JP4679136B2 - Novel polymerizable compound, process for producing the polymerizable compound, polymerizable composition containing the polymerizable compound, and cured product thereof - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a polymerizable compound, and more specifically, a polymerizable compound having improved polymerizability, such as an electrophotographic photosensitive member, an organic electroluminescent element, a cross-linking agent for various polymers, a paint, a coating, and an adhesive. The present invention relates to a polymerizable compound that can be particularly suitably used for an agent, a sealing material and the like, a method for producing the same, a polymerizable composition containing the polymerizable compound, and a cured product of the polymerizable composition.

  A compound having an N-arylamine structure is known to have a hole transport function and has been conventionally used in fields such as electrophotographic photoreceptors and organic electric field devices. For example, as a method for producing an electrophotographic photoreceptor, a method of producing a coating film by mixing a compound having an N-arylamine structure with a thermoplastic resin such as polycarbonate is disclosed (Patent Document 1).

  However, in this coating film manufacturing method, since the N-arylamine compound having properties similar to a plasticizer is mixed with a thermoplastic resin at a high concentration, the surface hardness and solvent resistance of the obtained coating film are lowered. Therefore, there has been a demand for a resin composition capable of obtaining a coating film with higher performance.

  In order to solve such drawbacks, a coating film manufacturing method is known in which a polymerizable functional group such as an acrylic group is introduced into a compound having an N-arylamine structure and cured by heat or light (Patent Document). 2).

  This method has made it possible to produce a coating film having excellent surface hardness and solvent resistance, but a relatively high concentration of a polymerization initiator is still required to cure the resin compound. This was attributed to the fact that the N-arylamine compound having an acrylic group did not have sufficient polymerizability. However, in order to fully exhibit the performance as an electrophotographic photoreceptor, it is necessary to reduce the polymerization initiator as much as possible (Patent Document 3), so it is necessary to improve the polymerizability of the N-arylamine compound itself. Met.

  On the other hand, it is known that a polymerizable compound having an acrylic group is susceptible to polymerization inhibition by oxygen. Particularly in the field of coating materials and the like, there is a drawback that surface tackiness due to polymerization inhibition tends to remain. For this reason, it has been considered desirable to cure the compounds under conditions that are generally free of oxygen. A compound in which an acrylic group is introduced into a compound having an N-arylamine structure has the same drawbacks. Therefore, the curing conditions for such a compound into which an acrylic group is introduced are also required to be in a non-oxygen atmosphere. I came.

  On the other hand, a compound having an alkenyl ether group such as an allyl ether group or a 1-propenyl ether group and a fumarate group in the same molecule has little polymerization inhibition due to oxygen and is excellent in polymerizability. Known (Patent Document 4). If these functional groups are introduced into a compound having an N-arylamine structure, it is considered that an N-arylamine compound having excellent polymerizability with little polymerization inhibition by oxygen can be obtained. There was no suggestion.

JP 2002-278100 A

JP 2001-166501 A

JP 2001-166501 A (6th page, 106th page)

JP 2002-256065 A

  An object of the present invention is to provide an N-arylamine compound capable of solving the above-described problems in the prior art.

  Another object of the present invention is to provide an N-arylamine compound having excellent polymerizability, a method for producing the compound, a polymerizable composition containing the compound, and the polymerizable composition having excellent surface hardness and solvent resistance. It is to provide a cured product.

  As a result of intensive studies, the present inventors have found that an N-arylamine compound having a specific polymerizable functional group has excellent polymerizability. As a result of further studies based on this discovery, the present inventors have found that a cured product of the polymerizable composition containing the compound is excellent not only in surface hardness but also in solvent resistance, and completed the present invention.

  That is, the present invention (I) finds an N-arylamine compound excellent in polymerizability by having a polymerizable functional group represented by the general formula (2) in the same molecule of the N-arylamine compound, The present invention has been completed.

General formula (2)

(In General Formula (2), each R ⁴ is independently a structure represented by General Formula (3) or General Formula (4), and X ¹ is each independently a carbon having 2 to 6 hydroxyl groups. Represents an organic residue derived from a polyhydric alcohol having 2 to 30 carbon atoms, Y ¹ independently represents Structural Formula (1) or Structural Formula (2), and X ² each independently represents 1 to 1 carbon atoms. Represents an alkylene chain having 4 carbon atoms, n ¹ represents an integer of ¹ to 10, and n ² represents an integer of 0 to 1.)

General formula (3)

(In General Formula (3), R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

General formula (4)

(In General Formula (4), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

Structural formula (1)

Structural formula (2)

  The present invention (II) is a method for producing the polymerizable compound of the present invention (I) described above.

  The present invention (III) is a polymerizable composition comprising the polymerizable compound of the present invention (I).

  The present invention (IV) is a cured product obtained by curing the above polymerizable composition.

  The present invention includes the following aspects, for example.

[1] A polymerizable compound having a structure represented by the general formula (1). General formula (1)

(In General Formula (1), at least one of R ¹ , R ² , and R ³ is an aryl group having a polymerizable functional group represented by General Formula (2), and the other is an alkyl group or aralkyl. And at least one selected from the group consisting of a group or an aryl group, provided that R ¹ , R ² and R ³ may be the same or different.)

General formula (2)

(In General Formula (2), each R ⁴ is independently a structure represented by General Formula (3) or General Formula (4), and X ¹ is each independently a carbon having 2 to 6 hydroxyl groups. Represents an organic residue derived from a polyhydric alcohol having 2 to 30 carbon atoms, Y ¹ independently represents Structural Formula (1) or Structural Formula (2), and X ² each independently represents 1 to 1 carbon atoms. Represents an alkylene chain having 4 carbon atoms, n ¹ represents an integer of ¹ to 10, and n ² represents an integer of 0 to 1.)

General formula (3)

(In General Formula (3), R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

General formula (4)

(In General Formula (4), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

Structural formula (1)

Structural formula (2)

[2] In R ⁴ of the general formula (2), the number of groups represented by the general formula (4) / {(number of groups represented by the general formula (3)) + (represented by the general formula (4) The polymerizable compound as described in [1], wherein the number of groups to be formed} is 0.6 or more.

[3] In Y ¹ of the general formula (2), (number of structures represented by the structural formula (2)) / ({number of structures represented by the structural formula (1)) + (structural formula (2) The polymerizable compound according to any one of [1] and [2], wherein the number of structures represented by:

[4] R ⁷ in the general formula (4) is methyl group, an ethyl group, characterized in that any one or more of the group consisting of n- propyl and iso- propyl [1] to [3] The polymerizable compound according to any one of the above.

[5] X ¹ in the general formula (2) is independently represented by an alkylene diol residue, an alicyclic diol residue, an aromatic diol residue, or the general formula (5). The polymerizable compound according to any one of [1] to [4].

General formula (5)

(R ⁸ and R ⁹ each independently represent a hydrogen atom or General Formula (6), and at least one of them is General Formula (6).)

General formula (6)

(In the general formula (6), R ¹⁰ represents a chlorine atom, a bromine atom, a fluorine atom, a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms.)

[6] R ¹ , R ² , and R ^{3 in the} general formula (1) are represented by any one of the general formula (7) to the general formula (12) The polymerizable compound according to any one of the above.

General formula (7)

General formula (8)

General formula (9)

General formula (10)

Formula (11)

Formula (12)

(In the general formula (7) to general formula (12), R ^{11 to} R ⁶¹ are each independently the general formula (2), chlorine atom, bromine atom, fluorine atom, hydrogen atom, methyl group, ethyl group, n-propyl. A group, an iso-propyl group, a group represented by general formula (13) or general formula (14);

Formula (13)

(In the formula, each X ³ independently represents an alkylene group having 1 to 4 carbon atoms, and n ³ represents an integer of 1 to 10.)

