JP2018154778A - Active energy ray polymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an active energy ray polymerizable composition that can form a cured product excellent in scratch resistance and has good storage stability and an excellent cure rate; and a cured product thereof.SOLUTION: The active energy ray polymerizable composition contains: a compound of a specific structure having a piperidine skeleton and an ether group or amino group having an alkyl group substituted with fluorine; and a radical-polymerizable compound.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an active energy ray-polymerizable composition, a cured product thereof, a compound for obtaining them, and a method for producing the same.

  Active energy ray polymerization technology has advantages such as high polymerization speed, generally good workability due to the absence of solvent, and energy saving, so building materials, packaging materials, printing materials, display materials, electrical In the fields of electronic component materials, optical devices, displays, etc., their fields of use are expanding.

  Although there are a wide variety of applications using the active energy ray polymerization technology, the inhibition of curing due to oxygen is the biggest problem in many applications. For example, the method of blending the thiol compound disclosed in Patent Document 1 has a problem in storage stability because of the high reactivity of the thiol group. In the method of compounding the tertiary organic phosphine compound disclosed in Patent Document 2, it is considered that the inhibition of curing is suppressed by capturing dissolved oxygen and inert radicals, but the dissolved oxygen is captured even in a stored state. Therefore, there was a problem in storage stability. In the method of blending a compound having a 2,2,6,6-tetramethylpiperidine skeleton disclosed in Patent Document 3, it is thought that curing inhibition is suppressed by capturing dissolved oxygen. However, the inhibitory effect on polymerization inhibition was not sufficient, and there was a problem in the curing rate.

JP 2006-154774 A JP2015-34245A JP 2006-138161 A

  An object of the present invention is to provide an active energy ray-polymerizable composition that can obtain a cured product excellent in scratch resistance, has good storage stability, and has an excellent curing rate. Moreover, it aims at providing the hardened | cured material of this composition.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention contains a compound (a1) represented by the following general formula (1) and / or a compound (a2) represented by the following general formula (2), and a radical polymerizable compound (B). It is related with the active energy ray polymeric composition obtained.

[In the formulas (1) and (2), R ¹¹ and R ²¹ represent an alkyl group or an alkoxy group, and R ^{12 to} R ¹⁵ and R ^{22 to} R ²⁵ each independently represents an alkyl group. R ¹⁶ and R ¹⁷ each independently represent hydrogen, an alkyl group substituted with at least 3 or more fluorine atoms, or a group represented by —R ¹⁸ COOR ¹⁹ , and R ²⁶ represents —COR ²⁷ . , R ²⁷ represents an alkyl group substituted with at least 3 fluorine atoms. R ¹⁸ represents an alkylene group, and R ¹⁹ represents an alkyl group substituted with at least 3 fluorine atoms. However, R ¹⁶ and R ¹⁷ are not hydrogen at the same time. ]

In the present invention, R ¹¹ and R ²¹ are each an alkyl group having 1 to 4 carbon atoms, and R ^{12 to} R ¹⁵ and R ^{22 to} R ²⁵ are each independently an alkyl group having 1 to 4 carbon atoms. There, R ¹⁶ and R ¹⁷ each independently represents a group represented by hydrogen or -R ¹⁸ COOR ^19, R ²⁶ represents -COR ^27, R ²⁷ is substituted with at least 3 or more fluorine And an alkyl group having 1 to 8 carbon atoms, R ¹⁸ is an alkylene group having 2 to 5 carbon atoms, and R ¹⁹ is an alkyl group having 1 to 8 carbon atoms substituted with at least 3 fluorine atoms. It is related with the said active energy ray polymeric composition which is.

  Moreover, this invention relates to the hardened | cured material of the said active energy ray polymeric composition.

  The present invention also relates to a compound represented by the following general formula (3) or the following general formula (4).

[In the general formula (3) and general formula (4), R ³¹ and R ⁴¹ represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ^{32 to} R ³⁵ and R ⁴² to R ⁴⁵ each independently represents an alkyl group having 1 to 4 carbon atoms, R ³⁶ and R ³⁷ each independently represent a group represented by hydrogen or -R ³⁸ COOR ^39, R ⁴⁶ are, —COR ⁴⁷ , wherein R ⁴⁷ represents an alkyl group having 1 to 8 carbon atoms substituted with at least 3 or more fluorine atoms. R ³⁸ represents an alkylene group having 2 to 5 carbon atoms, and R ³⁹ represents an alkyl group having 1 to 8 carbon atoms substituted with at least 3 fluorine atoms. However, R ³⁶ and R ³⁷ are not simultaneously hydrogen. ]

  In addition, the present invention provides a compound represented by the above general formula (3) in which a compound represented by the following general formula (3-1) and a compound represented by the following general formula (3-2) are reacted. It relates to a manufacturing method.

[In the formulas (3-1) and (3-2), R ³¹ represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ^{32 to} R ³⁵ are Each independently represents an alkyl group having 1 to 4 carbon atoms. R ³⁸¹ , R ³⁸² and R ³⁸³ each independently represent hydrogen or a methyl group. R ³⁹¹ represents a group represented by —COOR ³⁹ . R ³⁹ represents an alkyl group having 1 to 8 carbon atoms substituted with at least 3 or more fluorine atoms. ]

  In addition, the present invention provides a compound represented by the above general formula (4) in which a compound represented by the following general formula (4-1) and a compound represented by the following general formula (4-2) are reacted. It relates to a manufacturing method.

[In the general formulas (4-1) and (4-2), R ⁴¹ represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ^{42 to} R ⁴⁵ represent Each independently represents an alkyl group having 1 to 4 carbon atoms. X represents a halogen or a hydroxyl group. R ²⁶ represents an alkyl group having 1 to 8 carbon atoms substituted with at least 3 or more fluorine atoms. ]

  According to the present invention, a cured product having excellent scratch resistance can be obtained, and an active energy ray-polymerizable composition having good storage stability and an excellent curing rate can be provided. .

FIG. 1 is a ¹ H-NMR spectrum of the compound (1-1) obtained in Synthesis Example 1. FIG. 2 is an IR spectrum of the compound (1-1) obtained in Synthesis Example 1.

Hereinafter, embodiments of the present invention will be described.
In the present specification, “(meth) acryloyl”, “(meth) acrylic acid”, “(meth) acrylate”, and “(meth) acryloyloxy” are “acryloyl” unless otherwise specified. And / or “methacryloyl”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, and “acryloyloxy and / or methacryloyloxy”. Further, the “active energy ray polymerizable composition” may be abbreviated as “polymerizable composition”.

The present invention is an active energy ray-polymerizable composition comprising a compound (a1) represented by the following general formula (1) and / or a compound (a2) represented by the following general formula (2), and radical polymerization: And a functional compound (B). Here, the “active energy ray” means an energy ray in a broad sense that can provide energy necessary for activation for causing a chemical reaction, including ultraviolet rays, visible rays, infrared rays, electron beams, and radiation. . Although it does not specifically limit, In one Embodiment of this invention, it is preferable that the said active energy ray is a light energy ray containing an ultraviolet-ray. Hereinafter, each component which comprises the resin composition of this invention is explained in full detail.

<Compound (a1) (a2)>
The compound (a1) of the present invention is represented by the general formula (1), and the compound (a2) is represented by the general formula (2).
The compound (a1) and the compound (a2) have a 2,2,6,6-tetraalkylpiperidine skeleton, thereby trapping dissolved oxygen in the polymerizable composition, thereby suppressing inhibition of the polymerization reaction due to oxygen. And contributes to improving the reaction rate. Furthermore, by having fluorine atoms with small surface free energy in the same molecule, the transferability to the surface of the coating film etc. is improved, and it is effective on the coating film surface where the influence of the polymerization reaction inhibition by oxygen is the greatest. It becomes possible to suppress polymerization reaction inhibition by oxygen.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.
Among these, Preferably it is a C1-C4 alkyl group, More preferably, it is a methyl group, an ethyl group, More preferably, it is a methyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and butoxy.
Among these, Preferably it is a C1-C4 alkoxy group, More preferably, it is a methoxy group, an ethoxy group, More preferably, it is a methoxy group.

Examples of the alkyl group substituted with at least three or more fluorine include 2,2,2-trifluoroethyl propionate group, 2,2,3,3-tetrafluoropropyl propionate group, 2,2,3 , 3,4,4,5,5-octafluoropentylpropionate group, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylpro Pionate groups, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-pentadecafluorononylpropionate groups and the like can be mentioned.
Of these, preferably an alkyl group having 1 to 8 carbon atoms substituted with at least 3 or more fluorine atoms, more preferably 2,2,3,3,4,4,5,5-octafluoropentylpropionate. Group 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylpropionate, more preferably 3,3,4,4,5 5,6,6,7,7,8,8,8-tridecafluorooctylpropionate group.

Preferred groups for R ¹⁹ include 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 1H, 1H, 5H-octafluoropentyl group, 1H, 1H, 2H, Examples include 2H-tridecafluorooctyl group, 1H, 1H, 2H, 2H-pentadecafluorononyl group and the like.
Of these, preferably 1H, 1H, 2H, 2H-tridecafluorooctyl group, 1H, 1H, 2H, 2H-pentadecafluorononyl group, more preferably 1H, 1H, 2H, 2H-pentadecafluorononyl group is there.

Preferred groups for R ²⁷ include a pentadecafluoroheptanoyl group, a heptadecafluorooctanoyl group, a nonadecafluorononanoyl group, and the like.
Of these, a heptadecafluorooctanoyl group and a nonadecafluorononanoyl group are preferable, and a nonadecafluorononanoyl group is more preferable.

Examples of the alkylene group include a methylene group, an ethylene group, and an n-propylene group.
Of these, an alkylene group having 1 to 4 carbon atoms is preferable, and an ethylene group is more preferable.

  Specific examples of the compound (a1) represented by the general formula (1) include the following compounds, but are not limited thereto.

