation. For the electron beam irradiation, any method that can act on the electron beam polymerization compound and cause polymerization of the polymerizable substance can be used without particular limitation. The electron dose to be irradiated is preferably adjusted in the range of about 1 to 300 kGy as an absorbed dose. If it is less than 1 kGy, sufficient irradiation effect cannot be obtained, and irradiation exceeding 300 kGy is not preferable because there is a possibility of deteriorating the substrate. As an electron beam irradiation method, for example, a scanning method, a curtain beam method, a broad beam method, or the like is used, and the acceleration voltage when irradiating the electron beam needs to be controlled by the thickness of the substrate on the irradiation side. However, about 20 to 100 kV is appropriate.

For the microwave polymerization, a known method of Strauss et al. (Aust. J. Chem., 48, 1665-1692 (1995)) can be used. Microwaves can be generated by any of a variety of methods known in the microwave arts. In general, these methods rely on a klystron or magnetron acting as a microwave source. In general, the frequency of occurrence is in the range of about 300 MHz to 30 GHz and the corresponding wavelength is about 1 m to 1 mm. Theoretically, any frequency in this range can be used effectively, but it is preferred to use a commercially available range of frequencies, including about 850-950 MHz or about 2300-2600 MHz. .

Radiation polymerization is carried out by irradiating γ rays, X rays, α rays, and β rays. Usually, γ-ray irradiation of cobalt 60 is often used.

Furthermore, an energy source for initiating polymerization can be used in combination. For example, an electron beam and infrared rays are used together.

In addition to the thermal polymerization, the polymerization is usually carried out at around room temperature, but it can also be carried out while heating. In this case, acceleration of polymerization can be expected.

[Other ingredients]
Necessary in addition to the chain transfer agent composition, radical polymerizable compound and radical polymerization initiator of the present invention for radical polymerization of the radical polymerizable composition containing the chain transfer agent composition of the present invention and the radical polymerizable compound. If present, other components may be contained within a range not impairing the effects of the present invention. In addition to the components exemplified below, a colorant, a plasticizer, a tackifier, an antioxidant, various stabilizers, Fillers, antistatic agents, ultraviolet absorbers and the like can also be added.

For example, the surfactant is not particularly limited as long as it is a known surfactant. For example, alkyl sulfate ester salts, alkylaryl sulfonate salts, sulfosuccinate ester salts, fatty acid salts, polyoxyethylene alkylaryl Anionic surfactants such as sulfate ester salts and polyoxyethylene alkyl sulfate ester salts (herein, “salts” include potassium salt, sodium salt, ammonium salt, etc.), sorbitan esters, polyoxyethylene Examples thereof include hydrophilic nonionic surfactants such as alkyl ethers, polyoxyethylene alkylphenyl ethers, and polyoxyethylene alkyl esters. Any one of these may be used alone or two or more of them may be used in combination.

In the emulsion polymerization, as an emulsifier, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, ester of sodium sulfosuccinate, Abex anionic surfactant (Alcolac), alkylphenoxypolyethoxyethanol (HLB = 13 to 19), block copolymers of ethoxy fatty acid alcohol (HLB = 13 to 19), ethylene oxide and propylene oxide, and the like.

In addition, a water-soluble protective colloid may be used in the emulsion polymerization. Representative examples of such protective colloids include hydroxyethyl cellulose, poly (ethylene oxide-propylene oxide) polyvinyl alcohol, polyethylene oxazoline, polyvinyl pyrrolidone (PVP), and copolymers of the above compounds. The protective colloid is usually used in a proportion of 0.1 to 1.5% by weight with respect to the monomer.