General formula (14)

(In the formula, each X ⁴ independently represents an alkylene group having 1 to 4 carbon atoms, and n ⁴ represents an integer of 1 to 10.)

  [7] The polymerizable compound according to [1] to [6], further having at least one structure selected from the group consisting of Structural Formula (3) to Structural Formula (9).

Structural formula ( 6 )

Structural formula ( 7 )

Structural formula ( 8 )

Structural formula ( 9 )

Structural formula ( 10 )

Structural formula ( 11 )

Structural formula ( 12 )

  [8] The [1] to [7], wherein the carboxylic acid represented by the following general formula (15) is reacted with an arylamine compound having at least one hydroxyl group in the presence of a catalyst. A method for producing the polymerizable compound.

General formula (15)

(In the general formula (15), R ⁶² and R ⁶³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. X ⁵ is each independently a carbon number having 2 to 6 hydroxyl groups. 2 represents an organic residue derived from a polyhydric alcohol having 2 to 30 carbon atoms, Y ² independently represents Structural Formula (1) or Structural Formula (2), and n ⁵ represents an integer of 1 to 10. )

Structural formula (1)

Structural formula (2)

  [9] [1] to [7], wherein the carboxylic acid represented by the general formula (15) is reacted with an arylamine compound having at least one hydroxyl group in the presence of a condensing agent as a catalyst. ] The manufacturing method of the polymeric compound of description.

  [10] The method for producing a polymerizable compound as described in [9], wherein the condensing agent is sulfonyl chloride.

  [11] By subjecting the terminal group of the polymerizable compound according to [1] to [7] having the general formula (3) as a terminal group, an isomerization reaction of the terminal group in the presence of a catalyst, The manufacturing method of the polymeric compound which has general formula (4) in a terminal group characterized by converting a terminal group into General formula (4).

  [12] 60% or more of the general formula (3) in the polymerizable compound of any one of [1] to [7] having the general formula (3) as a terminal group is converted into a group of the general formula (4) in the isomerization reaction. [11] The method for producing a polymerizable compound according to [11], wherein

  [13] The method for producing a polymerizable compound as described in [11] or [12], wherein the catalyst used in the isomerization reaction is a catalyst containing at least one of palladium, rhodium, and ruthenium.

  [14] A polymerizable composition comprising the polymerizable compound according to any one of [1] to [7].

  [15] From 1% by mass to 99% by mass of the polymerizable compound according to any one of [1] to [7], and an unsaturated polyester, a (meth) acrylate compound, a vinyl ether compound, and a radical polymerizable monomer. A polymerizable composition comprising 1% by mass to 99% by mass of at least one compound selected from the group consisting of:

  [16] 100 parts by mass of the polymerizable compound according to [1] to [7], or the polymerizable composition according to [14] or [15], and 0.01 to 15 parts by mass of a radical polymerization initiator. A polymerizable composition comprising a part by mass.

  [17] A cured product obtained by curing the polymerizable compound according to [1] to [7] or the polymerizable composition according to any of [14] to [16].

  The polymerizable compound of the present invention having the above-described structure has an excellent characteristic that it has little polymerization inhibition due to oxygen and has excellent polymerizability based on the structure of the compound (particularly, a combination of functional groups). Since the polymerizable compound of the present invention has excellent polymerizability, it can be polymerized in air, for example, while reducing the amount of polymerization initiator used (or without using a polymerization initiator). Is possible. Therefore, the polymerizable compound of the present invention is suitable for various wide applications and uses (for example, a use in which the polymerization initiator is not substantially used or the use amount of the polymerization initiator is preferably reduced) taking advantage of the above characteristics. Can be used.

  In addition, the polymerizable compound of the present invention has a skeleton capable of exhibiting an excellent hole transport function, and the combination of the functional groups described above substantially inhibits the hole transport function. Therefore, impurities such as a polymerization initiator can be reduced. As a result, it can be particularly suitably used for applications utilizing the hole transport function (for example, a polymer for an electrophotographic photoreceptor).

  Hereinafter, the present invention will be described more specifically with reference to the drawings as necessary. In the following description, “parts” and “%” representing the quantity ratio are based on mass unless otherwise specified.

(Arylamine compound)
The polymerizable compound of the present invention is a compound having an arylamine skeleton as shown in the general formula (1). In the present invention, the “arylamine compound” refers to an amine compound in which an aryl group is directly bonded to the nitrogen atom of the amine compound. Furthermore, an aryl group refers to a “residue formed by loss of one hydrogen atom from an aromatic hydrocarbon” (namely, phenyl, naphthyl, etc. are collectively referred to as an aryl group; standard chemical terminology, reduced edition) (March 20, 20th edition, published on March 20, 2012)

(Invention (I))
First, the present invention (I) will be described. The present invention (I) is a polymerizable compound characterized by having at least one polymerizable functional group represented by the general formula (2) in the same molecule of the arylamine compound.

The arylamine structure described in the present invention can be represented as the general formula (1). General formula (1)

(In General Formula (1), at least one of R ¹ , R ² , and R ³ is an aryl group having a polymerizable functional group represented by General Formula (2), and the other is an alkyl group or aralkyl. And at least one selected from the group consisting of a group or an aryl group, provided that R ¹ , R ² and R ³ may be the same or different.)

  Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the aryl group include, but are not limited to, a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, and general formulas (7) to (12).

General formula (7)

General formula (8)

General formula (9)

General formula (10)

Formula (11)

Formula (12)

(In the general formula (7) to general formula (12), R ^{11 to} R ⁶¹ are each independently the general formula (2), chlorine atom, bromine atom, fluorine atom, hydrogen atom, methyl group, ethyl group, n-propyl. A group, an iso-propyl group, or a group represented by general formula (13) or general formula (14);

Formula (13)

(In the formula, each X ³ independently represents an alkylene group having 1 to 4 carbon atoms, and n ³ represents an integer of 1 to 10.)

General formula (14)

(In the formula, each X ⁴ independently represents an alkylene group having 1 to 4 carbon atoms, and n ⁴ represents an integer of 1 to 10.)

  Furthermore, examples of the arylamine structure excluding the polymerizable functional group of the general formula (2) from the arylamine compound of the present invention include compounds exemplified in JP-A No. 2001-166520, but the present invention is not limited to these. Is not to be done.

(Polymerizable functional group)
Next, the polymerizable functional group represented by the general formula (2) will be described.
General formula (2)

(In General Formula (2), each R ⁴ is independently a structure represented by General Formula (3) or General Formula (4), and X ¹ is each independently a carbon having 2 to 6 hydroxyl groups. Represents an organic residue derived from a polyhydric alcohol having 2 to 30 carbon atoms, Y ¹ independently represents Structural Formula (1) or Structural Formula (2), and X ² each independently represents 1 to 1 carbon atoms. Represents an alkylene chain having 4 carbon atoms, n ¹ represents an integer of ¹ to 10, and n ² represents an integer of 0 to 1.)

General formula (3)

(In General Formula (3), R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

General formula (4)

(In General Formula (4), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

Structural formula (1)

Structural formula (2)

R ^{4 in the} general formula (2) according to the present invention represents either the general formula (3) or the general formula (4).

R ⁵ and R ^{6 in} the general formula (3) each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In general formula (3), at least one of R ⁵ and R ⁶ is preferably a hydrogen atom or a methyl group and the other is at least a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an iso-propyl group. It is a kind. More preferably, at least one of R ⁵ and R ⁶ is a hydrogen atom and the other is a hydrogen atom or a methyl group, and most preferably both R ⁵ and R ⁶ are hydrogen atoms. An alkyl group having 4 or more carbon atoms is not preferred because the polymerizability may decrease.

R ⁷ in the general formula (4) represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. In the general formula (4), R ⁷ is preferably at least one of a hydrogen atom, a methyl group, an ethyl group, an n-propyl group and an iso-propyl group from the viewpoint of polymerizability. More preferably, R ⁷ is a hydrogen atom or a methyl group. An alkyl group having 4 or more carbon atoms is not preferred because the polymerizability may decrease.