  Specific examples of the compound (a2) represented by the general formula (2) include the following compounds, but are not limited thereto.

Compound (a1) and compound (a2) can be easily identified using conventionally known analytical methods such as infrared absorption spectrum (IR) measurement, elemental analysis measurement, and nuclear magnetic resonance absorption spectrum ( ¹ H-NMR) measurement. can do. Only one type of compound (a1) or compound (a2) may be used, or a plurality of types may be used in combination.

<Compound represented by general formula (3), compound represented by general formula (4)>
In the compound represented by the general formula (3) or the following general formula (4), substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or at least 3 fluorine atoms. The C1-C8 alkyl group and C2-C5 alkylene group which are made are synonymous with those groups in General formula (3) or following General formula (4).
The compound represented by the general formula (3) and the compound represented by the general formula (4) have a 2,2,6,6-tetraalkylpiperidine skeleton to capture dissolved oxygen in the polymerizable composition. By doing so, inhibition of polymerization reaction due to oxygen is suppressed, which contributes to improvement of the reaction rate. Furthermore, by having fluorine atoms with small surface free energy in the same molecule, the transferability to the surface of the coating film etc. is improved, and it is effective on the coating film surface where the influence of the polymerization reaction inhibition by oxygen is the greatest. It becomes possible to suppress polymerization reaction inhibition by oxygen.

Preferred groups for R ³⁹ include 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 1H, 1H, 5H-octafluoropentyl group, 1H, 1H, 2H, Examples include 2H-tridecafluorooctyl group, 1H, 1H, 2H, 2H-pentadecafluorononyl group and the like.
Of these, preferably 1H, 1H, 2H, 2H-tridecafluorooctyl group, 1H, 1H, 2H, 2H-pentadecafluorononyl group, more preferably 1H, 1H, 2H, 2H-pentadecafluorononyl group is there.

Preferred groups as R ⁴⁷ include a pentadecafluoroheptanoyl group, a heptadecafluorooctanoyl group, a nonadecafluorononanoyl group, and the like.
Of these, a heptadecafluorooctanoyl group and a nonadecafluorononanoyl group are preferable, and a nonadecafluorononanoyl group is more preferable.

<Radically polymerizable compound (B)>
In the present invention, the radical polymerizable compound (B) (hereinafter sometimes abbreviated as “compound (B)”) is a general term for compounds having at least one skeleton capable of radical polymerization.

The compound (B) is not particularly limited as long as it is a compound having at least one skeleton capable of radical polymerization. Examples of the compound (B) include (meth) acrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and other unsaturated carboxylic acids and their salts, esters, acid amides and acid anhydrides, Are urethane acrylates, acrylonitrile, styrene derivatives, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes and other (meth) acrylates, arylates, acid amides, styrenes, other vinyl compounds , Radically polymerizable cyclic compounds, oligomers, prepolymers and the like, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.

The compound (B) preferably contains bifunctional or higher (meth) acrylic acid esters from the viewpoint of polymerization rate. The compound (B) is divided into a compound (b1) having a hydroxyl group and having no cyclic structure, a compound (b2) having a hydroxyl group and having a cyclic structure, and a compound (b3) having no hydroxyl group.

[Compound (b1) having a hydroxyl group and no cyclic structure]
Among the compounds (B), examples of the compound (b1) having a hydroxyl group and not having a cyclic structure include 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, and (meth) acrylic. 2-hydroxypropyl acid, 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, (meth) acrylic 4-hydroxybutyl acid, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, (meth) acrylic acid 10-hydroxydecyl, (meth) 12-hydroxylauryl acrylate, ethyl (meth) acrylate-α- (hydroxymethyl), monofunctional (meth) acrylic acid It has a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone lactone to the acryloyl group or methacryloyl group-containing compound having the hydroxyl group such as lyserol or 2- (acryloyloxy) ethyl 6-hydroxyhexanonate (meta) ) Alkylene oxide addition (meth) acrylic acid in which alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide is repeatedly added to acrylic acid ester or the above-mentioned hydroxyl group-containing α, β-ethylenically unsaturated double bond group-containing compound Hydroxyl-containing aliphatic (meth) acrylic acid esters such as esters;

  For example, hydroxyl groups such as N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, N-hydroxyoctyl (meth) acrylamide, etc. (Meth) acrylamides; and the like, but are not particularly limited thereto. These may use only 1 type or may use multiple types together.

[Compound (b2) having a hydroxyl group and a cyclic structure]
Among the compounds (B), examples of the compound (b2) having a hydroxyl group and a cyclic structure include (meth) acrylic acid 1,2-cyclohexanedimethanol and (meth) acrylic acid 1,3-cyclohexanedimethanol. , (Meth) acrylic acid 1,4-cyclohexanedimethanol, (meth) acrylic acid 2-hydroxy-3-phenoxymethyl, (meth) acrylic acid 2-hydroxy-3-phenoxyethyl, (meth) acrylic acid 2-hydroxy -3-phenoxypropyl, 2-hydroxy-3-phenoxybutyl (meth) acrylate, 2-hydroxy-3-phenoxydecyl (meth) acrylate, 2-hydroxy-3-phenoxyoctadecyl (meth) acrylate, (meth ) Monohydroxyethyl phthalate acrylic acid, 2- (4-benzoyl-3-hydroxyphenoxy) (meth) acrylic acid ) (Meth) acrylic acid esters having a cyclic structure other than a hydroxyl group such as ethyl and a heterocyclic ring;

For example, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} butoxybenzophenone, 2,2′-dihydroxy-4- {2- Hydroxyl-containing benzophenone-based (meth) acrylic esters such as (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxy-4 ′-(2-hydroxyethoxy) benzophenone;

  For example, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl) -5-chloro -2H-benzotriazole, 2- (2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxypropylphenyl) -5-chloro-2H-benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -2H-benzotriazole, and 2- (2'-hydroxy -3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole Triazole (meth) acrylic acid esters;

  For example, 2,4-diphenyl-6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methylphenyl) -6- [2- Hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2-methoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy }]-S-triazine, 2,4-bis (2-ethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis ( 2-Ethoxyphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, 2,4-bis (2,4-dimethylphenyl) -6- [2- Hydroxy-4- {2- (meth) acryloyloxyate Xyl}]-S-triazine, 2,4-bis (2,4-diethoxylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy}]-S-triazine, and 2 , 4-Bis (2,4-diethylphenyl) -6- [2-hydroxy-4- {2- (meth) acryloyloxyethoxy})]-S-triazine and other hydroxyl group-containing triazine-based (meth) acrylic acid esters However, it is not particularly limited to these. These may use only 1 type or may use multiple types together.

[Compound without hydroxyl group (b3)]
Among the compounds (B), examples of the compound (b3) having no hydroxyl group include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, and (meth) acrylic. 3-carboxypropyl acid, 4-carboxybutyl (meth) acrylate, (meth) acrylic acid dimer, maleic acid, fumaric acid, monomethylmaleic acid, monomethylfumaric acid, aconitic acid, sorbic acid, cinnamic acid, α-chloro Sorbic acid, glutaconic acid, citraconic acid, mesaconic acid, itaconic acid, tiglic acid, angelic acid, senecioic acid, crotonic acid, isococrotonic acid, mucobromic acid, mucochloric acid, sorbic acid, muconic acid, aconitic acid, penicillic acid, gellanic acid Citronellic acid, 4-acrylamidobutanoic acid, 6-acrylamidohexanoic acid, 2- (me ) Acrylyloxyethyl succinate, mono (meth) acrylic acid ω-carboxypolycaprolactone ester, etc., polylactone-based (meth) acrylic acid ester, ethylene oxide or propylene oxide having a carboxyl group at the terminal by ring-opening addition of lactone ring An alkylene oxide addition-type succinic acid having a carboxyl group at the terminal and an aliphatic acryloyl group or methacryloyl group-containing carboxylic acid such as an ester of (meth) acrylic acid, which is repeatedly added with an alkylene oxide such as And acid anhydrides thereof;

For example, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyl Oxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, and other carboxyl group-containing alicyclic and aromatic acryloyl or methacryloyl group-containing carboxylic acids and acid anhydrides thereof ;

For example, (meth) acrylic acid hydrazide, 2- (2-furyl) -3- (5-nitro-2-furyl) (meth) acrylic acid hydrazide, β- (2-furanyl) (meth) acrylic acid N ² , N ² -bis (2-chloroethyl) hydrazide, p-vinylbenzhydrazide, N- (m-vinylphenyl) acrylohydrazide, 4-vinylbenzenesulfonic acid hydrazide, 2- [2- (5-nitro-2-furyl) ) Vinyl] -4--quinolinecarbohydrazide and other (meth) acrylic acid esters having a hydrazino group;

For example, N-methylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, N-propylaminoethyl (meth) acrylate, N-butylaminoethyl (meth) acrylate, (meth) acryl (Meth) acrylic acid esters having primary and / or secondary amino groups such as N-tributylaminoethyl acid, tetramethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl acrylate, etc .;

For example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, pentamethylpiperidinyl (meth) acrylate, 4- (pyrimidine (Meth) acrylic acid esters having a tertiary amino group such as -2-yl) piperazin-1-yl (meth) acrylate;

For example, it has primary and / or secondary amino groups such as monomethylaminoethyl (meth) acrylamide, monoethylaminoethyl (meth) acrylamide, monomethylaminopropyl (meth) acrylamide, monoethylaminopropyl (meth) acrylamide and the like. (Meth) acrylamides;

For example, (meth) acrylamides having a tertiary amino group such as dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide;

For example, heterocyclic acryloyl group of maleimide derivatives having both nitrogen atom and oxygen atom such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc. Or methacryloyl group-containing compounds;

