JP6787202B2 - Active energy ray-polymerizable composition - Google Patents

Description

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

The active energy ray polymerization technology has advantages such as a high polymerization rate, good workability due to being solvent-free in general, and energy saving. Therefore, building materials, packaging materials, printing materials, display materials, and electricity In the fields of electronic component materials, optical devices, displays, etc., the fields of application are expanding.

Although there are various uses using the active energy ray polymerization technology, hardening inhibition caused by oxygen is the biggest problem in many uses. For example, in the method of blending a thiol compound disclosed in Patent Document 1, there is a problem in storage stability because the reactivity of the thiol group is high. The method of blending a tertiary organic phosphine compound disclosed in Patent Document 2 is considered to suppress curing inhibition by capturing dissolved oxygen and inactive radicals, but captures dissolved oxygen even in a stored state. Therefore, there was a problem with storage stability. The method of blending a compound having a 2,2,6,6-tetramethylpiperidine skeleton disclosed in Patent Document 3 is considered to suppress curing inhibition by capturing dissolved oxygen, but the surface of the coating film However, the effect of suppressing polymerization inhibition was not sufficient, and there was a problem in the curing rate.

Japanese Unexamined Patent Publication No. 2006-154774 JP-A-2015-34245 Japanese Unexamined Patent Publication No. 2016-138161

The present invention is to provide an active energy ray-polymerizable composition which can obtain a cured product having excellent scratch resistance, has good storage stability, and has an excellent curing rate. Another object of the present invention is to provide a cured product of the composition.

The present inventor has completed the present invention as a result of diligent studies to solve the above problems. That is, the present invention contains the compound (a1) represented by the following general formula (1) and / or the compound (a2) represented by the following general formula (2) and the radically polymerizable compound (B). The present invention relates to an active energy ray-polymerizable composition.

[In the general 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 form an alkyl group. Represented, R ¹⁶ and R ¹⁷ each independently represent an alkyl group substituted with hydrogen, at least 3 or more fluorines or a group represented by −R ¹⁸ COOR ¹⁹ , and R ²⁶ represents −COR ²⁷ . , R ²⁷ represent an alkyl group substituted with at least 3 or more fluorines. R ¹⁸ represents an alkylene group and R ¹⁹ represents an alkyl group substituted with at least 3 or more fluorines. However, R ¹⁶ and R ¹⁷ do not become hydrogen at the same time. ]

Further, in the present invention, R ¹¹ and R ²¹ are alkyl groups having 1 to 4 carbon atoms, and R ^{12 to} R ¹⁵ and R ^{22 to} R ²⁵ are independently alkyl groups 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 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 or more fluorines. The present invention relates to the above-mentioned active energy ray-polymerizable composition.

The present invention also relates to a cured product of the above active energy ray-polymerizable 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 the 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. ~ R ⁴⁵ each independently represent 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 , and R ⁴⁶ is represents -COR ^47, R ⁴⁷ represents at least three fluorine substituted alkyl group having 1 to 8 carbon 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 or more fluorines. However, R ³⁶ and R ³⁷ do not become hydrogen at the same time. ]

Further, the present invention relates to a compound represented by the above general formula (3) in which a compound represented by the following general formula (3-1) is reacted with a compound represented by the following general formula (3-2). Regarding the manufacturing method.

[In the general formula (3-1) and the general formula (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 a hydrogen or 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 fluorines. ]

Further, the present invention relates to a compound represented by the above general formula (4) in which a compound represented by the following general formula (4-1) is reacted with a compound represented by the following general formula (4-2). Regarding the manufacturing method.

[In the general formula (4-1) and the general formula (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 are 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 fluorines. ]

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to obtain a cured product having excellent scratch resistance, and it has become possible to provide an active energy ray-polymerizable composition having good storage stability and an excellent curing rate. ..

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 addition, in this 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, which is radically polymerized with a compound (a1) represented by the following general formula (1) and / or a compound (a2) represented by the following general formula (2). It is characterized by containing the sex compound (B). Here, the "active energy ray" means an energy ray in a broad sense capable of providing the energy required for activation for causing a chemical reaction, including ultraviolet rays, visible rays, infrared rays, electron beams, and radiation. .. Although not particularly limited, in one embodiment of the present invention, the active energy ray is preferably a light energy ray containing ultraviolet rays. Hereinafter, each component constituting the resin composition of the present invention will be described in detail.

<Compounds (a1) and (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 capturing dissolved oxygen in the polymerizable composition and thereby suppressing inhibition of the polymerization reaction by oxygen. However, it contributes to the improvement of the reaction speed. Furthermore, by having a fluorine atom having a small surface free energy in the same molecule, the transferability to the surface in a coating film or the like is improved, and it is effective on the coating film surface where the influence of oxygen on the polymerization reaction inhibition is the largest. It is possible to suppress the inhibition of the polymerization reaction by oxygen.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group and the like.
Of these, an alkyl group having 1 to 4 carbon atoms is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is more preferable.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, butoxy and the like.
Of these, an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group and an ethoxy group are more preferable, and a methoxy group is more preferable.

Alkyl groups substituted with at least 3 or more fluorines include 2,2,2-trifluoroethylpropionate group, 2,2,3,3-tetrafluoropropylpropionate 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 fluorines, and more preferably 2,2,3,3,4,5,5-octafluoropentylpropionate. Group, 3,3,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylpropionate group, more preferably 3,3,4,5,5 , 5,6,6,7,7,8,8,8-Tridecafluorooctylpropionate group.