X ¹ described above represents an organic residue derived from a C 2 to C 30 polyhydric alcohol having 2 to 6 hydroxyl groups.

(Polyhydric alcohol)
Specific examples of the polyhydric alcohol for deriving the group X ¹ include ethylene glycol, neopentyl glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1, Alkylene diols such as 4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and substituted alkylene glycols include 1-phenylethylene glycol, 1,2-diphenylethylene glycol, and polyalkylenes thereof. Diol, 1,1-cyclohexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,3- Cyclohexane dimeta , Cycloaliphatic diols such as 1,4-cyclohexanedimethanol and tricyclodecane dimethanol, aromatic diols such as bisphenol A, bisphenol F, bisphenol S and benzenedimethanol, and ethylene oxide addition of these polyhydric alcohols , Propylene oxide adduct, cyclohexene oxide adduct, styrene oxide adduct and the like.

  In addition, trivalent alcohols such as trimethylolethane, trimethylolpropane and glycerin, tetravalent alcohols such as pentaerythritol, diglycerin and ditrimethylolpropane, hexavalent alcohols such as dipentaerythritol and sorbitol, and polyvalent alcohols thereof. Examples include polyhydric alcohols such as ethylene oxide adducts, propylene oxide adducts, cyclohexene oxide adducts, and styrene oxide adducts of alcohols.

Depending on the type of polyhydric alcohol, stereoisomers and geometric isomers may exist. For example, in the general formula (2), in the case where n ¹ = 2 and X ¹ is an organic residue derived from 1,2-cyclohexanediol, each substitutional positional relationship bonded to two cyclohexyl rings is cis-cis, cis -Trans and trans-trans are considered, and the whole molecule may be an optical isomer. In such a case, if necessary, the abundance ratio of a specific optical isomer may be increased using an optically active column or the like, or it may be used without such treatment.

Among these, X ¹ is an ethylene group (— (CH ₂ ) ₂ —), a 1,3-propylene group (— (CH ₂ ) ₃ —), a 1,2-propylene group (—CH ₂ —CH ( CH ₃₎ -) carbon number 2 alkylene group having 4 carbon atoms such as, 1,1-cyclohexylene group, 1,2-cyclohexylene group, 1,3-cyclohexylene, 1,4-cyclohexylene group, An organic residue derived from 1,1-cyclohexanedimethanol represented by the formula (—CH ₂ —C ₆ H ₁₀ —CH ₂ —), an organic residue derived from 1,2-cyclohexanedimethanol, 1 , C3-C8 cycloalkylene such as an organic residue derived from 1,3-cyclohexanedimethanol or an organic residue derived from 1,4-cyclohexanedimethanol is hardened in the cured product after polymerization. It is excellent in terms of size.

  Furthermore, in order to improve the refractive index of the cured product, an alkylene diol having a phenyl group or a phenylene group such as bisphenol A and an ethylene oxide adduct of bisphenol A, 1-phenyl-ethylene glycol, 1,2-diphenylene glycol, etc. preferable.

In general formula (2) n ¹ is an integer of 1 to 10, preferably 1 to 5. An n ¹ of 6 or more is not preferable because the viscosity increases and it is difficult to produce.

In the case where X ¹ is a trihydric or higher polyhydric alcohol organic residue, it is possible to take a branched structure such as the following general formula (16).

General formula (16)

(In general formula (16), n ⁶ represents an integer of 0 to 4)

(Terminal polymerizable group)
R ⁴ which is a polymerizable group at the end of the general formula (2) has poor radical polymerizability by itself, and curing proceeds by copolymerization with a fumarate group or a malate group. Therefore, generally R ⁴ group / (fumarate group or Those having a molar ratio of (malate group) close to 1 are excellent in the physical properties of the cured product. Preferably, the molar ratio of R ⁴ group / (fumarate group or malate group) is in the range of 0.2 to 2, more preferably in the range of 0.8 to 1.5.

R ⁴ independently represents general formula (3) or general formula (4). Therefore, the structure of the general formula (3) and the structure of the general formula (4) can coexist in the polymerizable compound in the present invention. The terminal having the structure of the general formula (4) can also be produced by isomerizing all or part of the structure of the general formula (3).

  Thus, when producing the polymerizable compound having the general formula (4) by isomerizing the polymerizable compound having the general formula (3), depending on the structure of the polymerizable compound having the general formula (3), In some cases, the polymerizable composition is composed of several present polymerizable compounds.

  For example, when an isomerization reaction is carried out using a polymerizable compound represented by the structural formula (3), the product is a polymerizability composed of the structural formula (3), the structural formula (4), and the structural formula (5). May be a composition. Even in that case, it can be used as a polymerizable composition without any particular purification.

Structural formula (3)

Structural formula (4)

Structural formula (5)

  The ratio between the general formula (3) and the general formula (4) in the polymerizable compound and the polymerizable composition is expressed by the number of groups represented by the general formula (4) / {(the general formula (3). The number of groups to be obtained) + (number of groups represented by the general formula (4))} is preferably 0.6 or more from the viewpoint of polymerizability. More preferably, the ratio between the general formula (3) and the general formula (4) is 0.8 or more.

This ratio can be controlled by the production method, but reconfirmation of the ratio in the number of groups represented by the general formula (3) and the number of groups represented by the general formula (4) in the product is For example, a proton nuclear magnetic resonance apparatus (hereinafter abbreviated as “ ¹ H-NMR”) is measured, and the peak attributed to the group represented by the general formula (3) and the group represented by the general formula (4) It is possible to reconfirm by comparing the area ratios.

R ⁵ and R ⁶ in the general formula (3) are preferably a hydrogen atom or a methyl group from the viewpoint of polymerizability, and more preferably both are hydrogen atoms.

Further, from the viewpoint of polymerizability, R ⁷ in the general formula (4) is preferably a methyl group (the general formula (4) as a whole is a 1-propenyl group).

Y ¹ in the general formula (2) independently represents the structural formula (1) and the structural formula (2). Therefore, the structure of the structural formula (1) and the structure of the structural formula (2) can coexist in the polymerizable compound in the present invention. From the viewpoint of ease of copolymerization with R ⁴ in the general formula (2), (number of structures represented by the structural formula (2)) / ({number of structures represented by the structural formula (1)) + (Number of structures represented by structural formula (2))} is preferably 0.6 or more, and more preferably 0.8 or more.

This ratio can be controlled by the production method, but the reconfirmation of the ratio of structural formula (1) and structural formula (2) in the product can be performed by measuring, for example, ¹ H-NMR to determine the structural formula (1 ) And the area ratio of peaks attributed to structural formula (2) can be reconfirmed.

X ² in the general formula (2) represents an alkylene group having 1 to 4 carbon atoms. Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group.

(Other polymerizable functional groups)
The polymerizable compound of the present invention is a compound having a polymerizable functional group represented by the general formula (2). Furthermore, you may have polymerizable functional groups other than General formula (2) in the same molecule. Specific examples of such polymerizable functional groups include the following. However, the present invention is not limited to these.

Structural formula (6)

Structural formula (7)

Structural formula (8)

Structural formula (9)

Structural formula (10)

Structural formula (11)

Structural formula (12)

(Invention (II))
Next, the present invention (II) will be described. The present invention (II) is a method for producing the polymerizable compound of the present invention (I).

  The production method of the polymerizable compound of the present invention (I) can be divided into the following two steps A) and B). That is,

A) A step of forming a polymerizable functional group in which R ⁴ is the general formula (3) in the general formula (2) on the compound having an arylamine structure;

  B) a step of forming a terminal polymerizable group represented by the general formula (4) by isomerization of the group represented by the general formula (3).

  Combining these two steps is not essential for producing the polymerizable compound of the present invention (I). That is, the polymerizable compound of the present invention (I) can be produced by only one of the steps A) or B).