For example, cyclohexyl (meth) acrylate, 1-methyl-1-cyclopentyl (meth) acrylate, 1-ethyl-1-cyclopentyl (meth) acrylate, 1-isopropyl-1-cyclopentyl (meth) acrylate, (meth ) 1-methyl-1-cyclohexyl acrylate, 1-ethyl-1-cyclohexyl (meth) acrylate, 1-isopropyl-1-cyclohexyl (meth) acrylate, 1-ethyl-1-cyclooctyl (meth) acrylate Benzyl (meth) acrylate, iso-bornyl (meth) acrylate, phenyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2-oxo-1,2-phenylethyl (meth) acrylate, 2-Oxo-1,2-diphenylethyl (meth) acrylate, 1-naphthyl (meth) acrylate, 2-naphthyl (meth) acrylate 1-naphthylmethyl (meth) acrylate, 1-anthryl (meth) acrylate, 2-anthryl (meth) acrylate, 9-anthryl (meth) acrylate, 9-anthrylmethyl (meth) acrylate, (meth ) 2-methyladamantyl-2-yl acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-ethyl (meth) acrylate Adamantyl-2-yl, 2-n-propyladamantyl-2-yl (meth) acrylate, 2-isopropyladamantyl-2-yl (meth) acrylate, 1- (adamantan-1-yl) (meth) acrylate -1-methylethyl, 1- (adamantan-1-yl) -1-ethylethyl (meth) acrylate, 1- (adamantan-1-yl) -1 (meth) acrylate -Methylpropyl, 1- (adamantan-1-yl) -1-ethylpropyl (meth) acrylate, (meth) acrylic acid-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] Non-2-yl, (meth) acrylic acid-5-oxo-4-oxa-tricyclo [5.2.1.0 ^3,8 ] dec-2-yl, (meth) acrylic acid dihydro-α-terpinyl , (Meth) acrylic acid-6-oxo-7-oxa-bicyclo [3.2.1] oct-2-yl, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [3.3.1]. ] Oct-2-yl, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyloxyhexyl phthalate, 2- ( (Meta) acrylo Oxy octyl phthalate, 2- (meth) acryloyloxy decyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, etc. (meth) cyclic acrylate;

For example, N- (4-carbamoylphenyl) (meth) acrylamide, β- (2-furyl) (meth) acrylamide, 2,3-bis (2-furyl) acrylamide, N- (9H-fluoren-2-yl) (Meth) acrylamide, N-[(R) -1-phenylethyl] (meth) acrylamide, N-[(S) -1-phenylethyl] (meth) acrylamide, (Z) -N-methyl-3- ( Phenyl) (meth) acrylamide, (Z) -3- (phenyl) (meth) acrylamide, N, N-diethyl-3-phenyl (meth) acrylamide, (Z) -N, N-dimethyl-3- (phenyl) (Meth) acrylamides containing cyclic structures such as (meth) acrylamide

  For example, (meth) acrylic acid cyclic esters containing a sulfonyl group such as sulfophenoxyethyl (meth) acrylate, sulfocyclohexyl (meth) acrylate, sulfobenzyl (meth) acrylate;

For example, (meth) acryloyloxyethyldimethylbenzylammonium-p-toluenesulfonate, (meth) acryloyloxyethyltrimethylammonium-p-toluenesulfonate, (meth) acryloylaminopropyltrimethylammonium-p-toluenesulfonate, phenyl-2- ( Metal salts and ammonium salts of (meth) acrylic acid cyclic esters containing a sulfonyl group such as (meth) acryloyloxyethyl phosphate;

For example, di (meth) acrylic acid tricyclodecane dihydroxymethyl, di (meth) acrylic acid tricyclodecane dihydroxymethyl dicaprolactonate, di (meth) acrylic acid 1,2-adamantanediol, di (meth) acrylic acid 1 , 3-adamantanediol, 1,4-adamantanediol di (meth) acrylate, tricyclodecanyl dimethylol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, di (meth) acrylate di Cyclopentenyl, dicyclopentenyloxyethyl di (meth) acrylate, 1,4-bis (2-hydroxypropyl) benzene di (meth) acrylate, 1,3-bis (2-hydroxy) di (meth) acrylate Propyl) benzene, tetraethylene oxide addition of di (meth) acrylic acid-2,2-bis (hydroxyphenyl) propane , Tetraethylene oxide adduct of 2,2-bis (hydroxyphenyl) methane di (meth) acrylate, tetraethylene oxide adduct of di (meth) acrylic acid-4,4′-sulfonyldiphenol, di (meth) Tetraethylene oxide adduct of acrylic acid-water-added 2,2-bis (hydroxyphenyl) propane, tetraethylene oxide adduct of di (meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) methane, (Meth) acrylic acid-water-added 2,2-bis (hydroxyphenyl) propane, di (2-methyl) propenoic acid-water-added 2,2-bis (hydroxyphenyl) methane, di (meth) acrylic acid-2,2 -Tetraethylene oxide adduct of bis (hydroxyphenyl) propane-Dicaprolactonate, di (meth) acrylic acid-2,2-bis (hydroxy) Bifunctional (meth) acrylic acid cyclic esters such as tetraethylene oxide adduct of diphenyl) -dicaprolactonate;

For example, heterocyclic (meth) acrylic acid esters containing nitrogen atoms such as pentamethylpiperidinyl (meth) acrylate and 4- (pyrimidin-2-yl) piperazin-1-yl (meth) acrylate;

For example, imide (meth) acrylate, 2- (4-oxazolin-3-yl) ethyl (meth) acrylate, di (meth) acrylic acid ethoxylated isocyanuric acid, tri (meth) acrylic acid ethoxylated isocyanuric acid, ε-caprolactone Heterocyclic structures containing oxygen atoms in addition to nitrogen atoms such as modified tris- (2-acryloyloxyethyl) isocyanurate, di (meth) acrylic acid isocyanuric acid ethylene oxide modification, tri (meth) acrylic acid isocyanuric acid ethylene oxide modification (Meth) acrylic acid esters having;

For example, 4-acryloylmorpholine, N- [2- (1H-imidazol-5-yl) ethyl] (meth) acrylamide, N- (oxetane-3-ylmethoxymethyl) (meth) acrylamide, N- (oxetane-2 -Heterocyclic acrylamides such as (ylmethoxymethyl) (meth) acrylamide;

For example, methyl (meth) acrylate, ethyl (meth) acrylate, 1-propyl (meth) acrylate, 2-propyl (meth) acrylate, n-butyl (meth) acrylate, sec- (meth) acrylic acid Butyl, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-amyl (meth) acrylate, iso-amyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, n-nonyl (meth) acrylate, (meth) acrylic iso-nonyl, decyl (meth) acrylate, (meth) ) Alkyl (meth) acrylates such as dodecyl acrylate, octadecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate;

For example, (meth) acrylic acid (meth) allyl, (meth) acrylic acid 1-butenyl, (meth) acrylic acid 2-butenyl, (meth) acrylic acid 3-butenyl, (meth) acrylic acid 1,3-methyl- 3-butenyl, 2-chloro-2-propenyl (meth) acrylate, 3-chloro-2-propenyl (meth) acrylate, 2- (2-propenyloxy) ethyl (meth) acrylate, 2- (meth) acrylic acid 2- Propenyl lactyl, 3,7-dimethyloct-6-en-1-yl (meth) acrylate, (meth) acrylic acid (E) -3,7-dimethyloct-2,6-dien-1-yl, (Meth) acrylic acid esters further containing an unsaturated group such as rosinyl (meth) acrylate, cinnamyl (meth) acrylate, vinyl (meth) acrylate;

  For example, perfluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluorobutyl (meth) acrylate, perfluorooctyl (meth) acrylate, (meth) Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-par (meth) acrylate Fluoromethyl-2-perfluoroethylmethyl, tripperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, (meth) acrylpropenoic acid 2-perfluorodecylethyl, 2- (perfluorohexadecyl) (meth) acrylate (Meth) acrylic acid perfluoroalkyl esters and the like;

For example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 3-propoxyethyl (meth) acrylate, 2-butoxy (meth) acrylate Alkoxy group-containing (meth) acrylic esters such as ethyl, 3-butoxyethyl (meth) acrylate, 4-butoxyethyl (meth) acrylate;

  For example, alkylene oxide-containing (meth) acrylic acid derivatives such as an alkylene oxide adduct of (meth) acrylic acid;

For example, (meth) acrylic acid (methoxycarbonyl) methyl, (meth) acrylic acid (methoxycarbonyl) ethyl, (meth) acrylic acid (methoxycarbonyl) propyl, (meth) acrylic acid (methoxycarbonyl) butyl, (meth) acrylic Acid (methoxycarbonyl) decyl, (meth) acrylic acid (ethoxycarbonyl) methyl, (meth) acrylic acid (ethoxycarbonyl) ethyl, (meth) acrylic acid (ethoxycarbonyl) propyl, (meth) acrylic acid (ethoxycarbonyl) butyl , (Meth) acrylic acid (ethoxycarbonyl) hexyl, (meth) acrylic acid (ethoxycarbonyl) octyl, 2- (ethoxycarbonyloxy) ethyl (meth) acrylate, 2- (ethoxycarbonyloxy) propyl (meth) acrylate , (Meth) acrylic acid 2- (ethoxycarbonyloxy) butyl, (meth) acrylic acid 2- ( (Toxycarbonyloxy) hexyl, 2- (ethoxycarbonyloxy) octyl (meth) acrylate, 2- (propoxycarbonyloxy) ethyl (meth) acrylate, 2- (butoxycarbonyloxy) ethyl (meth) acrylate, (meth ) Fatty acid having one carbonyl group such as 2- (butoxycarbonyloxy) butyl acrylate, 2- (octyloxycarbonyloxy) ethyl (meth) acrylate, 2- (octyloxycarbonyloxy) butyl (meth) acrylate Family (meth) acrylic acid esters;