Preferred groups for R ¹⁹ are 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 1H, 1H, 5H-octafluoropentyl group, 1H, 1H, 2H, Examples thereof include a 2H-tridecafluorooctyl group, a 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, a nonadecafluorononanoyl group, and more preferably a nonadecafluorononanoyl group are preferable.

Examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group and the like.
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, but are not limited to, the following compounds.

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

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. As the compound (a1) and the compound (a2), only one kind may be used, or a plurality of kinds may be used in combination.

<Compound represented by the general formula (3), compound represented by the general formula (4)>
Substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and at least 3 or more fluorines, which are groups in the formula in the compound represented by the general formula (3) or the following general formula (4). The alkyl group having 1 to 8 carbon atoms and the alkylene group having 2 to 5 carbon atoms are synonymous with those groups in the general formula (3) or the following general formula (4).
The compound represented by the general formula (3) and the compound represented by the general formula (4) capture the dissolved oxygen in the polymerizable composition by having a 2,2,6,6-tetraalkylpiperidine skeleton. By doing so, the inhibition of the polymerization reaction by oxygen is suppressed, which contributes to the improvement of the reaction rate. Furthermore, by having a fluorine atom having a small surface free energy in the same molecule, the transferability to the surface in a coating film or the like is improved, and it is effective on the coating film surface where the influence of oxygen on the polymerization reaction inhibition is the largest. It is possible to suppress the inhibition of the polymerization reaction by oxygen.

Preferred groups for R ³⁹ are 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 1H, 1H, 5H-octafluoropentyl group, 1H, 1H, 2H, Examples thereof include a 2H-tridecafluorooctyl group, a 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 ⁴⁷ include a pentadecafluoroheptanoyl group, a heptadecafluorooctanoyl group, a nonadecafluorononanoyl group and the like.
Of these, a heptadecafluorooctanoyl group, a nonadecafluorononanoyl group, and more preferably a nonadecafluorononanoyl group are preferable.

<Radical polymerizable compound (B)>
In the present invention, the radically polymerizable compound (B) (hereinafter, may be abbreviated as "compound (B)") is a general term for compounds having one or more radically polymerizable skeletons.

As the compound (B), any compound having one or more radically polymerizable skeletons can be used without particular limitation. Examples of the compound (B) include unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid, salts thereof, esters, acid amides and acid anhydrides, and further. Are (meth) acrylates such as urethane acrylates, acrylonitriles, styrene derivatives, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes, allylates, acid amides, styrenes, and other vinyl compounds. Classes, radically polymerizable cyclic compounds, oligomers, prepolymers and the like, but are not particularly limited thereto. Only one of these may be used, or a plurality of types may be used in combination.

The compound (B) preferably contains bifunctional or higher functional (meth) acrylic acid esters from the viewpoint of polymerization rate. The compound (B) is divided into a compound (b1) having a hydroxyl group and not having a cyclic structure, a compound (b2) having a hydroxyl group and having a cyclic structure, and a compound (b3) having no hydroxyl group.

[Compound having a hydroxyl group and not having a cyclic structure (b1)]
Among the compound (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, mono (meth) acrylic acid ester of cyclohexanedimethanol, 10-hydroxydecyl (meth) acrylate, (meth) The hydroxyl groups such as 12-hydroxylauryl acrylate, ethyl (meth) acrylate-α- (hydroxymethyl), glycerol monofunctional (meth) acrylate, or 2- (acryloyloxy) ethyl 6-hydroxyhexanonate can be used. Contains (meth) acrylic acid ester having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone lactone to the acryloyl group or methacryloyl group-containing compound, and the hydroxyl group-containing α, β-ethylenic unsaturated double bond group. Hydroxyl group-containing aliphatic (meth) acrylic acid esters such as alkylene oxide-added (meth) acrylic acid ester in which alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide are repeatedly added to the compound;

For example, it contains hydroxyl groups such as N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, N-hydroxyhexyl (meth) acrylamide, and N-hydroxyoctyl (meth) acrylamide. (Meta) acrylamides;, etc., but are not particularly limited thereto. Only one of these may be used, or a plurality of types may be used in combination.

[Compound having a hydroxyl group and having a cyclic structure (b2)]
Among the compound (B), examples of the compound (b2) having a hydroxyl group and having a cyclic structure include (meth) acrylate 1,2-cyclohexanedimethanol and (meth) acrylate 1,3-cyclohexanedimethanol. , (Meta) acrylate 1,4-cyclohexanedimethanol, (meth) acrylate 2-hydroxy-3-phenoxymethyl, (meth) acrylate 2-hydroxy-3-phenoxyethyl, (meth) acrylate 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 acrylate, 2- (4-benzoyl-3-hydroxyphenoxy) ethyl acrylate and other (meth) acrylic acid esters having a cyclic structure other than a heterocycle with a hydroxyl group;

For example, 2-hydroxy-4- {2- (meth) acryloyloxy} ethoxybenzophenone, 2-hydroxy-4- {2- (meth) acryloyloxy} butoxybenzophenone, 2,2'-dihydroxy-4- {2- Hydroxy group-containing benzophenone-based (meth) acrylic acid 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 Hydroxy-containing benzotriazole-based (meth) acrylic acid esters such as -3'-tert-butyl-5'-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole;

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) acryloyloxyethoxy}] -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 Hydroxy group-containing triazine (meth) acrylic acid esters such as, etc.;, etc., but are not particularly limited thereto. Only one of these may be used, or a plurality of types may be used in combination.