(Process A)
First, the step A) in the method for producing a polymerizable compound of the present invention (I) will be described.

The compound of the present invention (I) in which R ⁴ is represented by the general formula (3) is a reaction between the carboxylic acid represented by the general formula (15) and an arylamine compound having at least one hydroxyl group. Can be synthesized.

General formula (15)

(In the general formula (15), R ⁶² and R ⁶³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. X ⁵ is each independently a carbon number having 2 to 6 hydroxyl groups. 2 represents an organic residue derived from a polyhydric alcohol having 2 to 30 carbon atoms, Y ² independently represents Structural Formula (1) or Structural Formula (2), and n ⁵ represents an integer of 1 to 10. )

Structural formula (1)

Structural formula (2)

Preferred polyhydric alcohol or a X ^5, even in that may take a branched structure is the same as X ¹ in the general formula (1).

  The arylamine compound having at least one hydroxyl group is a compound in which at least one hydroxyl group is substituted in the arylamine compound exemplified in the description of the present invention (I).

First, a method for producing a compound of the general formula (15) in which Y ² is a maleic acid residue will be described.
As a method for producing a compound in which Y ² is a maleic acid residue in the general formula (15), it can be produced by addition reaction of an alcohol represented by the general formula (17) and maleic anhydride.

Formula (17)

(In the general formula (17), R ⁶⁴ and R ⁶⁵ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. X ⁶ is each independently a carbon number having 2 to 6 hydroxyl groups. 2 represents an organic residue derived from a polyhydric alcohol having 2 to 30 carbon atoms, and n ⁸ represents an integer of 1 to 10.)

The polyvalent alcohol preferable as X ⁶ and the point that a branched structure can be taken are the same as X ^{1 in the} general formula (1).

  The addition reaction of maleic anhydride and the alcohol represented by the general formula (17) can be carried out without a catalyst or under a catalyst. Examples of the catalyst include basic catalysts such as triethylamine and N, N-dimethylaminopyridine.

  The reaction temperature is 20 ° C to 150 ° C, preferably 40 ° C to 120 ° C. When the reaction temperature is less than 20 ° C., the progress of the reaction is slow and there is a possibility that it takes more time than necessary. On the other hand, when the reaction temperature exceeds 150 ° C., the yield of diester is increased, and the yield may be lowered.

  Moreover, there is no restriction | limiting in particular in the ratio of the preparation amount of maleic anhydride and alcohol represented by General formula (17). Generally, the alcohol represented by the general formula (17) is in the range of 0.2 molar equivalent to 10 molar equivalent, preferably 0.5 molar equivalent to 5 molar equivalent, more preferably 1 mole of maleic anhydride. Is in the range of 0.9 to 2 molar equivalents.

  If the ratio of the amount of the alcohol represented by the general formula (17) exceeds 10 molar equivalents, excess alcohol increases, and if it is less than 0.2 molar equivalents, unreacted maleic anhydride increases, economically. It is not preferable.

  It is also possible to add a solvent during this addition reaction. Examples of such a solvent include aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, dimethoxyethane, di (methoxyethyl) ether, tetrahydrofuran and 1,4-dioxane.

R ⁶⁴ and R ⁶⁵ of the alcohol represented by the general formula (17) are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In particular, it is desirable from the viewpoint of polymerizability that R ⁶⁴ and R ⁶⁵ are both hydrogen atoms.

  Specific examples of the alcohol represented by the general formula (17) include ethylene glycol monoallyl ether, propylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, 1,4-butylene glycol mono Allyl ether, cyclohexanediol monoallyl ether, cyclohexanedimethanol monoallyl ether, diethylene glycol monoallyl ether, dipropylene glycol monoallyl ether, 2-allyloxy-2-phenylethanol, 2-allyloxy-1-phenylethanol, 2-allyloxy -1,2-diphenylethanol and the like.

When X ⁶ is a trihydric or higher polyhydric alcohol organic residue, it can take a branched structure. Specific examples thereof include trimethylol ethane diallyl ether, trimethylol propane diallyl ether, pentaerythritol diallyl. Examples include ether, pentaerythritol triallyl ether, and ethylene oxide adducts and propylene oxide adducts of these alcohols.

Next, a method for producing a compound represented by general formula (15) in which Y ² is a fumaric acid residue will be described.

  The maleic acid monoester having an alkenyloxy group obtained above is a known acidic catalyst such as hydrochloric acid, basic catalyst such as morpholine, piperidine, diethylamine, etc., catalyst such as thiourea, chlorine, bromine, iodine, acid chloride, etc. It can be isomerized to a fumaric acid monoester having an alkenyloxy group.

  There is no restriction | limiting in particular in the reaction temperature of the said isomerization reaction. Generally, it is in the range of 30 ° C to 200 ° C, preferably 50 ° C to 150 ° C, more preferably 70 ° C to 120 ° C. When the reaction temperature exceeds 200 ° C., the risk of polymerization or decomposition reaction increases, which is not preferable.

  In this isomerization reaction, a known hindered phenol polymerization inhibitor or solvent may be used. Here, examples of the solvent used include aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, dimethoxyethane, di (methoxyethyl) ether, tetrahydrofuran and 1,4-dioxane, and acetic acid. Examples thereof include esters such as ethyl and butyl acetate, and ketones such as acetone and methyl ethyl ketone.

  The fumaric acid ester thus obtained can be purified by a treatment such as distillation, liquid separation or recrystallization.

(Esterification reaction)
Next, the esterification reaction in the step A) will be described.

Specific examples of the esterification reaction include the following three.
(I) A method of esterifying a carboxylic acid represented by the general formula (15) and an arylamine compound having at least one hydroxyl group in the presence of an acid catalyst.

  (Ii) A method in which the carboxylic acid represented by the general formula (15) is derivatized into an acid halide and then esterified by reacting with an arylamine compound having at least one hydroxyl group.

  (Iii) A method of esterifying a carboxylic acid represented by the general formula (15) and an arylamine compound having at least one hydroxyl group by using a condensing agent.

(Method (i))
First, the method (i) will be described.
Examples of the esterification catalyst that can be used in the method (i) include sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, ion exchange resin, mixed catalyst of boric acid and sulfuric acid, polyphosphoric acid, and trifluoric acid. Examples thereof include Lewis acids such as boron bromide etherate.

  The reaction can be carried out at normal pressure or under pressure or under reduced pressure, for example, 15 Pa to 1 MPa in absolute pressure. The reaction is allowed to proceed while distilling off by-product water at a reaction temperature of 20 ° C to 200 ° C, preferably 40 ° C to 150 ° C. If it is less than 20 ° C., the reaction is slow, and if it exceeds 200 ° C., by-products such as a polymer may increase.

  In the reaction, a solvent can also be used. Although there is no restriction | limiting in particular as a solvent, Specifically, benzene, hexane, a cyclohexane, toluene, xylene etc. can be mentioned, for example.

  Moreover, there is no restriction | limiting in particular in the preparation ratio of the carboxylic acid represented by General formula (15), and the arylamine compound which has at least 1 hydroxyl group. Depending on the reaction conditions, a polymerizable compound may be by-produced. For example, a part of the alcohol corresponding to the general formula (17) is eliminated from the ester moiety of the maleic acid monoester or fumaric acid monoester represented by the general formula (15). An esterification reaction is caused with the carboxyl group of the carboxylic acid represented, and the ester represented by the general formula (18) is by-produced and may be contained in the product, but without removing these, It can be used as a polymerization composition.

General formula (18)

(In the general formula (18), R ^{66 to} R ⁶⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X ⁷ and X ⁸ are each independently n ⁷ or n ^8. In the existing X ⁷ and X ⁸ , each independently represents an organic residue derived from a C2-C30 polyhydric alcohol having 2 to 6 hydroxyl groups, and Y ³ represents a structural formula (1 ) Or structural formula (2), and n ⁷ or n ⁸ represents an integer of 1 to 10.)