For example, 2-oxobutanoylethyl (meth) acrylate, 2-oxobutanoylpropyl (meth) acrylate, 2-oxobutanoylbutyl (meth) acrylate, 2-oxobutanoylhexyl (meth) acrylate, (Meth) acrylate 2-oxobutanoyloctyl, (meth) acrylate 2-oxobutanoyldecyl, (meth) acrylate 2-oxobutanoyldodecyl, (meth) acrylate 3-oxobutanoylethyl, (meth) ) 3-oxobutanoylpropyl acrylate, 3-oxobutanoylbutyl (meth) acrylate, 3-oxobutanoylhexyl (meth) acrylate, 3-oxobutanoyloctyl (meth) acrylate, (meth) acrylic 3-oxobutanoyl decyl acid, 3-oxobutanoyl dodecyl (meth) acrylate, 4-cyanooxobutane (meth) acrylate Ylethyl, 4-cyanooxobutanoylpropyl (meth) acrylate, 4-cyanooxobutanoylbutyl (meth) acrylate, 4-cyanooxobutanoylhexyl (meth) acrylate, 4-cyanooxo (meth) acrylate Butanoyloctyl, 2,3-di (oxobutanoyl) propyl (meth) acrylate, 2,3-di (oxobutanoyl) butyl (meth) acrylate, 2,3-di (oxo) (meth) acrylate Aliphatic (meth) acrylic acid esters having two carbonyl groups such as butanoyl) hexyl and 2,3-di (oxobutanoyl) octyl (meth) acrylate;

For example, (meth) acrylic acid-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] non-2-yl, (meth) acrylic acid-10-methoxycarbonyl -5-oxo-4-oxa-tricyclo [5.2.1.0 ^3,8 ] non-2-yl, (meth) acrylic acid-4-methoxycarbonyl-6-oxo-7-oxa-bicyclo [3 2.1] having a carbonyl group such as octa-2-yl, (meth) acrylic acid-4-methoxycarbonyl-7-oxo-8-oxa-bicyclo [3.3.1] oct-2-yl ( (Meth) acrylic acid cyclic esters;

  For example, N- (2-oxobutanoylethyl) (meth) acrylamide, N- (2-oxobutanoylpropyl) (meth) acrylamide, N- (2-oxobutanoylbutyl) (meth) acrylamide, N- ( (Meth) acrylamides having a carbonyl group such as 2-oxobutanoylhexyl) (meth) acrylamide, N- (2-oxobutanoyloctyl) (meth) acrylamide, diacetone (meth) acrylamide;

For example, (meth) acrylic acid phosphooxyethyl, (meth) acrylic acid phosphooxypropyl, (meth) acrylic acid phosphooxybutyl, (meth) acrylic acid-3-chloro-2-acid phosphooxyethyl, (Meth) acrylic acid-3-chloro-2-acid phosphooxypropyl, (meth) acrylic acid-3-chloro-2-acid phosphooxybutyl, (meth) acrylic acid phosphooxyethylene oxide (ethylene oxide addition moles: 4-10), (meth) acrylic acid acid phosphooxypropylene oxide (propylene oxide addition mole number: 4-10) and other phosphonic acid group-containing (meth) acrylic acid esters;

For example, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltripropoxysilane, 3- (meth) acryloyloxypropyltributoxysilane 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropylbutyldimethoxysilane, 3- (meth) acryloyloxypropylethyl dipropoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acrylic Yl trimethoxy silane, 3- (meth) acryloyloxy propyl trimethoxy propoxy alkoxysilyl group-containing (meth) acrylic acid esters such as silane;

For example, metal salts and ammonium of sulfonyl group-containing (meth) acrylic acid esters such as (meth) acryloyloxydimethylethylammonium ethyl sulfate, (meth) acryloylaminopropyltrimethylammonium sulfate, (meth) acryloylaminopropyltriethylammonium sulfate salt;

For example, di (meth) acrylic acid ethylene oxide, di (meth) acrylic acid triethylene oxide, di (meth) acrylic acid tetraethylene oxide, di (meth) acrylic acid polyethylene oxide, di (meth) acrylic acid propylene oxide, di (Meth) acrylic acid dipropylene oxide, di (meth) acrylic acid tripropylene oxide, di (meth) acrylic acid polypropylene oxide, di (meth) acrylic acid butene oxide, di (meth) acrylic acid pentane oxide, di (meth) 2,2-dimethylpropyl acrylate, hydroxypivalylhydroxypivalate di (meth) acrylate, hydroxypivalylhydroxypivalate hydroxypivalate dicaprolactonate, 1,6-hexane di (meth) acrylate Diol, di (meth) acrylic acid 1,2-hexane All, di (meth) acrylic acid 1,5-hexanediol, di (meth) acrylic acid 2,5-hexanediol, di (meth) acrylic acid 1,7-heptanediol, di (meth) acrylic acid 1,8 -Octanediol, di (meth) acrylic acid 1,2-octanediol, di (meth) acrylic acid 1,9-nonanediol, di (meth) acrylic acid 1,2-decanediol, di (meth) acrylic acid 1 , 10-decanediol, di (meth) acrylic acid 1,2-decanediol, di (meth) acrylic acid 1,12-dodecanediol, di (meth) acrylic acid 1,2-dodecanediol, di (meth) acrylic Acid 1,14-tetradecanediol, di (meth) acrylic acid 1,2-tetradecanediol, di (meth) acrylic acid 1,16-hexadecanediol, di (meth) acrylic acid 1,2-hexadecane All, di (meth) acrylate 2-methyl-2,4-pentanediol, di (meth) acrylate 3-methyl-1,5-pentanediol, di (meth) acrylate 2-methyl-2-propyl- 1,3-propanediol, 2,4-dimethyl-2,4-pentanediol di (meth) acrylate, 2,2-diethyl-1,3-propanediol di (meth) acrylate, di (meth) acryl Acid 2,2,4-trimethyl-1,3-pentanediol, dimethyloloctane di (meth) acrylate, 2-ethyl-1,3-hexanediol di (meth) acrylate, di (meth) acrylic acid 2 , 5-dimethyl-2,5-hexanediol, 2-methyl-1,8-octanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, Di (meth) acrylic 2,4-diethyl-1,5-pentanediol, 2-methyl-2-propyl-1,3-propanediol di (meth) acrylate, 2,4-dimethyl-2,4-di (meth) acrylate Pentanediol, 2,2-diethyl-1,3-propanediol di (meth) acrylate, 2,2,4-trimethyl-1,3-pentanediol di (meth) acrylate, di (meth) acrylate di Methyloloctane, 2-ethyl-1,3-hexanediol di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 2-butyl-2 di (meth) acrylate -Bifunctional such as ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, 1,1,1-trishydroxymethylethane di (meth) acrylate ( (Meta) Acry Esters;

For example, 1,2,3-propanetriol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate, 2-methylpentane-2,4-diol tri (meth) acrylate Tricaprolactonate, 2,2-dimethylpropane-1,3-diol tri (meth) acrylate, trimethylolhexane tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, tri (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol, tri (meth) acrylic acid 1,1,1-trishydroxymethylethane, tri (meth) acrylic acid 1,1,1-trishydroxymethylpropane, etc. Trifunctional (meth) acrylic acid esters;

For example, tetra (meth) acrylate pentaerythritol, tetra (meth) acrylate ethoxylated pentaerythritol, tetra (meth) acrylate ditrimethylolpropane, hexa (meth) acrylate dipentaerythritol, tetra (meth) acrylate 2, 2-bis (hydroxymethyl) 1,3-propanediol, tetra (meth) acrylic acid 2,2-bis (hydroxymethyl) 1,3-propanediol tetracaprolactonate, tetra (meth) acrylic acid di1, 2,3-propanetriol, tetra (meth) acrylate di-2-methylpentane-2,4-diol, tetra (meth) acrylate di-2-methylpentane-2,4-diol tetracaprolactonate, Di, 2-dimethylpropane-1,3-diol, meth) acrylic acid, tetra (meth) acrylic acid Trimethylol butane, tetra (meth) acrylate ditrimethylol hexane, tetra (meth) acrylate ditrimethylol octane, tetra (meth) acrylate di-2,2-bis (hydroxymethyl) 1,3-propanediol, hexa (meth) ) Di2,2-bis (hydroxymethyl) 1,3-propanediol acrylate, tri 2,2-bis (hydroxymethyl) 1,3-propanediol hexa (meth) acrylate, trimethyl hepta (meth) acrylate 2,2-bis (hydroxymethyl) 1,3-propanediol, octa (meth) acrylate tri-2,2-bis (hydroxymethyl) 1,3-propanediol, hepta (meth) acrylate di-2,2- Polyfunctional (meth) acrylic acid esters such as bis (hydroxymethyl) 1,3-propanediol polyalkylene oxide;

  For example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-propyl (Meth) acrylamide, N-tert-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-nonyl (meth) acrylamide, N-tricosyl (meth) acrylamide, N-nonadecyl (Meth) acrylamide, N-docosyl (meth) acrylamide, N-methylene (meth) acrylamide, N-tridecyl (meth) acrylamide, N- (5,5-dimethylhexyl) (meth) acrylamide, crotonamide, maleinamide, Fumaramide, Mesaconamide, Citraconami , Itaconamide, 2-methylprop-2-enoylamine, N, N-dimethyl (meth) acrylamide, N, N-diethyl- (meth) acrylamide, N- [3- (N ′, N′-dimethylamino) propyl] -Aliphatic (meth) acrylamides such as (meth) acrylamide, N- (dibutylaminomethyl) (meth) acrylamide, N-vinylmethanamide, N-vinylacetamide;