[Compound having no hydroxyl group (b3)]
Among the compounds (B), examples of the compound (b3) having no hydroxyl group include (meth) acrylic acid, 2-carboxyethyl (meth) acrylic acid, 2-carboxypropyl (meth) acrylic acid, and (meth) acrylic. Acid 3-carboxypropyl, (meth) acrylic acid 4-carboxybutyl, (meth) acrylic acid dimer, maleic acid, fumaric acid, monomethylmaleic acid, monomethylfumaric acid, aconitic acid, sorbic acid, silicic acid, α-chloro Sorbic acid, glutaconic acid, citraconic acid, mesaconic acid, itaconic acid, tigric acid, angelica acid, senesioic acid, crotonic acid, isoccrotonic acid, mucobromic acid, mucochloric acid, sorbic acid, muconic acid, aconite acid, penicic acid, geranoic acid , Citroneric acid, 4-acrylamide butanoic acid, 6-acrylamide hexanoic acid, 2- (meth) acryloyloxyethyl succinate, mono (meth) acrylic acid ω-carboxypolycaprolactone ester, etc. Polylactone-based (meth) acrylic acid ester having a group at the end, alkylene oxide-added succinic acid having a carboxyl group at the end, to which alkylene oxides such as ethylene oxide and propylene oxide are repeatedly added, and (meth) acrylic acid Acrylic acid group-containing aliphatic acrylic acid group or methacrylic acid group-containing carboxylic acid containing carboxyl group such as ester with and its acid anhydride;

For example, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropylphthalate, 2- (meth) acryloyloxybutylphthalate, 2- (meth) acryloyl. Acryloyl group or acryloyl group-containing carboxylic acids having a carboxyl group-containing alicyclic or aromatic ring such as oxyhexylphthalate, 2- (meth) acryloyloxyoctylphthalate, 2- (meth) acryloyloxydecylphthalate and their acid anhydrides. ;

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--quinolin Carbohydrazide (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) acrylic. (Meta) acrylic acid esters having primary and / or secondary amino groups such as N-tributylaminoethyl acid, tetramethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl acrylate;

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

For example, it has a primary and / or secondary amino group such as monomethylaminoethyl (meth) acrylamide, monoethylaminoethyl (meth) acrylamide, monomethylaminopropyl (meth) acrylamide, and monoethylaminopropyl (meth) acrylamide. (Meta) acrylamides;

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

Heterocyclic acryloyl groups of maleimide derivatives having both nitrogen and oxygen atoms, such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc. Or maleimide 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 , (Meta) benzyl acrylate, (meth) acrylate iso-bornyl, (meth) acrylate phenyl, (meth) acrylate 2-phenoxyethyl, (meth) acrylate 2-oxo-1,2-phenylethyl, 2-Oxo-1,2-diphenylethyl (meth) acrylic acid, 1-naphthyl (meth) acrylic acid, 2-naphthyl (meth) acrylic acid, 1-naphthylmethyl (meth) acrylic acid, 1 (meth) acrylic acid -Anthryl, 2-anthryl (meth) acrylate, 9-anthryl (meth) acrylate, 9-anthrylmethyl (meth) acrylate, 2-methyladamantyl-2-yl (meth) acrylate, (meth) acrylic Dicyclopentanyl acid, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-ethyladamantyl-2-yl (meth) acrylate, 2-n-propyl (meth) acrylate Adamanthyl-2-yl, 2-isopropyl (meth) acrylate, adamantyl-2-yl, 1- (meth) acrylate-1- (adamantan-1-yl) -1-methylethyl, 1- (meth) acrylate 1- (adamantan-) 1-Il) -1-ethylethyl, 1- (meth) acrylate 1- (adamantan-1-yl) -1-methylpropyl, (meth) acrylate 1- (adamantan-1-yl) -1-ethylpropyl, ( Meta) Acrylic Acid-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] Nona-2-yl, (Meta) Acrylic Acid-5-oxo-4-oxa-tricyclo [5. 2.1.0 ^3,8 ] Deca-2-yl, dihydro-α-terpinyl (meth) acrylic acid, -6-oxo-7-oxa-bicyclo (meth) acrylic acid [3.2.1] octa- 2-yl, (meth) acrylic acid-7-oxo-8-oxa-bicyclo [3.3.1] octa-2-yl, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyp Lopilphthalate, 2- (meth) acryloyloxybutyl phthalate, 2- (meth) acryloyloxyhexyl phthalate, 2- (meth) acryloyloxyoctyl phthalate, 2- (meth) acryloyloxydecyl phthalate, 2- (meth) acryloyl (Meta) acrylic acid cyclic esters such as oxyethyl hexahydrophthalate;

For example, N- (4-carbamoylphenyl) (meth) acrylamide, β- (2-furyl) (meth) acrylamide, 2,3-bis (2-furyl) acrylamide, N- (9H-fluoren-2-yl). (Meta) 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) (Meta) 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) acryloyloxyethyl dimethylbenzylammonium-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 acryloyloxyethyl phosphate;