In suspension polymerization, a dispersion stabilizer can also be used. Examples of the dispersion stabilizer include water-soluble or oil-soluble partially saponified polyvinyl alcohol; water-soluble cellulose such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose; acrylic acid polymer, methyl vinyl ether-maleic anhydride Water-soluble polymers such as polymers, styrene-maleic anhydride copolymers, gelatin; oil-soluble emulsifiers such as sorbitan monolaurate, sorbitan monostearate, glycerin monostearate, ethylene oxide propylene oxide block copolymers, polyoxyethylene sorbitan Water-soluble emulsifiers such as monolaurate, polyoxyethylene glycerol oleate, sodium laurate; sulfates such as barium sulfate and calcium sulfate Carbonates such as barium carbonate, calcium carbonate and magnesium carbonate; phosphates such as calcium phosphate; metal oxides such as aluminum oxide and titanium oxide; metals such as aluminum hydroxide, magnesium hydroxide and ferric hydroxide Inorganic compounds such as hydroxides can be used, and these can be used alone or in combination of two or more.

In addition, upon polymerization, the reaction system includes starch / cellulose, starch / cellulose derivatives, polyvinyl alcohol, polyacrylic acid (salt), polyacrylic acid (salt) cross-linked hydrophilic polymer 0 to 50% by weight ( Monomers) and other 0 to 10% by weight of various foaming agents such as carbonic acid (hydrogen) salts, carbon dioxide, azo compounds, inert organic solvents; chelating agents; inorganic fine particles such as kaolin, talc and silicon dioxide Polyvalent metal salts such as polyaluminum chloride, aluminum sulfate and magnesium sulfate may be added.

Moreover, in the range which does not impair the effect of this invention, you may contain components, such as chain transfer agents other than the chain transfer agent which has the condensed polycyclic aromatic skeleton of this invention.

These other components can be used alone or in combination of two or more at the same time for the chain transfer agent composition of the present invention. These other components can be appropriately selected according to the type and application of the radical polymerizable compound to be applied.

<Manufacturing mode>
By radical polymerization of the radical polymerizable composition containing the chain transfer agent composition of the present invention and the radical polymerizable compound, or by radical polymerization of the radical polymerizable compound in the presence of the chain transfer agent composition, A polymer having a residue derived from a chain transfer agent having a condensed polycyclic aromatic skeleton can be produced at the terminal of the polymer to be produced or a part of the main chain.

As a production mode of a polymer having a residue derived from a chain transfer agent having a condensed polycyclic aromatic skeleton at a polymer terminal or a part of the main chain, bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, or slurry A method such as polymerization can be used. Moreover, it can be used even when polymerizing batchwise or continuously.

The atmosphere during the polymerization preferably removes molecular oxygen and is generally used under reduced pressure or in the presence of an inert gas. Examples of the inert gas include nitrogen, argon, helium, carbon dioxide and the like.

<Polymer having condensed polycyclic aromatic skeleton at terminal>
The polymer produced by the above polymerization method using the chain transfer agent composition of the present invention is a condensed polycycle which is a residue derived from the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention at the terminal as described above. It is possible to impart an aromatic skeleton. That is, the chain transfer agent having a condensed polycyclic aromatic skeleton in the chain transfer agent composition of the present invention has a terminal structure derived from the chain transfer agent because it is added to the polymer growth terminal and chain-transferred. . Therefore, it is possible to synthesize a polymer having a residue derived from the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention at the terminal, and further to the functionality of the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention. Groups can be imparted to the polymer. Generates the chemical and physical properties of the condensed polycyclic aromatic skeleton and functional groups, such as affinity, reactivity, heat resistance, optical properties, and chemical stability, derived from the condensed polycyclic aromatic skeleton and functional groups It can be applied to a polymer and used as a functional polymer.

That is, the chain transfer agent having a condensed polycyclic aromatic skeleton of the present invention can provide a terminal functionalized polymer having a reactive group.