For example, N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-methoxypropyl (meth) acrylamide, N-methoxybutyl (meth) acrylamide, N-methoxyhexyl (meth) acrylamide, N-methoxy Octyl (meth) acrylamide, N-methoxydecyl (meth) acrylamide, N-methoxydodecyl (meth) acrylamide, N-methoxyoctadecyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide N-ethoxypropyl (meth) acrylamide, N-ethoxybutyl (meth) acrylamide, N-ethoxyhexyl (meth) acrylamide, N-ethoxyoctyl (meth) acrylamide, N-isopropoxymethyl (meth) acrylamide, N Isopropoxyethyl (meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-isopropoxybutyl (meth) acrylamide, N-isopropoxyhexyl (meth) acrylamide, N-isopropoxyoctyl (meth) acrylamide, N- Butoxymethyl (meth) acrylamide, N-butoxyethyl (meth) acrylamide, N-butoxypropyl (meth) acrylamide, N-butoxybutyl (meth) acrylamide, N-butoxyhexyl (meth) acrylamide, N-butoxyoctyl (meth) Acrylamide, N-isobutoxymethyl (meth) acrylamide, N-isobutoxyethyl (meth) acrylamide, N-isobutoxypropyl (meth) acrylamide, N-isobutoxybutyl (meth) acrylamide, N-isobutoxyhex Sil (meth) acrylamide, N-isobutoxyoctyl (meth) acrylamide, N- (pentoxymethyl) (meth) acrylamide, N-1-methyl-2-methoxyethyl (meth) acrylamide, N, N-di (methoxy) N-alkoxy group-containing (meth) acrylamides such as methyl) meth) acrylamide and N, N-di (ethoxymethyl) (meth) acrylamide;

  For example, (meth) acrylamides containing sulfonic acids such as (meth) acrylamide sulfonic acid, tert-butyl- (meth) acrylamide sulfonic acid, (meth) acrylamide-2-methyl-1-propanesulfonic acid;

  Examples of the compound include acryloyl group or methacryloyl group-containing compounds having a nitrile group such as (meth) acrylonitrile and 2-cyanoethyl (meth) acrylate, but are not particularly limited thereto.

Further, for example, o-di (meth) allylbisphenol A, hydrogenated bisphenol A in which an aromatic ring structure is hydrogenated, and the like are also included in the compound (b3) if they have one or more skeletons capable of radical polymerization. These may use only 1 type or may use multiple types together.

<Cationically polymerizable compound (C)>
In one embodiment of the polymerizable composition of the present invention, the polymerizable composition contains a cationically polymerizable compound (C) (hereinafter sometimes abbreviated as “compound (C)”) in addition to the above essential components. But you can.

Compound (C) contains one or more functional groups that are cationically polymerized by an acid catalyst, and these can be used without any particular limitation. The compound (C) is preferably a cyclic hetero compound (c) from the viewpoint of reactivity by active energy rays, and a compound having one or more cyclic ether groups is particularly preferably used among the cyclic hetero compounds.

  Among the cyclic hetero compounds (c), an epoxy group-containing compound (c1) which is a cyclic hetero compound having a three-membered cyclic ether group, an oxetanyl group-containing compound (c2) which is a four-membered cyclic ether, and a cyclic ether having five or more members. There exists a compound (c4) which has a hetero group other than a compound (c3) 2 or more oxygen or oxygen.

[Epoxy group-containing compound (c1) which is a cyclic hetero compound having a 3-membered cyclic ether group]
Examples of the epoxy group-containing compound (c1) include oxirane, methyloxirane, phenyloxirane, 1,2-diphenyloxirane, methylideneoxirane, oxiranylmethyl, oxiranylmethanol, oxiranecarboxylic acid, (chloromethyl) oxirane. , (Bromomethyl) oxirane, oxiranylacetonitrile, 2,2 ′-(dimethylmethylene) bis [(p-phenylene) oxymethylene] bisoxirane, 2,2 ′-[methylenebis (2,1-phenyleneoxymethylene)] Oxirane compounds such as bisoxirane, or epoxy group-containing compounds in which a hydrogen atom of an oxirane ring such as glycidyl ether, glycidyl ester or glycidylamine is substituted with a methylene bond group or a methine bond group;

  For example, epoxy group-containing compounds having a cycloalkane ring such as 2- (cyclohexylmethyl) oxirane and 2-ethoxy-3- (cyclohexylmethyl) oxirane;

  For example, alicyclic epoxy group-containing compounds having no aromatic ring such as 7-oxabicyclo [4.1.0] heptane and 3-methyl-7-oxabicyclo [4.1.0] heptane;

  For example, an alicyclic system having an aromatic ring such as 3-phenyl-7-oxabicyclo [4.1.0] heptane-3-carboxylate, 4-ethylphenyl 7-oxabicyclo [4.1.0] heptane Examples thereof include epoxy group-containing compounds.

[Oxetanyl group-containing compound which is a 4-membered ring ether (c2)]
Examples of the oxetanyl group-containing compound (c2) include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, di (1-ethyl-3- Oxetanyl) methyl ether and the like.

[Cyclic ether compound having 5 or more members (c3)]
Examples of the cyclic ether compound (c3) having 5 or more members include 2-methyltetrahydrofuran, 2,5-diethoxytetrahydrofuran, tetrahydrofuran-2,2-dimethanol 3-methyl-2,4 (3H, 5H)- Flange-on etc. are mentioned.

[Compound (c4) having two or more oxygen or hetero groups other than oxygen]
Examples of the compound (c4) having two or more oxygen or hetero groups other than oxygen include a cyclic ester compound, a cyclic formal compound, a cyclic carbonate compound, and a fluorine-containing cyclic compound. The cyclic formal compound is preferably a compound selected from dioxolanes, dioxanes and trioxanes.
Industrially, propiolactone, caprolactone, 1,3-dioxolane, 1,2-dioxane, 1,4-dioxane, ethylene carbonate, propylene carbonate, glycerin carbonate and the like are preferably used in terms of reactivity.

  Examples of the cationically polymerizable compound (c) include (c1), (c2), (c3) and (c4), and are not particularly limited, but include an epoxy group-containing compound (c1) or an oxetanyl group-containing compound ( c2) is preferred. In addition, the epoxy group-containing compound (c1) or the oxetanyl group-containing compound (c2) has a large steric distortion and tends to cause a nucleophilic ring-opening reaction. Therefore, since the crosslinking density can be improved at the time of polymerization, the cohesive force is easily improved, which is industrially preferable. These may be used alone or in combination of two or more depending on the purpose of use.

<Active energy ray polymerization initiator (E)>
The polymerizable composition of the present invention can be cured by a polymerization reaction that proceeds by irradiation with various activation energy rays. However, the polymerizable composition may contain an active energy ray polymerization initiator (E) (hereinafter sometimes abbreviated as “initiator (E)”) as necessary. By using the initiator (E), the polymerization reaction can be accelerated. In one embodiment of the present invention, the activation energy is preferably ultraviolet rays, and when the polymerization reaction is allowed to proceed by irradiation with ultraviolet rays, the polymerizable composition preferably contains an initiator (E). In the present invention, as the initiator (E), a compound arbitrarily selected from compounds known as active energy ray polymerization initiators can be used.

  Among the initiators (E), examples of the photo radical generator (e1) include 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthfluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4- Chlorobenzophenone, 4,4′-diaminobenzophenone, benzoinpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2 -Methyl-1-phenylpropan-1-one, 4-thioxanthone, camphorquinone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and the like.

  Examples of commercially available products include Irgacure 184,907,651,1700,1800,819,369, and 261 (manufactured by BASF), DAROCUR-TPO (manufactured by BASF, 2,4,6-trimethylbenzoyl- Diphenyl-phosphine oxide), Darocur-1173 (manufactured by Merck), Ezacure KIP150, and TZT (manufactured by Nippon Shibel Hegner), Kayacure BMS, Kayacure DMBI (manufactured by Nippon Kayaku Co., Ltd.) and the like.

Further, when the cationically polymerizable compound (C) or the epoxy-modified vegetable oil is used as the cationically polymerizable compound, it is preferable to include the photoacid generator (e2) in the initiator (E). Examples of the photoacid generator (e2) include sulfonium salts such as UVACURE1590 (manufactured by Daicel Cytec), CPI-110P (manufactured by San Apro), IRGACURE250 (manufactured by Ciba Specialty Chemicals), WPI-113 ( Examples include iodonium salts such as Wako Pure Chemical Industries, Ltd., RP-2074 (Rhodia Japan Co., Ltd.), etc. This is preferable because it forms a product.

  In this invention, the above-mentioned compound can be used individually or in combination of 2 or more types as an initiator (E). The mixing ratio of the initiator (E) is preferably in the range of 0.01 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, with the total amount of the polymerizable composition as 100 parts by mass, from the viewpoint of reactivity. Range.

  The polymerizable composition of the present invention does not substantially contain an organic solvent. The polymerizable composition preferably contains no organic solvent at all, but the initiator (E) is often poorly soluble in the polymerizable component. Therefore, a small amount of an organic solvent may be included to dissolve the initiator (E). The total amount of the polymerizable composition is 100 parts by mass, and the content of the organic solvent is preferably within 5 parts by mass.

  Furthermore, in order to improve the performance of the initiator (E), an active energy ray sensitizer may be used in combination. As typical examples of the active energy ray sensitizer, benzophenone derivatives, unsaturated ketone derivatives typified by chalcone derivatives and dibenzalacetone, benzyl and camphorquinone, etc. Polymethine dyes such as 2-diketone derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives , Acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphy Derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives , Tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes and the like. Other specific examples include Okawara Shin et al., “Dye Handbook” (1986, Kodansha), Nobu Okawara et al., "Chemicals of Functional Dyes" (1981, CMC), Chusaburo Ikemori et al., "Special Functional Materials" (1986, CMC) However, it is not limited to these, and other dyes and sensitizers that absorb light from the ultraviolet to the near-infrared region are included, and these may be used in any ratio as necessary. The above may be used.

Among the sensitizers, thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4′-dimethylbenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-bis. (Diethylamino) benzophenone and the like can be mentioned. Examples of coumarins include coumarin 1, coumarin 338 and coumarin 102. Examples of ketocoumarins include 3,3′-carbonylbis (7-diethylaminocoumarin). Raised Although it is Rukoto, but is not limited thereto.