Structural formula (1)

Structural formula (2)

  After the esterification reaction, purification can be performed to remove impurities and unreacted substances. As a purification method, for example, an unreacted general formula is obtained by dissolving a polymerizable compound in an organic solvent such as benzene, toluene, cyclohexane, diethyl ether, dibutyl ether, methyl acetate, ethyl acetate, and washing with water and alkali. The carboxylic acid represented by (15) and the by-product carboxylic acids can be removed as salts.

  Purity by decantation and reprecipitation of the product with organic solvents such as aliphatic hydrocarbons such as hexane and octane, column purification using silica gel, etc., purification by thin layer chromatography, etc. Can give.

(Method (ii))
Next, the method (ii) will be described.
The method (ii) is a method in which the carboxylic acid represented by the general formula (15) is derivatized into an acid halide and then esterified by reacting with an arylamine compound having at least one hydroxyl group.

  There is no restriction | limiting in particular as the derivatization method to an acid halide, It can derivatize by the well-known method using thionyl chloride, phosphoryl chloride, phosphorus pentachloride, phosphorus trichloride, phosgene, etc.

  In particular, when thionyl chloride is used, zinc chloride, pyridine, iodine, triethylamine or the like may be used in combination as a catalyst. It is also known that a mixture of thionyl chloride and dimethylformamide and a mixture of thionyl chloride and hexamethylphosphoric triamide are good reagents for synthesizing acid halides.

  The polymerizable compound of the present invention can be produced by reacting the acid halide thus derivatized with an arylamine compound having at least one hydroxyl group by a known method.

(Method (iii))
Finally, the method (iii) will be described.
The method (iii) is a method in which the carboxylic acid represented by the general formula (15) is reacted with an arylamine compound having at least one hydroxyl group using a condensing agent for esterification.

  Specific examples of the condensing agent used in the method (iii) include, but are not limited to, dicyclohexylcarbodiimide, trifluoroacetic anhydride, sulfonyl chloride, and the like. Any generally known condensing agent can be used without particular limitation.

  Examples of the sulfonyl chloride used here include p-toluenesulfonyl chloride, methanesulfonyl chloride, trifluoromethanesulfonyl chloride and the like.

  Although there is no restriction | limiting in particular in the preparation amount of carboxylic acid represented by General formula (15), and a sulfonyl chloride, Generally sulfonyl chloride more than an equivalent is used. Preferably, the sulfonyl chloride is in the range of 1 to 2 molar equivalents relative to the carboxylic acid.

  Moreover, there is no restriction | limiting in particular in the preparation ratio of the carboxylic acid etc. which are represented by General formula (15), and the arylamine compound which has at least 1 hydroxyl group. Preferably, the hydroxyl group (—OH) to be esterified of the arylamine compound having at least one hydroxyl group with respect to the carboxyl group (—COOH) of the carboxylic acid is in the range of 0.2 molar equivalent to 2 molar equivalents, more preferably. It is in the range of 0.4 molar equivalent to 1.2 molar equivalent.

  The solvent used in this case is not particularly limited as long as it does not inhibit the reaction. Specific examples include ethers such as tetrahydrofuran and 1,4-dioxane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chloroform, dichloromethane and dichloroethane, dimethylformamide and dimethylsulfoxide. Can do.

  Examples of the base include alkali metals such as sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate.

  The amount of the base is preferably in the range of 1 molar equivalent to 5 molar equivalents relative to the carboxylic acid represented by the general formula (15), although depending on the type.

  The reaction temperature is -20 ° C to 100 ° C, preferably 0 ° C to 50 ° C. If it exceeds 100 ° C, side reactions increase, and if it is less than -20 ° C, the reaction may be delayed, which is not preferable.

  The resulting product can be purified to remove impurities. As a purification method, for example, a method in which a product is dissolved in an organic solvent such as benzene, toluene, xylene, cyclohexane, methyl acetate, ethyl acetate, diethyl ether, dichloroethane, chloroform, and washed with water, alkali, acid, Moreover, the method of wash | cleaning a product with organic solvents, such as aliphatic hydrocarbons, such as hexane and octane, and the method of reprecipitation can be mentioned. Furthermore, purity can be increased by performing column purification using silica gel or the like, or purification by thin layer chromatography or the like.

The above is the description of the step of forming a polymerizable functional group having the general formula (2) and R ⁴ of the general formula (3) on the A) arylamine compound.

(Process B)
Next, the step of forming the terminal polymerizable group represented by the general formula (4) by isomerization of the group represented by the general formula (3) will be described.

The polymerizable compound of the present invention in which R ⁴ of the present invention (I) is represented by the general formula (4) isomerizes the terminal group of the polymerizable compound of the present invention in which R ⁴ is represented by the general formula (3). It can be manufactured by the method.

(Isomerization reaction)
Hereinafter, the isomerization reaction will be described.
The isomerization reaction from the general formula (3) to the general formula (4) can be performed by using a known complex of elements such as palladium, rhodium, ruthenium or the like and a supported catalyst in which these elements are supported on a support. .

  There is no restriction | limiting in particular as a support | carrier used for such a supported catalyst, What is necessary is just a porous substance generally used as a support | carrier. Specific examples include silica, alumina, silica alumina, zeolite, activated carbon, titania, magnesia, and other inorganic compounds.

  The amount of the element supported on the carrier is preferably 0.05% by mass to 20% by mass and more preferably 2% by mass to 10% by mass with respect to the total amount of the catalyst. If the supported amount is less than 0.05% by mass, the reaction time is delayed, and if it exceeds 20% by mass, more elements are not involved in the isomerization reaction, which is not preferable.

The amount of the supported catalyst thus obtained is preferably 0.01% by mass to 50% by mass relative to the polymerizable compound of the present invention in which R ^{1 of} the end group is the general formula (3). The mass% to 30 mass% is more preferable. If the amount of the catalyst is less than 0.01% by mass, the reaction time is delayed, and if it exceeds 50% by mass, the number of catalysts not involved in the isomerization reaction increases. Further, as the isomerization catalyst, a single catalyst or two or more catalysts can be used.

  There is no particular limitation on the reaction temperature of the isomerization reaction. Generally, it is 30 degreeC-200 degreeC, Preferably it is 60 degreeC-180 degreeC, More preferably, it is the range of 80 degreeC-160 degreeC. If the reaction temperature is less than 30 ° C, the reaction is slow, and if it exceeds 200 ° C, polymerization may occur during isomerization, which is not preferable.

  The isomerization reaction in the present invention can be carried out in a solvent. Solvents used include aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, dimethoxyethane, di (methoxyethyl) ether, tetrahydrofuran and 1,4-dioxane, ethyl acetate, butyl acetate and the like. Examples include esters, ketones such as acetone and methyl ethyl ketone, and alcohols such as methanol, ethanol, and isopropanol. When these solvents are used, two or more kinds of solvents may be mixed.

  This isomerization reaction can be carried out at normal pressure or under pressure, for example, at 1 KPa to 1 MPa.

  In addition, a polymerization inhibitor may be added to suppress polymerization during the isomerization reaction. Polymerization inhibitors include p-benzoquinone, naphthoquinone, quinones such as 2,5-diphenyl-p-benzoquinone, polyhydric phenols such as hydroquinone, p-t-butylcatechol, 2,5-di-t-butylhydroquinone And phenols such as hydroquinone monomethyl ether, di-t-butylparacresol, and α-naphthol.

(Invention (III))
Next, the present invention (III) will be described.
The present invention (III) is a polymerizable composition comprising the polymerizable compound of the present invention (I).

(Other ingredients)
In addition to the polymerizable compound of the present invention (I), the polymerizable composition of the present invention (III) can contain a radically polymerizable compound or a radical polymerization initiator, if necessary.