For example, by using the chain transfer agent composition of the present invention, a condensed polycyclic aromatic skeleton is introduced into the polymer, but the ultraviolet absorption ability, fluorescence characteristics, high refractive index, etc. derived from the condensed polycyclic aromatic skeleton These properties can be imparted to the polymer. Further, by using the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention, a hydrophobic group is introduced into the terminal of the polymer, or a group having both a hydrophilic group and a hydrophobic group is introduced. Can do.

In general, it is well known that radicals are generated through a decomposition reaction by applying heat, light, mechanical energy, etc. to a polymer (Takayuki Otsu, “Chemistry of Polymer Synthesis” (Chemical Doujin, 1979), page 245, 250, 260). At that time, by applying the chain transfer agent composition of the present invention, it is possible to prevent gelation of the polymer or to graft a functional group. For example, methods described in JP-A-54-100449, JP-A-6-256430 and the like can be used. Specifically, a thermoplastic polymer is melt-kneaded to give thermal energy and mechanical energy, and while cutting the polymer chain, the chain transfer agent of the present invention is applied as an additive to prevent polymer gelation. , Functional groups can be grafted.

Example 1
4 g of commercially available styrene (Wako special grade) as a radical polymerizable compound was put in a test tube, and 1% by mass of azobisisobutyronitrile (Wako special grade) as an initiator and a chain transfer agent with respect to this radical polymerizable compound. 500 mass ppm of 1,4-naphthoquinone and further 500 mass ppm of isopropyl alcohol as a chain transfer aid were added to obtain a radical polymerizable composition. The test tube containing the radical polymerizable composition was capped with a septum, and nitrogen was bubbled through the composition at a rate of 15 mL / min for 20 minutes. Then, the test tube was immersed in a heated oil bath while nitrogen was passed, and the solution temperature in the test tube was kept at 60 ° C., and the elapsed time after the immersion of the test tube was taken as the polymerization time. A product with a polymerization time of 5 hours was dissolved in tetrahydrofuran (Wako Special Grade) at a predetermined concentration, and a refractometer (RI) (JASCO-made RI-2031), a multi-wavelength ultraviolet spectrometer (JASCO-made MD-) 2010), and gel permeation chromatography (manufactured by JASCO Corporation) equipped with a GPC column (Shodex GPC KF-806L manufactured by Showa Denko) was used to characterize the produced polymer. Among these, a refractometer was used as a detector, and the polymerization rate was measured from the average molecular weight of the produced polymer, its distribution and its peak area. Furthermore, using a multi-wavelength ultraviolet spectrometer as a detector, the ultraviolet absorption spectrum of the produced polymer was measured, and the presence or absence of absorption at a wavelength of 350 to 500 nm derived from the condensed polycyclic aromatic skeleton was measured. These measurement results are shown in Table 1. In addition, in order to see the behavior in the late stage of polymerization, a chromatogram of GPC after 5 hours of polymerization time is shown in FIG. For comparison, FIG. 1 also shows a chromatogram of Comparative Example 2 described later.

(Examples 2-9, Comparative Examples 1-5)
The same operation as in Example 1 was performed except that the type of chain transfer agent to be added, the amount of chain transfer agent added, the type of chain transfer aid, and the amount of chain transfer aid added were changed as shown in Table 1. The measurement results are shown in Table 1.

From Example 1 and Comparative Example 1, it can be seen that the chain transfer agent composition of the present invention has an excellent chain transfer effect. Moreover, from Example 1 and Comparative Examples 2 and 5, the chain transfer effect is superior to the case where each of the chain transfer agent and the chain transfer auxiliary agent constituting the chain transfer composition of the present invention is added alone. I understand that. When isopropyl alcohol alone in Comparative Example 5 is added, almost no chain transfer effect is observed. Further, FIG. 1 shows the polymerization distribution of the polymers obtained in Example 1 and Comparative Example 2. By adding isopropyl alcohol which hardly shows a chain transfer effect by itself, the formation of a high molecular weight component of the produced polymer. It can be seen that a synergistic molecular weight lowering effect that cannot be obtained alone can be obtained.