<Silane compound (F)>
The resin composition of the present invention may contain a silane compound (F). A known silane compound can be used as the silane compound (F). For example, alkyl alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, methylpropyldiisopropoxysilane, methylpropyldiacetoxysilane, etc .;

  For example, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltriacetoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, diphenyldi Aryl alkoxysilanes such as acetoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylphenyldiisopropoxysilane, methylphenyldiacetoxysilane;

Examples thereof include dimethoxymethylsilane and tris (dimethylamino) silane.

Moreover, it is also possible to use a commercial product as the silane compound (F), and it is also possible to use an oligomeric silane obtained by oligomerizing a mixture of two or more silanes by hydrolysis and condensation. include. The silane compound (F) can be used alone or as a mixture of two or more.

<Antioxidant (G)>
The polymerizable composition in the present invention may further contain an antioxidant. By containing the antioxidant (G), coloring of the cured resin after active energy ray polymerization over time can be suppressed.
Examples of the antioxidant include phenolic antioxidants such as ADK STAB AO-50 and ADK STAB AO-80 (manufactured by ADEKA), phosphorus such as ADK STAB PEP-8 (manufactured by ADEKA) and IRGAFOS 168 (manufactured by BASF). Commercially available products such as sulfur-based antioxidants such as sulfur-based antioxidants and IRGANOX-PS-800FD (manufactured by BASF) are not limited thereto.

<Coloring material (J)>
The polymerizable composition of the present invention may contain a color material (J) in addition to the above components. In the present invention, the color material (J) is a general term for materials in which dyes and pigments are dispersed. By using the coloring material (J), it is possible to impart not only design properties but also various functionalities such as thermal properties, electrical properties, and optical properties, depending on the dyes and pigments contained therein.

The coloring material (J) is used by dispersing a dye or pigment in a high concentration with a dispersing resin. As such dyes and pigments, for example, achromatic pigments such as carbon black, titanium oxide, and calcium carbonate, or chromatic organic pigments and dyes can be used.
Examples of organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa Yellow, Benzidine Yellow, and pyrazolone red,
Soluble azo pigments such as Ritolol Red, Helio Bordeaux, Pigment Scarlet, Permanent Red 2B,
Derivatives from vat dyes such as alizarin, indanthrone, thioindigo maroon,
Phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green,
Quinacridone organic pigments such as quinacridone red and quinacridone magenta;
Perylene organic pigments such as perylene red and perylene scarlet,
Isoindolinone organic pigments such as isoindolinone yellow and isoindolinone orange;
Pyranthrone organic pigments such as pyranthrone red and pyranthrone orange, thioindigo organic pigments, condensed azo organic pigments, benzimidazolone organic pigments,
Quinophthalone organic pigments such as quinophthalone yellow,
Isoindoline organic pigments such as isoindoline yellow,
Other pigments include organic pigments such as Flavanthrone Yellow, Acylamide Yellow, Nickel Azo Yellow, Copper Azomethine Yellow, Perinone Orange, Anthrone Orange, Dianthraquinonyl Red, Dioxazine Violet.

Examples of the dye include azo dyes, rhodamine dyes, quinoline dyes, thiazine dyes, thiazole dyes, xanthene dyes, and nigrosine dyes.
These dye derivatives can be used without any particular problem.

Of the coloring material (J), a general acrylic resin is used as the dispersion resin, and in some cases, a surfactant, the above compound (B), or the compound (C) is also used in combination. The acrylic resin does not have a skeleton capable of radical polymerization or a skeleton capable of cationic polymerization, and is not included in the compound (B) and the compound (C).
The dispersion resin is preferably used in the range of 10 to 60 parts by mass in terms of non-volatile content with respect to 100 parts by mass of the dye or pigment. Moreover, when using together a compound (B) or a compound (C), it is preferable to use in 100-800 mass parts in conversion of a non volatile matter with respect to 100 mass parts of dyes and pigments.

In order to stabilize the dispersion of dyes and pigments, polar resins can be used as necessary.
Examples of such polar resins include polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, poly (meth) acrylic acid, (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymers, and styrene-maleic acid copolymers. , Styrene-maleic acid- (meth) acrylic acid alkyl ester copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate- (meth) acrylic acid copolymer, polystyrene sulfonic acid, sodium polystyrene sulfonate, styrene sulfonic acid -Hydrophilic vinyl copolymer resins such as maleic acid copolymer and polyitaconic acid;

For example, a polyester resin obtained by a polycondensation reaction of a polyvalent carboxylic acid and a polyol, and the entire resin is balanced between polar and nonpolar by introducing a polar group;
Cellulose derivatives such as methyl cellulose, ethyl cellulose, propyl cellulose, ethyl methyl cellulose, hydroxyalkyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, alkali metal carboxymethyl cellulose, alkali metal cellulose sulfate, cellulose graft polymer;
Polypeptides such as polyglutamic acid and polyaspartic acid;
Amide ester salts such as salts of long chain polyaminoamides and polar acid esters, salts of long chain polyaminoamides and high molecular weight acid esters, naphthalenesulfonic acid formalin condensates, stearylamine acetate, etc .;
However, it is not particularly limited to these. These can be used alone or in combination of two or more.

Examples of polar resins that are commercially available as dispersion resins include “Anti-Terra-U (polyaminoamide phosphate)”, “Anti-Terra-203 / 204 (high molecular weight polycarboxylate)” manufactured by Avicia, Disperbyk-101 (polyaminoamide phosphate and acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 110, 111 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, "166, 170 (polymer copolymer)", "400", "Bykumen" (high molecular weight unsaturated acid ester), "BYK-P104, P105 (high molecular weight unsaturated acid polycarboxylic acid)", "P104S, 240S" (High molecular weight unsaturated acid polycarboxylic acid and silicon system) "," Lactimon (long chain amine, unsaturated acid polycarboxylic acid and silico ) "And the like.
Further, “Efka CHEMICALS” “Efka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766”, “Efka Polymer 100 (modified polyacrylate), 150 (aliphatic) System modified polymer), 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylate), 745 (copper phthalocyanine system) "," Floren TG-710 (urethane oligomer), "Flownon manufactured by Kyoeisha Chemical Co., Ltd. “SH-290, SP-1000”, “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon KS-860, 873SN, 874 (polymer dispersing agent), # 2150 (manufactured by Enomoto Kasei Co., Ltd.) Aliphatic polycarboxylic acid), # 7004 (polyether ester type) ”.

<Additive (Q)>
If the resin composition of the present invention is within a range not impairing the effects of the present invention, various additives (Q) can be appropriately blended in addition to the above-described components. For example, blending organic or inorganic fillers from the viewpoints of polymerization cure shrinkage reduction, thermal expansion coefficient reduction, dimensional stability improvement, elastic modulus improvement, viscosity adjustment, thermal conductivity improvement, strength improvement, toughness improvement, coloring improvement, etc. it can. As such a filler, polymers, ceramics, metals, metal oxides, metal salts, and the like can be used, and the shape is not particularly limited, such as particles and fibers. In addition, in the blending of the above polymer, as a filler, such as a flexibility imparting agent, a plasticizer, a flame retardant, a storage stabilizer, a thixotropy imparting agent, a dispersion stabilizer, a fluidity imparting agent, an antifoaming agent, etc. Alternatively, it can be dissolved, semi-dissolved or micro-dispersed in the polymerizable composition as a polymer blend or polymer alloy.

<Manufacture of an active energy ray polymerizable composition>
The polymerizable composition of the present invention comprises the above compound (A) and compound (B) as essential components, and further, if necessary, compound (C), initiator (E), silane compound (F), antioxidant It can be produced by mixing the agent (G), the colorant (J) and other various additives (Q) and then uniformly mixing them.

The active energy ray polymerizable composition in the present invention preferably contains 0.1 to 10 parts by mass of the compound (A) in 100 parts by mass of the total amount of the polymerizable composition, and 1 to 7 parts by mass of the compound (A). It is more preferable to contain. If the compound (A) is 0.1 parts by mass or more in 100 parts by mass of the total amount of the polymerizable composition, the curing rate can be reduced by suppressing curing inhibition due to dissolved oxygen in the polymerizable composition during photocuring. Improvement can be expected, and a sufficient cohesive force can be easily obtained, and a cured product having excellent toughness can be expected.

When the polymerizable composition is stirred and mixed, it may be prepared by stirring and mixing using a general-purpose device such as a uniaxial or multiaxial extruder, kneader, or dissolver equipped with a decompression device. Good. Usually, the temperature at the time of stirring and mixing is preferably set to 10 to 60 ° C.

The polymerizable composition of the present invention can be used in any form of liquid, paste and film.
In addition, although it is preferable that the polymeric composition in this invention does not contain an organic solvent substantially, it is also possible to contain an organic solvent. For example, further adding organic solvents such as methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, cyclohexane, toluene, xylene and other hydrocarbon solvents, water, The viscosity of the polymerizable composition can be adjusted, or the polymerizable composition can be heated to lower the viscosity.

  Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. Unless otherwise specified, “parts” and “%” in Examples and Comparative Examples represent “parts by mass” and “% by mass”, respectively.

All ¹ H-NMR measurements in the examples were performed in deuterated chloroform using JNM-ECX400P manufactured by JEOL. All IR measurements were performed using Spectrum One from PerkinElmer. All elemental analysis measurements in the examples were performed using 2400 · CHN manufactured by PerkinElmer.

<Manufacture of colorant (J) dispersion>
[Production Examples 1 and 2]
After stirring the compound (B) and the dispersion resin and confirming that the dispersion resin was completely dissolved, the pigment was added, and after stirring with a high speed mixer or the like, the resulting mill base was mixed with a horizontal sand mill. The dispersion was produced for about 2 hours. Table 1 shows the composition of the dispersion (pigment dispersion) of the produced coloring material (J) (the numerical value represents parts by mass). In Table 1, a blank means no blending.