  Examples of the radical polymerizable compound include unsaturated polyesters, oligomers having (meth) acrylate groups, and radical polymerizable monomers.

(Unsaturated polyester)
The unsaturated polyester is obtained by polycondensation reaction of an α, β-unsaturated polybasic acid or acid anhydride with a saturated polybasic acid or a polyhydric alcohol.

(Α, β-unsaturated polybasic acid)
Examples of the α, β-unsaturated polybasic acid include maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride and the like. Moreover, as saturated polybasic acid used together as an acid component, saturated aliphatic dicarboxylic acid such as succinic acid, adipic acid, sebacic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic anhydride, Aromatic polycarboxylic acids such as 2,6-naphthalenedicarboxylic acid, endic acid anhydride, 1,2-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid . Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, 1,2-propanediol or 1,3-propanediol, dipropylene glycol, 1,3-butanediol or 1,4-butanediol, neopentyl glycol, 2-methyl Aliphatic diols such as 1,3-propanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,6-nonanediol or 1,9-nonanediol, 1,4-cyclohexane Alicyclic diols such as dimethanol, tricyclodecane dimethanol, hydrogenated bisphenol A, aromatic diols such as ethylene oxide and propylene oxide adducts of bisphenol A, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbi Lumpur, trihydric or higher alcohols such as dipentaerythritol and the like.

  Other unsaturated polyesters include those obtained by transesterification of the saturated polybasic acids and dialkyl esters of unsaturated polybasic acids with polyhydric alcohols. In this case, the alkyl group is usually a methyl group, an ethyl group, a propyl group, a butyl group or the like.

(Oligomer having (meth) acrylate group)
The oligomer having the above (meth) acrylate group is a compound having two or more (meth) acryloyl groups in the structure, specifically, urethane (meth) acrylate, polyhydric alcohol and polybasic acid or its Polyester (meth) acrylate obtained by reacting (meth) acrylic acid with polyester (meth) acrylate obtained by reaction of anhydride and (meth) acrylic acid, polyhydric alcohol obtained by adding ethylene oxide or propylene oxide to a hydroxyl group-containing compound ) Acrylate, epoxy compound and (meth) acrylic acid or epoxy (meth) acrylate obtained by reacting carboxyl group-containing (meth) acrylate, and ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neo Nethyl glycol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Examples thereof include polyfunctional (meth) acrylates such as dipentaerythritol hexa (meth) acrylate, and silicon (meth) acrylate having a siloxane group and a (meth) acryloyl group.

(Urethane (meth) acrylate)
Furthermore, the urethane (meth) acrylate of the present invention is a known one, and can be obtained by reacting a polyhydric alcohol, a polyisocyanate, hydroxyethyl (meth) acrylate, and hydroxypropyl (meth) acrylate. The polyhydric alcohol is, for example, the same as described in the polyhydric alcohol of the unsaturated polyester, and as the polyisocyanate, toluene diisocyanate, 4,4′-diphenylmethane isocyanate, xylene diisocyanate, hexamethylene diisocyanate, isophorone. Diisocyanate etc. are mentioned.

  Examples of the polybasic acid and polyhydric alcohol used as a raw material for the polyester (meth) acrylate and polyether (meth) acrylate of the present invention include the same as those described for the unsaturated polyester.

  Examples of the epoxy compound used as a raw material for the epoxy (meth) acrylate of the present invention include bisphenol A type, bisphenol S type, bisphenol F type bisphenol glycidyl ether, novolac type glycidyl ether and other epoxy resin compounds. Are known.

(Radical polymerizable monomer)
The radical polymerizable monomer of the present invention has a polymerizable unsaturated group, and specifically includes methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl ( Monofunctional (meth) acrylates such as (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, aromatic vinyl compounds such as styrene, α-styrene, methoxystyrene, divinylbenzene, Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl stearate, vinyl caproate and other aliphatic carboxylic acid vinyl esters, cyclohexane carboxylic acid vinyl ester and other alicyclic vinyl esters, benzoic acid vinyl ester, t -Butyl benzoate vinyl ester Aromatic vinyl esters, hydroxyethyl vinyl esters, hydroxypropyl vinyl esters, hydroxybutyl vinyl esters, etc., hydroxyalkyl vinyl esters, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl fumarate, itacon Allyl compounds such as diallyl acid, triallyl trimelliate, triallyl cyanurate, triallyl isocyanurate, diallyl carbonate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, N-methylmaleimide, N-cyclohexylmaleimide N-phenylmaleimide, N-laurylmaleimide, N-2-methylphenylmaleimide, N-2-chlorofu Maleimides such as nilmaleimide, N-2-methoxyphenylmaleimide, N, N-4,4′-diphenylmethanebismaleimide, maleic acid, fumaric acid, maleic anhydride, dimethyl maleate, diethyl maleate, dimethyl fumarate, Examples thereof include fumaric acid esters represented by unsaturated dibasic acids such as diethyl fumarate, dimethyl itaconate and diethyl itaconate.

These radically polymerizable monomers can be used alone or in combination.
The amount of the polymerizable compound of the present invention (I) used in the polymerizable composition of the present invention (III) is determined in the polymerizable composition (that is, based on the total weight of the polymerizable composition = 100% by mass). The active compound is preferably 1% by mass to 99% by mass, and more preferably 5% by mass to 80% by mass.

(Radical polymerization initiator)
The radical polymerization initiator that can be used in the polymerizable composition of the present invention (III) can be any radical polymerization initiator as long as it generates radicals by heat, ultraviolet rays, electron beams, or radiation, for example. It is.

  Examples of radical polymerization initiators that can be used for thermal radical polymerization include azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobisisovaleronitrile, methyl ethyl ketone peroxide, and methyl isobutyl ketone peroxide. Ketone peroxides such as oxide, cyclohexanone peroxide, diacyl peroxides such as benzoyl peroxide, decanoyl peroxide, lauroyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide Dialkyl peroxides such as 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-di-t-butylperoxycyclohexane, 2,2-di (t-butyl) Peroxy) butoxy, such as butane , T-butyl peroxypivalate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, di-t-butyl peroxyhexahydroterephthalate, di-t-butyl Peroxyazelate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, di-t-butylperoxytrimethyladipate, t-butylper Oxy-2-ethylhexanoate, t-hexylperoxy alkylperoxyesters such as 2-ethylhexanoate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, t-butylperoxyisopropylcarbonate Such as percarbonates The

  In particular, in film formation such as coating by heat, it is possible to cause self-crosslinking without using a radical polymerization initiator.

  Examples of radical polymerization initiators that can be used for polymerization by ultraviolet rays and electron beams include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxy-cyclohexyl-phenylketone, 2-methyl-1- [4- (Methylthio) phenyl] -2-monforinopropanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-hydroxy-2-methyl- Acetophenone derivatives such as 1-phenyl-propan-1-one, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4-trimethylsilylbenzophenone, benzophenone derivatives such as 4-benzoyl-4′-methyl-diphenyl sulfide, benzoin , Benzoin ethyl Examples include benzoin derivatives such as ether, benzoin propyl ether, benzoin isobutyl ether, and benzoin isopropyl ether, methylphenylglyoxylate, benzoin dimethyl ketal, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like.

  The amount of these polymerization initiators used is preferably 0.01% by mass to 15% by mass, more preferably 0.1% by mass to 10% by mass, based on the mass of the polymerizable composition of the present invention (III). Range.

(Additive)
Moreover, when superposing | polymerizing the polymeric composition of this invention, various additives can be added as needed according to the intended purpose. For example, an ultraviolet absorber, an antioxidant, a colorant, a lubricant, an antistatic agent, an inorganic filler such as silica, alumina, or aluminum hydroxide may be used in combination.

  The polymerizable composition of the present invention (III) can be cured by a curing method such as coating using a roll coater or spin coater, cast molding method, stereolithography method, etc., using ultraviolet rays, electron beams or heat.