For example, di (meth) acrylic acid tricyclodecanedihydroxymethyl, di (meth) acrylic acid tricyclodecanedihydroxymethyl dicaprolactonate, di (meth) acrylic acid 1,2-adamantandiol, di (meth) acrylic acid 1 , 3-adamantandiol, di (meth) acrylate 1,4-adamantandiol, di (meth) acrylate tricyclodecanyl dimethylol, di (meth) acrylate dicyclopentanyl, 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 Tetraethylene oxide adduct of propyl) benzene, di (meth) acrylic acid-2,2-bis (hydroxyphenyl) propane, tetraethylene oxide adduct of di (meth) acrylic acid 2,2-bis (hydroxyphenyl) methane , Di (meth) acrylic acid-4,4'-sulfonyl diphenol tetraethylene oxide adduct, di (meth) acrylic acid-hydrated 2,2-bis (hydroxyphenyl) propane tetraethylene oxide adduct, di (Meta) acrylic acid-hydrated 2,2-bis (hydroxyphenyl) methane tetraethylene oxide adduct, di (meth) acrylic acid-hydrated 2,2-bis (hydroxyphenyl) propane, di (2-methyl) ) Propenic acid-hydrated 2,2-bis (hydroxyphenyl) methane, di (meth) acrylic acid-2,2-bis (hydroxyphenyl) propane tetraethylene oxide adduct-dicaprolactonate, di (meth) Bifunctional (meth) acrylic acid cyclic esters such as tetraethylene oxide adduct of acrylic acid-2,2-bis (hydroxyphenyl) methane-dicaprolactonate;

Heterocyclic (meth) acrylic acid esters containing nitrogen atoms, such as pentamethylpiperidinyl (meth) acrylate, 4- (pyrimidine-2-yl) piperazin-1-yl (meth) acrylate;

For example, imide (meth) acrylate, 2- (4-oxazoline-3-yl) ethyl (meth) acrylate, di (meth) acrylic acid ethoxylated isocyanuric acid, tri (meth) acrylic acid ethoxylated isocyanuric acid, ε-caprolactone. A heterocyclic structure containing oxygen atoms in addition to nitrogen atoms such as modified tris- (2-acryloyloxyethyl) isocyanurate, di (meth) acrylic acid isocyanuric acid ethylene oxide modification, and tri (meth) acrylic acid isocyanuric acid ethylene oxide modification. Has (meth) acrylic acid esters;

For example, 4-acryloyl morpholine, 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) acrylate. 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 acrylate, n-nonyl (meth) acrylate, iso-nonyl (meth) acrylate, decyl (meth) acrylate, (meth) ) Alkyl esters of (meth) acrylic acid 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-Chlor 2-propenyl (meth) acrylate, 3-Chlor 2-propenyl (meth) acrylate, 2- (2-propenyloxy) ethyl (meth) acrylate, 2-2-propenyl (meth) acrylate Propenyl lactyl, (meth) acrylic acid 3,7-dimethylocta-6-ene-1-yl, (meth) acrylic acid (E) -3,7-dimethylocta-2,6-dien-1-yl, (Meta) acrylic acid esters containing further unsaturated groups such as (meth) acrylateyl, cinnamyl (meth) acrylate, and (meth) vinyl 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-perfluoroethyl ethyl (meth) acrylate, 2-per (meth) acrylate Fluoromethyl-2-perfluoroethylmethyl, triperfluoromethylmethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, (meth) acrylic propenic acid (Meta) acrylic acid perfluoroalkyl esters such as 2-perfluorodecylethyl, 2-perfluorohexadecylethyl (meth) acrylic acid;

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 acid esters such as ethyl, 3-butoxyethyl (meth) acrylic acid, and 4-butoxyethyl (meth) acrylic acid;

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 , (Meta) acrylic acid (ethoxycarbonyl) hexyl, (meth) acrylic acid (ethoxycarbonyl) octyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) ethyl, (meth) acrylic acid 2- (ethoxycarbonyloxy) propyl , (Meta) Acrylic Acid 2- (ethoxycarbonyloxy) Butyl, (Meta) Acrylic Acid 2- (ethoxycarbonyloxy) Hexyl, (Meta) Acrylic Acid 2- (ethoxycarbonyloxy) Octyl, (Meta) Acrylic Acid 2- (Propoxycarbonyloxy) ethyl, (meth) acrylate 2- (butoxycarbonyloxy) ethyl, (meth) acrylate 2- (butoxycarbonyloxy) butyl, (meth) acrylate 2- (octyloxycarbonyloxy) ethyl, (Meta) Acrylic Acid 2- (Octyloxycarbonyloxy) An aliphatic (meth) acrylic acid ester having one carbonyl group such as butyl;