Moreover, it turns out that the same chain transfer effect has appeared also by various chain transfer agents and chain transfer adjuvants so that Examples 2-6 and 9 may show.

As can be seen from Examples 1 to 9 and Comparative Examples 1 to 5, the produced polymer absorbs light at a wavelength of 350 to 500 nm only when the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention is used. As shown, it can be seen that the produced polymer has a condensed polycyclic aromatic skeleton derived from the chain transfer agent having the condensed polycyclic aromatic skeleton of the present invention in the polymer.

(Example 10)
9.4 g of commercially available styrene (Wako Special Grade) and 3.1 g of butyl acrylate (Wako Special Grade) are mixed as a radical polymerizable monomer, and 0.5% by mass of 1,4-naphthoquinone is used as a chain transfer agent for this mixture. Further, 10% by mass of isopropyl alcohol was added as a chain transfer aid to obtain a radical polymerizable composition. On the other hand, 0.0625 g of ammonium peroxodisulfate (Wako Special Grade) as an initiator and 0.25 g of sodium dodecylbenzenesulfonate as a surfactant were added to 100 g of pure water to prepare an aqueous solution. These radically polymerizable composition and aqueous solution were put into a separable flask equipped with a 300 ml condenser, and nitrogen was bubbled through the composition at a rate of 15 mL / min for 20 minutes in a glass tube. Then, with the nitrogen vented, the separable flask was immersed in a heated oil bath and held for 52 hours so that the liquid temperature in the separable flask became 90 ° C., and this was regarded as the polymerization time. After immersion in the separable flask, 0.0625 g of ammonium peroxodisulfate was further added after 1 hour. The product is dissolved in tetrahydrofuran (Wako special grade) at a predetermined concentration, and a refractometer (RI) (JASCO-made RI-2031), a multi-wavelength ultraviolet spectrometer (JASCO-made MD-2010), and GPC are used as detectors. The produced polymer was characterized using gel permeation chromatography (manufactured by JASCO) equipped with a column (Showex DPC Shodex GPC KF-806L). Among these, a refractometer was used as a detector, and the polymerization rate was measured from the average molecular weight of the produced polymer, its distribution and its peak area. Furthermore, using a multi-wavelength ultraviolet spectrometer as a detector, the ultraviolet absorption spectrum of the produced polymer was measured, and the presence or absence of absorption at a wavelength of 350 to 500 nm derived from the condensed polycyclic aromatic skeleton was measured. The measurement results are shown in Table 2.

(Examples 11 and 12, Comparative Examples 6 and 7)
The same operation as in Example 10 was performed except that the addition amount of the chain transfer agent to be added, the type of chain transfer aid, and the addition amount of the chain transfer aid were changed as shown in Table 2, and the measurement results are shown in Table 2. It was shown to.

From Examples 10 to 12, it can be confirmed that the chain transfer effect of the chain transfer agent composition of the present invention is high even in heterogeneous polymerization, for example, emulsion polymerization, as a polymerization mode. Moreover, from Example 10 and Comparative Example 7, it can be seen that a synergistic molecular weight reduction effect that cannot be obtained by each of the chain transfer agent and the chain transfer auxiliary agent is obtained.

Claims (12)

A chain transfer agent having a condensed polycyclic aromatic skeleton represented by the following general formula (1); an aliphatic alcohol compound having 1 to 8 carbon atoms; an aliphatic ketone compound having 2 to 8 carbon atoms; -8 fatty acid ester compounds, C4-C10 aliphatic saturated hydrocarbon compounds, C6-C10 aromatic hydrocarbon compounds, C3-C10 aliphatic ether compounds, terpenoid compounds, styrene oligomers system compound, a thiol compound having a carbon number of 4 to 14, one or two or more chain transfer aid selected from the group consisting of an aromatic amine compound 8-14 aliphatic amines and carbon atoms 2 to 8 carbon atoms A chain transfer agent composition characterized by comprising.