  Further, the polymerizable composition of the present invention may use a solvent if it is necessary to reduce the viscosity by a curing method. Examples of the solvent used include aromatic hydrocarbons such as toluene and xylene, acetates such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, tetrahydrofuran , Ethers such as 1,4-dioxane, and alcohols such as ethyl alcohol, (iso) propyl alcohol, and butyl alcohol.

(Invention (IV))
Finally, the present invention (IV) will be described. The present invention (IV) is a cured product obtained by curing the polymerizable composition of the present invention (III).

  The cured product of the present invention (IV) is useful as an organic electronic device represented by an electrophotographic photoreceptor and an organic electroluminescent element. Furthermore, since it is a polymerizable composition, it is a wood coating, a film coating, a metal coating, a plastic coating, an inorganic coating, a hard coating, an optical fiber coating, a coating material such as a gel coating agent, a paint material such as painting or printing ink, and an optical modeling material. It can be widely used in the field of curable resins such as optical materials such as optical discs, spectacle lenses and prisms, adhesives, photoresists, sealants, molding materials and the like. There is no restriction | limiting in particular as a base material to coat. Specific examples include metal, glass, plastic, and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples without departing from the gist of the present invention.

The following equipment was used for measurement of various data.
(Used equipment)
¹ H-NMR
Model used: JEOL EX-400 (400 MHz)

  It was dissolved in deuterated chloroform and measured using tetramethylsilane as an internal standard substance.

FT-IR
Model used: Spectrum GX manufactured by PerkinElmer
Measurement was performed by a liquid film method using a KBr plate.

GPC (gel permeation chromatography)
Model used:
Pump Showa Denko Co., Ltd. DS-4
Differential refractive index detector RI-71 manufactured by Showa Denko K.K.
Column used: KG, K-801, K-802 (all manufactured by Showa Denko KK)
Three are connected and used Eluent: Chloroform Column temperature: 40 ° C
Flow rate: 1mL
Measuring method: Mn and Mw were measured in terms of polystyrene.

Example 1
A 3 L glass flask was charged with 500 g of maleic anhydride, 573 g of ethylene glycol monoallyl ether, and 0.05 g of hydroquinone monomethyl ether, and the mixture was heated and stirred at 50 ° C. for 24 hours in a nitrogen atmosphere. To the obtained reaction product, 1 kg of 1,4-dioxane, 10 g of concentrated hydrochloric acid and 0.1 g of hydroquinone monomethyl ether were added, and the mixture was heated and stirred at 100 ° C. for 1 hour. Thereafter, 1,4-dioxane was distilled off under reduced pressure, and 1 kg of toluene and 1 kg of water were added to the reaction product for liquid separation. When toluene was distilled off from the organic layer under reduced pressure, 1020 g was obtained as a pale yellow liquid. Analysis by NMR and FT-IR confirmed that it was mono (2-allyloxyethyl) fumarate.

Structural formula (13)

(Example 2)
To a 1 L round bottom flask equipped with a stirrer, a magnetic stirrer, a Dimroth condenser, and a nitrogen introduction tube were added 118.19 g of cyclohexanediol monoallyl ether, 148.71 g of maleic anhydride, 268 mg of hydroquinone monomethyl ether, and 363 g of toluene. The mixture was heated and stirred at 110 ° C. for 24 hours in an atmosphere. Concentrated hydrochloric acid 12.6 g and hydroquinone monomethyl ether 267 mg were added to the obtained reaction product, and the mixture was heated to reflux for 5 hours under a nitrogen atmosphere. After cooling, the precipitated white precipitate was filtered off with a 0.1 μm membrane filter, and the filtrate was separated with water (500 mL × 3 times). The obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure using an evaporator to obtain 162.49 g as a pale yellow viscous liquid.

Structural formula (14)

(Example 3)
Into a 1 L glass flask equipped with a nitrogen introduction tube, an induction stirrer, and a thermometer, 44.4 g of mono (2-allyloxyethyl) fumarate obtained in Example 1 and 500 g of THF (tetrahydrofuran) were charged, and the reaction system was heated. Was replaced with nitrogen, and 154 g of potassium carbonate was added. After the end of exotherm, the mixture was stirred for 1 hour, and the reaction solution was cooled with ice water. When the temperature of the reaction solution became 10 ° C. or lower, 42.3 g of p-toluenesulfonyl chloride was added and stirred for 30 minutes. Thereafter, 20 g of an arylamine compound having a hydroxyl group represented by the structural formula (15) was added and stirred. The reaction solution was returned to room temperature and further stirred for 10 hours. Next, the reaction solution was concentrated, and the concentrated solution was transferred to a separatory funnel, and 500 g of ethyl acetate was added thereto, followed by separation washing with water. Thereafter, the organic layer was concentrated under reduced pressure to obtain a yellow viscous liquid. The obtained crude product was subjected to column purification.

1 kg of silica gel (WAKO-GEL C-200 manufactured by Wako Pure Chemical Industries, Ltd.) was slurried with hexane and packed in a column chromatograph tube having a diameter of 15 cm. The crude product obtained above was placed on the top of the column chromatography tube, and the crude product was eluted while applying a gradient from ethyl acetate / hexane = 1/10 to 1/2, and TLC (Pre-coated TLC Plates manufactured by MERCK) was used. Fractions having an Rf value of 0.45 (developing solution: ethyl acetate / hexane = 1/5) by SILICA GEL 60 F-254) were collected and concentrated under reduced pressure using an evaporator to obtain 39.8 g as a pale yellow oil. Obtained. The product was confirmed by ¹ H-NMR and FT-IR to be a compound represented by the structural formula (16).

Structural formula (15)

Structural formula (16)

(Example 4 to Example 6)
Synthesis was performed in the same manner as in Example 3 except that the raw material, an arylamine compound having a hydroxyl group, and the type of carboxylic acid were changed, and the compounds shown in the following table were synthesized.

Structural formula (17)

Structural formula (3)

Structural formula (18)

Structural formula (19)

Structural formula (20)

(Example 7)
In a 20 mL autoclave, 3.1 g of the compound represented by the structural formula (16) obtained in Example 3, 9.0 g of toluene, 0.9 g of Pd—Al ₂ O ₃ with 5% Pd loading, 6 mg of hydroquinone monomethyl ether The reaction system was purged with nitrogen, and then the autoclave was immersed in an oil bath at 140 ° C. and heated for 3 hours. After cooling, Pd—Al ₂ O ₃ was removed from the reaction solution by filtration, and toluene was distilled off from the filtrate under reduced pressure to obtain 2.8 g of a pale yellow viscous liquid. ¹ H-NMR was measured, and it was confirmed that 87% of the allyl group was isomerized to the 1-propenyl group by comparing the peaks of the allyl group and the 1-propenyl group.

(Examples 8 to 10)
According to the following table | surface, the isomerization reaction was performed similarly to Example 7, and the compound which has 1-propenyl group was synthesize | combined.

(Example 11)
A 100 mL flask equipped with a nitrogen blowing tube, induction stirrer, Dimroth condenser, and septum cap is charged with 20 g of an arylamine compound having a hydroxyl group represented by the structural formula (17) and 20 g of toluene, and the oil bath temperature is set to 100 ° C. And stirred with heating. From the septum cap, 2.4 g of fumaryl chloride was added with a syringe. Thereafter, the mixture was heated and stirred for 6 hours. Low-boiling substances were distilled off from the reaction solution under reduced pressure, and chloroform was added to the resulting yellow viscous liquid to prepare a solution. The solution was added into a large amount of methanol and reprecipitation was performed. The precipitate was separated by filtration and vacuum dried to obtain a pale yellow solid.