For example, 2-oxobutanoylethyl (meth) acrylate, 2-oxobutanoylpropyl (meth) acrylate, 2-oxobutanoylbutyl (meth) acrylate, 2-oxobutanoylhexyl (meth) acrylate, 2-oxobutanoyloctyl (meth) acrylate, 2-oxobutanoyldecyl (meth) acrylate, 2-oxobutanoyldodecyl (meth) acrylate, 3-oxobutanoylethyl (meth) acrylate, (meth) ) 3-oxobutanoylpropyl acrylate, 3-oxobutanoylbutyl (meth) acrylate, 3-oxobutanoylhexyl (meth) acrylate, 3-oxobutanoyloctyl (meth) acrylate, (meth) acrylic 3-oxobutanoyldecyl acid, 3-oxobutanoyldodecyl (meth) acrylic acid, 4-cyanooxobutanoylethyl (meth) acrylic acid, 4-cyanooxobutanoylpropyl (meth) acrylic acid, (meth) acrylic Acid 4-cyanooxobutanoylbutyl, (meth) acrylic acid 4-cyanooxobutanoylhexyl, (meth) acrylic acid 4-cyanooxobutanoyloctyl, (meth) acrylic acid 2,3-di (oxobutanoyl) Propyl, 2,3-di (oxobutanoyl) butyl (meth) acrylic acid, 2,3-di (oxobutanoyl) hexyl (meth) acrylic acid, 2,3-di (oxobutanoyl) (meth) acrylic acid ) An aliphatic (meth) acrylic acid ester having two carbonyl groups such as octyl;

For example, (meth) acrylic acid-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] nona-2-yl, (meth) acrylic acid-10-methoxycarbonyl -5-oxo-4-oxa-tricyclo [5.2.1.0 ^3,8 ] nona-2-yl, (meth) acrylic acid-4-methoxycarbonyl-6-oxo-7-oxa-bicyclo [3] .2.1] It has a carbonyl group such as octa-2-yl, (meth) acrylate-4-methoxycarbonyl-7-oxo-8-oxa-bicyclo [3.3.1] octa-2-yl ( Meta) Acrylic acid cyclic esters;

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

For example, acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, acid phosphooxybutyl (meth) acrylate, -3-chloro-2-acid phosphooxyethyl (meth) acrylate, ( Meta) Acrylic acid-3-chloro-2-acid Phosphonoxypropyl, (Meta) Acrylic acid-3-chloro-2-acid Phosphonoxybutyl, (Meta) Acrylic acid Acid Phosphonoxyethylene oxide (Number of moles of ethyleneoxide added: Phosphonate group-containing (meth) acrylic acid esters such as 4 to 10), (meth) acrylic acid acid phosphooxypropylene oxide (number of moles added with propylene oxide: 4 to 10);

For example, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltripropoxysilane, 3- (meth) acryloyloxypropyltributoxysisilane. , 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropylethyldimethoxysilane, 3- (meth) acryloyloxypropylbutyldimethoxysilane, 3- (Meta) acryloyloxypropylethyl dipropoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, (Meth) acrylic acid esters containing alkoxysilyl groups such as 3- (meth) acryloyloxypropyltripropoxysilane;

For example, metal salts and ammonium of (meth) acrylic acid esters containing a sulfonyl group such as (meth) acryloyloxydimethylethylammonium ethyl sulfate, (meth) acryloylaminopropyltrimethylammonium sulfate, and (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. Dipropylene oxide of (meth) acrylic acid, tripropylene oxide of di (meth) acrylic acid, polypropylene oxide of di (meth) acrylic acid, butene oxide of di (meth) acrylic acid, penten oxide of di (meth) acrylic acid, di (meth) 2,2-Dimethylpropyl Acrylic Acid, Di (Meta) Acrylic Acid Hydroxypivalyl hydroxypivalate, Di (Meta) Acrylic Acid Hydroxy Pivalyl Hydroxypivalate Dicaprolactonate, Di (Meta) Acrylic Acid 1,6-hexane Diol, di (meth) acrylic acid 1,2-hexanediol, 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-Decandiol, 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-hexadecanediol, di (meth) acrylic acid 2-methyl-2,4-pentanediol, di (meth) acrylic acid 3-methyl-1,5-pentanediol, di (meth) acrylic acid 2-Methyl-2-propyl-1,3-propanediol, di (meth) acrylic acid 2,4-dimethyl-2,4-pentanediol, di (meth) acrylic acid 2,2-diethyl-1,3- Propanediol, di (meth) acrylic acid 2,2,4-trimethyl-1,3-pentanediol, dimethylol octane di (meth) acrylic acid, 2-ethyl-1,3-hexanediol di (meth) acrylic acid , Di (meth) acrylic acid 2,5-dimethyl-2,5-hexanediol, di (meth) acrylic acid 2-methi Lu-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2,4-diethyl-1,5-pentanediol di (meth) acrylate, di 2-Methyl-2-propyl-1,3-propanediol (meth) acrylic acid, 2,4-dimethyl-2,4-pentanediol di (meth) acrylic acid, 2,2-diethyl di (meth) acrylic acid -1,3-Propanediol, di (meth) acrylate 2,2,4-trimethyl-1,3-pentanediol, dimethylol octane di (meth) acrylate, 2-ethyl-1 di (meth) acrylate , 3-Hexanediol, di (meth) acrylic acid 2,5-dimethyl-2,5-hexanediol, di (meth) acrylate 2-butyl-2-ethyl-1,3-propanediol, di (meth) Bifunctional (meth) acrylic acid esters such as 2,4-diethyl-1,5-pentanediol acrylic acid and 1,1,1-trishydroxymethylethane di (meth) acrylic acid;