<Example>
<Synthesis of Compound (a1) (a2)>
[Synthesis Examples 1 to 27]
The present invention will be specifically described with reference to synthesis examples, but the present invention is not limited to the following synthesis examples.

A reaction vessel equipped with a stirrer and a thermometer was charged with 2 parts of 4-amino-1,2,2,6,6-pentamethylpiperidine and 1.8 parts of 2,2,2-trifluoroethyl acrylate at 23 ° C. And stirred. It was made to react at 23 degreeC overnight, it confirmed that reaction was complete by < ¹ > H-NMR, and 3.8 parts of compounds (1-1) were obtained. The structure of the obtained compound (1-1) was confirmed by ¹ H-NMR, IR, and elemental analysis. FIG. 1 shows the ¹ H-NMR spectrum of the compound (1-1), FIG. 2 shows the IR spectrum, and Table 2 shows the elemental analysis values.

  A reaction vessel equipped with a stirrer and a thermometer was charged with 2 parts of 4-amino-1,2,2,6,6-pentamethylpiperidine and 1.6 parts of 1,1,1-trifluoromethyl acrylate at 23 ° C. And stirred. Thereafter, 3.6 parts of compound (1-2) was obtained in the same manner as in Synthesis Example 1.

  A reaction vessel equipped with a stirrer and a thermometer was charged with 2 parts of 4-amino-1,2,2,6,6-pentamethylpiperidine and 2.2 parts of 2,2,3,3-tetrafluoropropyl acrylate, Stir at 23 ° C. Thereafter, 4.2 parts of compound (1-3) was obtained in the same manner as in Synthesis Example 1.

  A reaction vessel equipped with a stirrer and a thermometer was charged with 2 parts of 4-amino-1,2,2,6,6-pentamethylpiperidine, 3.4 parts of 1H, 1H, 5H-octafluoropentyl acrylate, and 23 ° C. And stirred. Thereafter, in the same manner as in Synthesis Example 1, 5.4 parts of compound (1-4) was obtained.

  In a reaction vessel equipped with a stirrer and a thermometer, 2 parts of 4-amino-1,2,2,6,6-pentamethylpiperidine, 4.9 parts of 1H, 1H, 2H, 2H-tridecafluorooctyl acrylate are added. Charged and stirred at 23 ° C. Thereafter, in the same manner as in Synthesis Example 1, 6.9 parts of compound (1-5) was obtained.

  A reaction vessel equipped with a stirrer and a thermometer was charged with 2 parts of 4-amino-1,2,2,6,6-pentamethylpiperidine and 5.5 parts of 1H, 1H, 2H, 2H-pentadecafluorononyl acrylate. , And stirred at 23 ° C. Thereafter, in the same manner as in Synthesis Example 1, 7.5 parts of compound (1-6) was obtained.

  A reaction vessel equipped with a stirrer and a thermometer was charged with 2 parts of 4-amino-1,2,2,6,6-pentamethylpiperidine and 3.6 parts of 2,2,2-trifluoroethyl acrylate at 23 ° C. And stirred. Thereafter, in the same manner as in Synthesis Example 1, 5.6 parts of compound (1-7) was obtained.

  A reaction vessel equipped with a stirrer and a thermometer was charged with 2 parts of 4-amino-1,2,2,6,6-pentamethylpiperidine and 3.3 parts of 1,1,1-trifluoromethyl acrylate at 23 ° C. And stirred. Thereafter, 5.3 parts of compound (1-8) was obtained in the same manner as in Synthesis Example 1.

  A reaction vessel equipped with a stirrer and a thermometer was charged with 2 parts of 4-amino-1,2,2,6,6-pentamethylpiperidine and 4.4 parts of 2,2,3,3-tetrafluoropropyl acrylate, Stir at 23 ° C. Thereafter, in the same manner as in Synthesis Example 1, 6.4 parts of compound (1-9) was obtained.

  A reaction vessel equipped with a stirrer and a thermometer was charged with 2 parts of 4-amino-1,2,2,6,6-pentamethylpiperidine, 6.7 parts of 1H, 1H, 5H-octafluoropentyl acrylate, and 23 ° C. And stirred. Thereafter, 8.7 parts of compound (1-10) was obtained in the same manner as in Synthesis Example 1.

  In a reaction vessel equipped with a stirrer and a thermometer, 2 parts of 4-amino-1,2,2,6,6-pentamethylpiperidine, 9.8 parts of 1H, 1H, 2H, 2H-tridecafluorooctyl acrylate are added. Charged and stirred at 23 ° C. Thereafter, 11.8 parts of compound (1-11) was obtained in the same manner as in Synthesis Example 1.

  A reaction vessel equipped with a stirrer and a thermometer was charged with 2 parts of 4-amino-1,2,2,6,6-pentamethylpiperidine, 11 parts of 1H, 1H, 2H, 2H-pentadecafluorononyl acrylate, 23 Stir at ° C. Thereafter, 13 parts of Compound (1-12) were obtained in the same manner as in Synthesis Example 1.

  In a reaction vessel equipped with a stirrer and a thermometer, 2 parts of 4-amino-1-ethyl-2,2,6,6-pentamethylpiperidine, 1H, 1H, 2H, 2H-tridecafluorooctyl acrylate 4.5 Parts were charged and stirred at 23 ° C. Thereafter, in the same manner as in Synthesis Example 1, 6.5 parts of compound (1-13) was obtained.

  In a reaction vessel equipped with a stirrer and a thermometer, 2 parts of 4-amino-1-butyl-2,2,6,6-pentamethylpiperidine, 1H, 1H, 2H, 2H-tridecafluorooctyl acrylate 3.9 Parts were charged and stirred at 23 ° C. Thereafter, in the same manner as in Synthesis Example 1, 5.9 parts of compound (1-14) was obtained.

  In a reaction vessel equipped with a stirrer and a thermometer, 2 parts of 4-amino-1-methoxy-2,2,6,6-pentamethylpiperidine, 1H, 1H, 2H, 2H-tridecafluorooctyl acrylate 4.5 Parts were charged and stirred at 23 ° C. Thereafter, in the same manner as in Synthesis Example 1, 6.5 parts of compound (1-15) was obtained.

  In a reaction vessel equipped with a stirrer and a thermometer, 2 parts of 4-amino-1-ethoxy-2,2,6,6-pentamethylpiperidine, 1H, 1H, 2H, 2H-tridecafluorooctyl acrylate 4.2 Parts were charged and stirred at 23 ° C. Thereafter, in the same manner as in Synthesis Example 1, 6.2 parts of compound (1-16) was obtained.

  In a reaction vessel equipped with a stirrer and a thermometer, 2 parts of 4-amino-1-butoxy-2,2,6,6-pentamethylpiperidine, 1H, 1H, 2H, 2H-tridecafluorooctyl acrylate 3.7 Parts were charged and stirred at 23 ° C. Thereafter, in the same manner as in Synthesis Example 1, 5.7 parts of compound (1-17) was obtained.

A reaction vessel equipped with a stirrer and a thermometer was charged with 2 parts of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, 1.8 parts of triethylamine, and 20 parts of tetrahydrofuran, and stirred at room temperature. Thereafter, 2.3 parts of trifluoroacetyl chloride was added dropwise over 20 minutes under cooling and stirring to 0 ° C. The reaction was carried out at 0 ° C. for 3 hours, and it was confirmed by IR that the reaction was complete. The reaction solution was transferred to a separatory funnel, water was added, and the mixture was extracted with ethyl acetate. The extract was washed with saturated sodium bicarbonate and water, dried over magnesium sulfate, and then the solvent was distilled off with an evaporator to obtain 2.9 parts of compound (2-1).

A reaction vessel equipped with a stirrer and a thermometer was charged with 2 parts of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, 1.8 parts of triethylamine, and 20 parts of tetrahydrofuran, and stirred at room temperature. Then, 4.1 parts of perfluorobutyryl chloride was dripped over 20 minutes, cooling and stirring to 0 degreeC. Thereafter, in the same manner as in Synthesis Example 16, 4.1 parts of compound (2-2) was obtained.

A reaction vessel equipped with a stirrer and a thermometer was charged with 2 parts of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, 1.8 parts of triethylamine, and 20 parts of tetrahydrofuran, and stirred at room temperature. Thereafter, 7.6 parts by mass of pentadecafluorooctanoyl chloride was added dropwise over 20 minutes while cooling and stirring to 0 ° C. Thereafter, 6.5 parts of compound (2-3) was obtained in the same manner as in Synthesis Example 16.

A reaction vessel equipped with a stirrer and a thermometer was charged with 2 parts of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, 1.8 parts of triethylamine, and 20 parts of tetrahydrofuran, and stirred at room temperature. Thereafter, 8.5 parts by mass of hepadecafluorononanoyl chloride was added dropwise over 20 minutes while cooling and stirring to 0 ° C. Thereafter, 7.0 parts of compound (2-4) were obtained in the same manner as in Synthesis Example 16.

A reaction vessel equipped with a stirrer and a thermometer was charged with 2 parts of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, 1.8 parts of triethylamine, and 20 parts of tetrahydrofuran, and stirred at room temperature. Thereafter, 9.3 parts by mass of nonadecafluorodecanoyl chloride was added dropwise over 20 minutes while cooling and stirring to 0 ° C. Thereafter, in the same manner as in Synthesis Example 16, 7.6 parts of compound (2-5) was obtained.

A reaction vessel equipped with a stirrer and a thermometer was charged with 2 parts of 4-hydroxy-1-methoxy-2,2,6,6-pentamethylpiperidine, 1.6 parts of triethylamine and 20 parts of tetrahydrofuran, and stirred at room temperature. Then, 3.8 parts of perfluorobutyryl chloride was dripped over 20 minutes, cooling and stirring to 0 degreeC. Thereafter, 4 parts of compound (2-6) were obtained in the same manner as in Synthesis Example 16.