  A 500 mL glass flask equipped with a nitrogen inlet tube, an induction stirrer, and a thermometer was charged with 43.4 g of fumaric acid mono (2-allyloxycyclohexyl) obtained in Example 2 and 100 g of THF, and the reaction system was purged with nitrogen. Thereafter, 116.7 g of potassium carbonate was added. After the exotherm was over, the mixture was stirred for 30 minutes, and the reaction solution was cooled with ice water. When the temperature of the reaction solution reached 10 ° C. or lower, 32.5 g of p-toluenesulfonyl chloride was added and stirred for 30 minutes. Thereafter, 15 g of the pale yellow solid obtained previously was added and stirred. The reaction solution was returned to room temperature and further stirred for 22 hours. Next, the reaction solution was concentrated, and the concentrated solution was transferred to a separatory funnel, and 500 g of chloroform was added thereto, followed by separation and washing with water. Thereafter, chloroform was distilled off under reduced pressure, and toluene was then added and dissolved. The obtained toluene solution was added into a large amount of methanol to perform reprecipitation. The precipitate was separated by filtration and vacuum dried to obtain a pale yellow solid.

¹ H-NMR, FT-IR and GPC of this product were measured and confirmed to be a compound represented by the structural formula (21).

Mn: 2980
Mw: 4120
Mw / Mn: 1.38
Structural formula (21)

(Examples 12 to 17 and Comparative Example 1)
The polymerizable compound of the present invention obtained in the above Examples or a composition containing the same was applied on a glass substrate and thermally cured, and the surface hardness of the cured film was examined. The surface hardness was in accordance with the pencil scratch test of JIS K5400.

  Further, a tack-free one having no stickiness on the cured surface was designated as “tackiness ◯”, and one having a tackiness as “x”. For the solvent resistance, the cured surface was wiped with absorbent cotton moistened with acetone.

The coating film described in Comparative Example 1 was prepared as follows. (Comparative Example 1)
10 parts by weight of a polycarbonate resin (Mn = 20000) having a repeating unit having the structure represented by the structural formula (22), 10 parts of an arylamine compound represented by the structural formula (23), 50 parts by weight of monochlorobenzene and dichloromethane It melt | dissolved in 30 mass parts mixed solvent, this composition was apply | coated on the glass base | substrate, it was made to dry at 110 degreeC for 1 hour, and the coating film was created.

Structural formula (22)

Structural formula (23)

  The results obtained as described above are shown in Table 3 below.

Claims (20)

A polymerizable compound having a structure represented by the general formula (1).
General formula (1)

(In the general formula (1), at least one of R ¹ , R ² and R ³ is an aryl group having a polymerizable functional group represented by the general formula (2), and the other is an alkyl group. And at least one selected from the group consisting of a group, an aralkyl group, and an aryl group, provided that R ¹ , R ² and R ³ may be the same or different, wherein the alkyl group is a methyl group, An ethyl group, an n-propyl group or an iso-propyl group, an aralkyl group is a benzyl group or a phenethyl group, an aryl group is a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group and the general formula (7) It is at least one selected from the group consisting of groups represented by formula (8).
General formula (2)

(In General Formula (2), each R ⁴ is independently a structure represented by General Formula (3) or General Formula (4), and X ¹ is each independently a carbon having 2 to 6 hydroxyl groups. Represents an organic residue derived from a polyhydric alcohol having 2 to 30 carbon atoms, Y ¹ independently represents Structural Formula (1) or Structural Formula (2), and X ² each independently represents 1 to 1 carbon atoms. Represents an alkylene chain having 4 carbon atoms, n ¹ represents an integer of ¹ to 10, and n ² represents an integer of 0 to 1.)
General formula (3)

(In General Formula (3), R ⁵ and R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)
General formula (4)

(In General Formula (4), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
Structural formula (1)

Structural formula (2)

General formula (7)

General formula (8)

(In General Formula (7) and General Formula (8), R ^{11 to} R ²⁵ are each independently General Formula (2), a chlorine atom, a bromine atom, a fluorine atom, a hydrogen atom, a methyl group, an ethyl group, or n-propyl. A group, an iso-propyl group, a group represented by general formula (13) or general formula (14);
Formula (13)

(In the formula, each X ³ independently represents an alkylene group having 1 to 4 carbon atoms, and n ³ represents an integer of 1 to 10.)
General formula (14)

(In the formula, each X ⁴ independently represents an alkylene group having 1 to 4 carbon atoms, and n ⁴ represents an integer of 1 to 10.) In R ⁴ of the general formula (2), the number of groups represented by the general formula (4) / {(the number of groups represented by the general formula (3)) + (the group represented by the general formula (4) The polymerizable compound according to claim 1, wherein the number of In Y ¹ of the general formula (2), (the number of structures represented by the structural formula (2)) / ({the number of structures represented by the structural formula (1)) + (the structural formula (2)] The polymerizable compound according to claim 1, wherein the number of structures is equal to or greater than 0.6. 4. The R ^{7 in the} general formula (4) is any one or more members selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group. Polymerizable compound. X ¹ in the general formula (2) are each independently a polymerizable compound according to any one of claims 1 to 4, characterized in residues der Rukoto residues or cycloaliphatic diol alkylene diol. The polymerizable compound according to claim ¹ , wherein R ¹ , R ² , and R ^{3 in the} general formula (1) are represented by the general formula (7) or the general formula (8) . . A polymerizable compound having a structure represented by the structural formula (16).
Structural formula (16)

A polymerizable compound having a structure represented by the structural formula (3).
Structural formula (3)

A polymerizable compound having a structure represented by the structural formula (19).
Structural formula (19)

A polymerizable compound having a structure represented by the structural formula (20).
Structural formula (20)

A polymerizable compound having a structure represented by the structural formula (21).
Structural formula (21)

The polymerization according to any one of claims 1 to 11, wherein a carboxylic acid represented by the following general formula (15) is reacted with an arylamine compound having at least one hydroxyl group in the presence of a catalyst. Method for producing a chemical compound.
General formula (15)

(In the general formula (15), R ⁶² and R ⁶³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. X ⁵ is each independently a carbon number having 2 to 6 hydroxyl groups. 2 represents an organic residue derived from a polyhydric alcohol having 2 to 30 carbon atoms, Y ² independently represents Structural Formula (1) or Structural Formula (2), and n ⁵ represents an integer of 1 to 10. )
Structural formula (1)

Structural formula (2)

The polymerizable compound according to claim 12 , wherein the carboxylic acid represented by the general formula (15) is reacted with an arylamine compound having at least one hydroxyl group in the presence of a condensing agent as a catalyst. Manufacturing method. The method for producing a polymerizable compound according to claim 13 , wherein the condensing agent is sulfonyl chloride. The terminal group of the polymerizable compound according to any one of claims 1 to 11 having the general formula (3) as a terminal group is subjected to an isomerization reaction of the terminal group in the presence of a catalyst. Is converted to the general formula (4), and a method for producing a polymerizable compound having the general formula (4) at a terminal group. Converting 60% or more of the general formula (3) in the polymerizable compound according to any one of claims 1 to 11 having a general formula (3) as a terminal group into a group of the general formula (4) in an isomerization reaction. The method for producing a polymerizable compound according to claim 15 . The method for producing a polymerizable compound according to claim 15 or 16 , wherein the catalyst used in the isomerization reaction is a catalyst containing at least one of palladium, rhodium, and ruthenium. 1 wt% to 99 wt% of the polymerizable compound according to any one of claims 1 to 11 and unsaturated polyesters, selected from (meth) acrylate compounds, vinyl compounds, and the group consisting of radically polymerizable monomers A polymerizable composition comprising 1% by mass to 99% by mass of at least one compound. It contains 100 parts by mass of the polymerizable compound according to any one of claims 1 to 11 or the polymerizable composition according to claim 18 and 0.01 to 15 parts by mass of a radical polymerization initiator. A polymerizable composition characterized. The hardened | cured material formed by hardening | curing the polymeric compound in any one of Claims 1-11, or the polymeric composition of Claim 18 or Claim 19 .