For example, tri (meth) acrylic acid 1,2,3-propanetriol, tri (meth) acrylic acid 2-methylpentane-2,4-diol, tri (meth) acrylic acid 2-methylpentane-2,4-diol. Tricaprolactonate, tri (meth) acrylic acid 2,2-dimethylpropane-1,3-diol, tri (meth) acrylic acid trimethylol hexane, tri (meth) acrylic acid trimethylol octane, 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, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxylated tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetra (meth) acrylate 2, 2-Bis (Hydroxymethyl) 1,3-Propanediol, Tetra (Meta) Acrylic Acid 2,2-Bis (Hydroxymethyl) 1,3-Propandiol Tetracaprolactonate, Tetra (Meta) Acrylic Acid Di1, 2,3-Propanetriol, di2-methylpentane tetra (meth) acrylate-2,4-diol, di2-methylpentane tetra (meth) acrylate-2,4-diol tetracaprolactonate, tetra ( Di2,2-dimethylpropane-1,3-diol (meth) acrylate, ditrimethylolbutane tetra (meth) acrylate, ditrimethylolhexane tetra (meth) acrylate, ditrimethylol octane tetra (meth) acrylate, tetra (meth) Di 2,2-bis (hydroxymethyl) 1,3-propanediol meta) acrylic acid, di-2,2-bis (hydroxymethyl) 1,3-propanediol hexa (meth) acrylic acid, hexa (meth) acrylic acid Tri 2,2-bis (hydroxymethyl) 1,3-propanediol, hepta (meth) acrylate Tri 2,2-bis (hydroxymethyl) 1,3-propanediol, octa (meth) acrylate tri 2,2 -Polyfunctional (meth) acrylic acid esters such as bis (hydroxymethyl) 1,3-propanediol and hepta (meth) acrylic acid di2,2-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. (Meta) acrylamide, N-tert-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N-nonyl (meth) acrylamide, N-tricosyl (meth) acrylamide, N-nonadecil (Meta) acrylamide, N-docosyl (meth) acrylamide, N-methylene (meth) acrylamide, N-tridecyl (meth) acrylamide, N- (5,5-dimethylhexyl) (meth) acrylamide, crotonamide, maleeamide, Fumalamide, mesaconamide, citraconamide, itaconamide, 2-methylpropa-2-enoylamine, N, N-dimethyl (meth) acrylamide, N, N-diethyl- (meth) acrylamide, N- [3- (N', N' -Dimethylamino) propyl]-(meth) acrylamide, N- (dibutylaminomethyl) (meth) acrylamide, N-vinylmethaneamide, N-vinylacetamide and other aliphatic (meth) acrylamides;

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-iso Propoxyethyl (meth) acrylamide, N-isopropoxypropyl (meth) acrylamide, N-isopropoxybutyl (meth) acrylamide, N-isopropoxyhexyl (meth) acrylamide, N-isopropoxyoctyl (meth) acrylamide, N-butoxy Methyl (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-isobutoxyhexyl (meth) acrylamide , N-isobutoxyoctyl (meth) acrylamide, N- (pentoxymethyl) (meth) acrylamide, N-1-methyl-2-methoxyethyl (meth) acrylamide, N, N-di (methoxymethyl) meta) acrylamide , N-alkoxy group-containing (meth) acrylamides such as 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 thereof include, but are not limited to, acryloyl group or methacryloyl group-containing compounds having a nitrile group such as (meth) acrylonitrile and 2-cyanoethyl (meth) acrylate.

Further, for example, o-di (meth) allyl bisphenol A, hydrogenated hydrogenated bisphenol A having an aromatic ring structure, and the like are also included in compound (b3) if they have one or more radically polymerizable skeletons. Only one of these may be used, or a plurality of types may be used in combination.

<Cationopolymerizable compound (C)>
In one embodiment of the polymerizable composition of the present invention, the polymerizable composition contains a cationically polymerizable compound (C) (hereinafter, may be abbreviated as “Compound (C)”) in addition to the above-mentioned essential components. It may be.

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

Among the cyclic heterocompounds (c), an epoxy group-containing compound (c1) which is a cyclic heterocompound having a 3-membered cyclic ether group, an oxetanyl group-containing compound (c2) which is a 4-membered ring ether, and a cyclic ether having a 5-membered ring or more. There is a compound (c3) and a compound (c4) having two or more oxygen or a heterogroup other than oxygen.

[Epoxy group-containing compound (c1), which is a cyclic heterocompound having a 3-membered cyclic ether group]
Examples of the epoxy group-containing compound (c1) include oxylan, methyloxylan, phenyloxylane, 1,2-diphenyloxylan, methylideneoxylan, oxylanylmethyl, oxylanylmethanol, oxylanecarboxylic acid, and (chloromethyl) oxylane. , (Bromomethyl) oxylane, oxylanyl acetonitrile, 2,2'-(dimethylmethylene) bis [(p-phenylene) oxymethylene] bisoxylane, 2,2'-[methylenebis (2,1-phenyleneoxymethylene)] Oxylan compounds such as bisoxylane, or epoxy group-containing compounds in which the hydrogen atom of the oxylan ring such as glycidyl ether, glycidyl ester, and glycidylamine is substituted with a methylene group or a methine group;

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

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 and 4-ethylphenyl7-oxabicyclo [4.1.0] heptane. Examples thereof include epoxy group-containing compounds.