A reaction vessel equipped with a stirrer and a thermometer was charged with 2 parts of 4-hydroxy-1-methoxy-2,2,6,6-pentamethylpiperidine, 1.4 parts of triethylamine and 20 parts of tetrahydrofuran, and stirred at room temperature. Thereafter, 3.3 parts of perfluorobutyryl chloride was added dropwise over 20 minutes while cooling and stirring to 0 ° C. Thereafter, 3.7 parts of compound (2-7) were obtained in the same manner as in Synthesis Example 16.

A reaction vessel equipped with a stirrer and a thermometer was charged with 2 parts of 4-hydroxy-1-ethoxy-2,2,6,6-pentamethylpiperidine, 1.8 parts of triethylamine, and 20 parts of tetrahydrofuran, and stirred at room temperature. Thereafter, 3.7 parts by mass of pentadecafluorooctanoyl chloride was added dropwise over 20 minutes with cooling and stirring to 0 ° C. Thereafter, in the same manner as in Synthesis Example 16, 3.8 parts of compound (2-8) was obtained.

A reaction vessel equipped with a stirrer and a thermometer was charged with 2 parts of 4-hydroxy-1-ethoxy-2,2,6,6-pentamethylpiperidine, 1.8 parts of triethylamine, and 20 parts of tetrahydrofuran, and stirred at room temperature. Thereafter, 3.5 parts of pentadecafluorooctanoyl chloride was added dropwise over 20 minutes while cooling and stirring to 0 ° C. Thereafter, in the same manner as in Synthesis Example 16, 3.8 parts of compound (2-9) was obtained.

A reaction vessel equipped with a stirrer and a thermometer was charged with 2 parts of 4-hydroxy-1-ethoxy-2,2,6,6-pentamethylpiperidine, 1.3 parts of triethylamine, and 20 parts of tetrahydrofuran, and stirred at room temperature. Thereafter, 3 parts of pentadecafluorooctanoyl chloride were added dropwise over 20 minutes under cooling and stirring to 0 ° C. Thereafter, 3.6 parts of compound (2-10) were obtained in the same manner as in Synthesis Example 16.
The compounds (1-2) to (1-17) and the compounds (2-1) to (2-10) obtained above were each similarly to compound (1-1) in ¹ H-NMR, IR And the structure was confirmed by elemental analysis. The elemental analysis values are shown in Table 2.

[Examples 1 to 40] [Comparative Examples 1 to 4]
<Production of polymerizable composition>
[Composition Examples 1-44]
Into a light-shielded 300 ml mayonnaise bottle substituted with an oxygen concentration of 10% or less, compound (a1) and / or compound (a2), compound (B), compound (C), initiator (E), silane compound ( F), antioxidant (G), colorant (J) and other various additives (Q) were charged in the ratios shown in Table 3, and thoroughly agitated with a stirrer and sufficiently defoamed. The polymerizable composition shown in the formulation examples was obtained. In Table 3, a blank represents no blending. Among them, Formulation Examples 5 to 44 are polymerizable compositions of the present invention corresponding to Examples 1 to 40, respectively, and Formulation Examples 1 to 4 are polymerizable of the present invention corresponding to Comparative Examples 1 to 4, respectively. It is a polymerizable composition that is not a composition. Table 4 shows the abbreviations used in Table 3.

<Evaluation of polymerizable composition>
With respect to the polymerizable composition shown in Table 3, the curing rate, storage stability, and scratch resistance were measured by the following methods, and the results are shown in Table 5.

《Curing speed》
The applicator was used to apply the polymerizable composition onto a polyethylene terephthalate (PET) film so that the coating film thickness was 10 μm, thereby preparing a coated product. The coated product was irradiated with ultraviolet rays of 0.2 J / cm ² (wavelength: 365 nm) at a conveyor speed of 10 m / min using a belt conveyor type ultraviolet irradiation device (metal halide lamp 100 W / cm1 lamp). Irradiation was repeated by touching the surface of the cured product after irradiation until stickiness disappeared, and the curing rate was evaluated in three stages. It can be determined that the lower the number of irradiations, the better the curability. Other than the evaluation “x”, there is no problem in actual use.
A: 1 to 3 times.
○: 4 to 6 times.
Δ: 7 to 9 times.
X: 10 times or more.

<Storage stability>
The polymerizable composition immediately after production was stored at 60 ° C. for 5 days, and then the state of the polymerizable composition was visually observed.
○: No change. Good.
X: Thickening or gelation. Bad.

《Abrasion resistance》
The polymerizable composition is applied on a glass plate using an applicator so that the coating thickness is 250 μm, and irradiated with ultraviolet rays of 0.3 J / cm ² (wavelength: 365 nm) to obtain a glass laminated cured film. The specimen was stored for 24 hours at 23 ° C. and 50% relative humidity to obtain a test piece. Measurement In a constant temperature and humidity chamber at 23 ° C. and 50% relative humidity, the test piece was rubbed 10 times with # 0000 steel wool while applying a load of 250 g / cm ² to conduct a scratch resistance test. It was. The presence or absence of scratches and the degree of scratches were visually observed and used as an index of scratch resistance.
Evaluation was performed in four stages. It can be judged that the smaller the number of scratches, the better the scratch resistance. Other than the evaluation “x”, there is no problem in actual use.
(Double-circle): There is no generating of a crack. No problem at all.
○: 5 or less scratches occur. There are some, but no problem.
Δ: 6 to 10 scratches are generated. Can be used practically.
X: 11 or more scratches occur. There is a problem in practical use.

  In Table 5, “curing speed” evaluates the polymerization speed. When the polymerization rate is slow and many unreacted double bonds are present in the composition, the film remains sticky even after light irradiation. “Storage stability” evaluates stability at 60 ° C. storage. “Abrasion resistance” is an evaluation of the hardness of the surface of the cured product.

When the polymerizable composition of the present invention is polymerized and cured with active energy rays, it exhibits an excellent curing rate as shown in Table 5, and excellent results in all items of storage stability and scratch resistance. (Examples 1-40). In particular, when Formulation Example 8 was used, the most excellent results were shown (Example 4). On the other hand, when a polymerizable composition other than the present invention is polymerized and cured with active energy rays, there are difficulties in curing speed, storage stability, and scratch resistance, and it may be difficult to use. Recognize.

Claims (6)

Active energy ray polymerization comprising a compound (a1) represented by the following general formula (1) and / or a compound (a2) represented by the following general formula (2) and a radical polymerizable compound (B) Sex composition.
[In the formulas (1) and (2), R ¹¹ and R ²¹ represent an alkyl group or an alkoxy group, and R ^{12 to} R ¹⁵ and R ^{22 to} R ²⁵ each independently represents an alkyl group. R ¹⁶ and R ¹⁷ each independently represent hydrogen, an alkyl group substituted with at least 3 or more fluorine atoms, or a group represented by —R ¹⁸ COOR ¹⁹ , and R ²⁶ represents —COR ²⁷ . , R ²⁷ represents an alkyl group substituted with at least 3 fluorine atoms. R ¹⁸ represents an alkylene group, and R ¹⁹ represents an alkyl group substituted with at least 3 fluorine atoms. However, R ¹⁶ and R ¹⁷ are not hydrogen at the same time. ] R ¹¹ and R ²¹ is an alkyl group having 1 to 4 carbon atoms, R ¹² to R ¹⁵ and R ²² to R ²⁵ are each independently an alkyl group having 1 to 4 carbon atoms, R ¹⁶ and R ^17, each independently represents a group represented by hydrogen or -R ¹⁸ COOR ^19, R ²⁶ represents -COR ^27, R ²⁷ has a carbon number of 1 substituted with at least three fluorine The alkyl group having 8 carbon atoms, R ¹⁸ is an alkylene group having 2 to 5 carbon atoms, and R ¹⁹ is an alkyl group having 1 to 8 carbon atoms substituted with at least 3 fluorine atoms. Active energy ray-polymerizable composition. Hardened | cured material of the active energy ray polymeric composition of Claim 1 or 2. The compound represented by the following general formula (3) or the following general formula (4).
[In the general formula (3) and general formula (4), R ³¹ and R ⁴¹ represent an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ^{32 to} R ³⁵ and R ⁴² to R ⁴⁵ each independently represents an alkyl group having 1 to 4 carbon atoms, R ³⁶ and R ³⁷ each independently represent a group represented by hydrogen or -R ³⁸ COOR ^39, R ⁴⁶ are, —COR ⁴⁷ , wherein R ⁴⁷ represents an alkyl group having 1 to 8 carbon atoms substituted with at least 3 or more fluorine atoms. R ³⁸ represents an alkylene group having 2 to 5 carbon atoms, and R ³⁹ represents an alkyl group having 1 to 8 carbon atoms substituted with at least 3 fluorine atoms. However, R ³⁶ and R ³⁷ are not simultaneously hydrogen. ] The manufacturing method of the compound represented by General formula (3) of Claim 4 with which the compound represented by the following general formula (3-1) and the compound represented by the following general formula (3-2) are made to react. .
[In the formulas (3-1) and (3-2), R ³¹ represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ^{32 to} R ³⁵ are Each independently represents an alkyl group having 1 to 4 carbon atoms. R ³⁸¹ , R ³⁸² and R ³⁸³ each independently represent hydrogen or a methyl group. R ³⁹¹ represents a group represented by —COOR ³⁹ . R ³⁹ represents an alkyl group having 1 to 8 carbon atoms substituted with at least 3 or more fluorine atoms. ] The manufacturing method of the compound represented by General formula (4) of Claim 4 with which the compound represented by the following general formula (4-1) and the compound represented by the following general formula (4-2) are made to react. .
[In the general formulas (4-1) and (4-2), R ⁴¹ represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ^{42 to} R ⁴⁵ represent Each independently represents an alkyl group having 1 to 4 carbon atoms. X represents a halogen or a hydroxyl group. R ²⁶ represents an alkyl group having 1 to 8 carbon atoms substituted with at least 3 or more fluorine atoms. ]