(In the formula (1), n represents an integer of 1 to 4, and when there are a plurality of Rs, each independently represents a hydrogen atom, alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, aryloxy group or halogen. X and Y each independently represent a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an amino group, or a halogen atom, but X and Y are bonded to each other instead of the substituent. A saturated or unsaturated 6-membered ring may be formed, and the 6-membered ring formed by X and Y further has an alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, aryloxy group or halogen atom. May be substituted.) The chain transfer agent composition according to claim 1, wherein in general formula (1), n is 4, R is a hydrogen atom, and X and Y are hydrogen atoms. The chain transfer agent composition according to claim 1, wherein, in the general formula (1), X is a hydroxy group, an alkyl group, an alkoxy group, an amino group, or a halogen atom, and Y is a hydrogen atom. The chain transfer according to claim 1, wherein in general formula (1), n is 4, R is a hydrogen atom, X is a hydroxy group or a methyl group, and Y is a hydrogen atom. Agent composition. The chain transfer according to claim 1, wherein in general formula (1), n is 4, R is a hydrogen atom, X is a chlorine atom, and Y is a chlorine atom or an amino group. Agent composition. At least a chain transfer agent having a condensed polycyclic aromatic skeleton represented by the following general formula (2) or (3), an aliphatic alcohol compound having 1 to 8 carbon atoms, and an aliphatic ketone compound having 2 to 8 carbon atoms , Ester compounds of fatty acids having 1 to 8 carbon atoms, aliphatic saturated hydrocarbon compounds having 4 to 10 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, aliphatic ether compounds having 3 to 10 carbon atoms, terpenoids compounds, styrene oligomeric compound, a thiol compound having a carbon number of 4 to 14, aliphatic amines and one or more chain selected from the group consisting of an aromatic amine compound of 8-14 carbon atoms having 2 to 8 carbon atoms A chain transfer agent composition comprising a transfer aid.

(In the formula (2), n represents an integer of 1 to 4, and when there are a plurality of R, each independently represents a hydrogen atom, alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, aryloxy group or halogen. Represents an atom, and Q represents a hydrogen atom, an alkyl group or a halogen atom.)

(In the formula (3), n represents an integer of 1 to 4, and when there are a plurality of R, each independently represents a hydrogen atom, alkyl group, aryl group, aralkyl group, hydroxy group, alkoxy group, aryloxy group or halogen. Represents an atom, and Q represents a hydrogen atom, an alkyl group or a halogen atom.) The chain transfer aid is one or more selected from the group consisting of an aliphatic alcohol compound having 1 to 8 carbon atoms, an aliphatic ether compound having 3 to 10 carbon atoms, a terpenoid compound and a styrene oligomer compound. The chain transfer agent composition according to any one of claims 1 to 6, wherein The chain transfer aid is one or more selected from the group consisting of isopropyl alcohol, isobutanol, tetrahydrofuran, α-methylstyrene dimer and terpinolene, according to any one of claims 1 to 6. A chain transfer agent composition. The chain transfer agent composition according to any one of claims 1 to 6, wherein the chain transfer aid is isopropyl alcohol or tetrahydrofuran. The chain transfer agent composition according to any one of claims 1 to 9, a radical photopolymerization initiator (excluding a quinone compound) or a thermal radical polymerization initiator (excluding peroxide and hydroperoxide), and radical polymerization. characterized in that it contains a sex compound, a radical polymerizable composition. The radically polymerizable composition according to claim 10, wherein the radically polymerizable compound is (meth) acrylic acid, (meth) acrylic acid ester or styrene. A radically polymerizable compound is radically polymerized in the presence of the chain transfer agent composition according to any one of claims 1 to 9, wherein a condensed polycyclic aroma is added to a terminal of the polymer or a part of a main chain. Of producing a polymer having a residue derived from a chain transfer agent having a family skeleton.