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

[Cyclic ether compound with 5 or more membered rings (c3)]
Examples of the cyclic ether compound (c3) having a 5-membered ring or more include 2-methyltetrahydrofuran, 2,5-diethoxytetrahydrofuran, tetrahydrofuran-2,2-dimethanol 3-methyl-2,4 (3H, 5H)-. Tetrahydrofuran and the like can be mentioned.

[Compound having two or more oxygens or heterogroups other than oxygen (c4)]
Examples of the compound (c4) having two or more oxygen or a heterogroup 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 the epoxy group-containing compound (c1) or the oxetanyl group-containing compound (c1) is not particularly limited. c2) is preferable. Further, the epoxy group-containing compound (c1) or the oxetanyl group-containing compound (c2) has a large steric strain and is likely to cause a nucleophilic ring-opening reaction. Therefore, since the crosslink density can be improved during polymerization, the cohesive force is likely to be 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 advancing the polymerization reaction by irradiation with various activation energy rays. However, the above-mentioned polymerizable composition may contain an active energy ray polymerization initiator (E) (hereinafter, may be abbreviated as "initiator (E)"), if necessary. The polymerization reaction can be promoted by using the initiator (E). 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 the initiator (E). In the present invention, as the initiator (E), a compound arbitrarily selected from known compounds as an active energy ray polymerization initiator can be used.

Among the initiators (E), the photoradical generator (e1) includes, for example, 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthfluorenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-. Chlorobenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2 Examples thereof include −methyl-1-phenylpropan-1-one, 4-thioxanthone, camphorquinone, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one.

As commercially available products, for example, 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), DaroCure-1173 (manufactured by Merck & Co., Ltd.), EzaCure KIP150, and TZT (manufactured by Nippon Kayaku Hegner), KayaCure BMS, and KayaCure DMBI (manufactured by Nippon Kayaku Co., Ltd.).

When the cationically polymerizable compound (C) or the epoxy-modified vegetable oil is used as the cationically polymerizable compound, it is preferable to contain the photoacid generator (e2) among the initiators (E). Examples of the photoacid generator (e2) include sulfonium salts such as UVACURE1590 (manufactured by Daicel Cytec) and CPI-110P (manufactured by San-Apro), IRGACURE250 (manufactured by Ciba Specialty Chemicals), and WPI-113 (manufactured by Ciba Specialty Chemicals). Examples include iodonium salts (manufactured by Wako Junyaku Co., Ltd.) and RP-2074 (manufactured by Rhodia Japan), and when used in combination, polymerization cross-linking progresses and curing with excellent durability against heat and humidity It is preferable because it forms an object.

In the present invention, the above-mentioned compounds can be used alone or in combination of two or more as the initiator (E). From the viewpoint of reactivity, the blending 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 being 100 parts by mass. Is the range of.

The polymerizable composition of the present invention is substantially free of organic solvents. The polymerizable composition preferably does not contain any organic solvent, but the initiator (E) is often poorly soluble in the polymerizable component. Therefore, a small amount of organic solvent may be contained 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 5 parts by mass or less.

Further, in order to improve the performance of the initiator (E), an active energy ray sensitizer may be used in combination. Examples of active energy ray sensitizers include benzophenone derivatives, unsaturated ketone derivatives such as chalcone derivatives and dibenzalacetone, and benzyl and camphorquinone. Polymethine dyes such as 2-diketone derivative, benzoin derivative, fluorene derivative, naphthoquinone derivative, anthraquinone derivative, xanthene derivative, thioxanthene derivative, xantone derivative, thioxanthone derivative, coumarin derivative, ketocoumarin derivative, cyanine derivative, merocyanine derivative, oxonoal derivative, etc. , Acridine derivatives, azine derivatives, thiadine derivatives, oxazine derivatives, indolin derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, Phthalocyanin derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrrium derivative, tetraphyllin derivative, anulene derivative, spiropyrane derivative, spiroxazine derivative, thiospiropyrane derivative, metal Alene complexes, organic ruthenium complexes, etc. are mentioned, and more specific examples are Nobu Okawara et al., "Dye Handbook" (1986, Kodansha), Nobu Okawara et al., "Chemistry of Functional Dyes" (1981, Sea). The pigments and sensitizers described in "Special Functional Materials" (1986, CMC), edited by MC), Chuzaburo Ikemori et al., Are not limited to these, and are not limited to these, and are also used in the ultraviolet to near-infrared region. Examples thereof include dyes and sensitizers that absorb the light of the above, and two or more of these may be used in any ratio as required.

Among the sensitizers described above, the thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 1-chloro-4-propoxythioxanthone. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4'-dimethylbenzophenone, 4,4'-dimethoxybenzophenone, and 4,4'-bis. Examples of coumarins include (diethylamino) benzophenone, and examples of coumarins include coumarin 1, coumarin 338, and coumarin 102. Examples of coumarins include 3,3'-carbonylbis (7-diethylaminocoumarin) and the like. However, it is not limited to these.

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

For example, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltriacetoxysilane, triltrimethoxysilane, trilltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiisopropoxysilane, diphenyldi. Aryl-based alkoxysilanes such as acetoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, methylphenyldiisopropoxysilane, and methylphenyldiacetoxysilane;

For example, dimethoxymethylsilane, tris (dimethylamino) silane and the like can be mentioned.

Further, as the silane compound (F), it is possible to use a commercially available product, and it is also possible to use an oligomeric silane obtained by hydrolyzing and condensing a mixture of two or more kinds of silanes to form an oligomer. include. The silane compound (F) can also be used alone or as a mixture of two or more kinds.

<Antioxidant (G)>
The polymerizable composition in the present invention may further contain an antioxidant. By containing the antioxidant (G), it is possible to suppress the coloration of the cured resin product over time after the active energy ray polymerization.
Examples of the antioxidant include phenolic antioxidants such as Adekastab AO-50 and Adekastab AO-80 (manufactured by Adeka), and phosphorus such as Adekastab PEP-8 (manufactured by BASF) and IRGAFOS168 (manufactured by BASF). Commercially available products such as a sulfur-based antioxidant and a sulfur-based antioxidant such as IRGANOX-PS-800FD (manufactured by BASF) can be mentioned, but the present invention is not limited thereto.

<Color material (J)>
The polymerizable composition of the present invention may contain a coloring material (J) in addition to the above components. In the present invention, the coloring 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 functions such as thermal properties, electrical properties, and optical properties depending on the dyes and pigments contained.

The coloring material (J) is used by dispersing dyes and pigments in a dispersion resin at a high concentration. 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.
For example, organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, hanza ero, benzidine ero, and pyrazolone red.
Soluble azo pigments such as Ritol Red, Helio Bordeaux, Pigment Scarlet, Permanent Red 2B,
Derivatives from vat dyes such as alizarin, indigo maroon, thioindigo maroon,
Phthalocyanine-based organic pigments such as phthalocyanine blue and phthalocyanine green,
Quinacridone organic pigments such as quinacridone red and quinacridone magenta,
Perylene-based organic pigments such as perylene red and perylene scarlet,
Isoindolinone-based organic pigments such as Isoindolinone Yellow and Isoindolinone Orange,
Pyranthron organic pigments such as Pyranthron red and Pyranthron orange, thioindigo organic pigments, condensed azo organic pigments, benzimidazolone organic pigments
Kinophthalone-based organic pigments such as quinophthalone yellow,
Isoindoline organic pigments such as isoindoline yellow,
Examples of other pigments include organic pigments such as flavanthrone ero, acylamide ero, nickel azo ero, copper azomethine ero, perinone orange, anthrone orange, dianthraquinonyl red, and dioxazine violet.

For example, examples of the dye include an azo dye, a rhodamine dye, a quinoline dye, a thiazine dye, a thiazole dye, a xanthene dye, and a niglosin dye.
Any of these dye derivatives can be used without any particular problem.

Among the coloring materials (J), a general acrylic resin is used as the dispersion resin, and in some cases, a surfactant, the above compound (B), compound (C), or the like is also used in combination. The acrylic resin does not have a radically polymerizable skeleton or a cationically polymerizable skeleton, and is not included in the compound (B) and the compound (C).
The dispersed 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. When the compound (B) or the compound (C) is used in combination, it is preferably used in the range of 100 to 800 parts by mass in terms of non-volatile content with respect to 100 parts by mass of the dye or pigment.

If necessary, a polar resin can be used to stabilize the dispersion of dyes and pigments.
Examples of such polar resins include polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, poly (meth) acrylic acid, (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymer, and styrene-maleic acid copolymer. , 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 -A hydrophilic vinyl-based copolymer resin 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, in which the entire resin is balanced in polarity / non-polarity by introducing a polar group;
Cellulose derivatives such as methyl cellulose, ethyl cellulose, propyl cellulose, ethyl methyl cellulose, hydroxyalkyl cellulose, hydroxypropyl methyl cellulose, carboxymethyls cellulose, alkali metal carboxymethyl cellulose, alkali metal cellulose sulfate, cellulose graft polymer;
Polypeptides such as polyglutamic acid and polyaspartic acid;
Long-chain polyaminoamide and polar acid ester salt, long-chain polyaminoamide and high-molecular-weight acid ester salt, naphthalene sulfonic acid formarin condensate salt, stearylamine acetate and other amide ester salts;
Etc., but are not particularly limited to these. These can be used alone or in combination of two or more.

Examples of the polar resin commercially available as the dispersion resin include "Anti-Terra-U (polyaminoamide phosphate)", "Anti-Terra-203 / 204 (high molecular weight polycarboxylic acid salt)" and "Abyssia". Disperbyk-101 (polyaminoamide phosphate and acid ester), 107 (hydroxyl-containing carboxylic acid ester), 110, 111 (acid group-containing copolymer), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (high molecular weight 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 type) "," Lactimon (long-chain amine, unsaturated acid polycarboxylic acid and silicon) ".
In addition, "Fuka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766", "Fuka Polymer 100 (modified polyacrylate), 150 (aliphatic)" manufactured by Efka CHEMICALS. System-modified polymer), 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylate), 745 (copper phthalocyanine), Kyoeisha Chemical Co., Ltd. "Floren TG-710 (urethane oligomer)," Fronon SH-290, SP-1000 "," Polyflow No. 50E, No. 300 (acrylic copolymer) ", Kusumoto Kasei Co., Ltd." Disparon KS-860, 873SN, 874 (polymer dispersant), # 2150 ( (Acrylic polyvalent carboxylic acid), # 7004 (polyether ester type) ”.

<Additive (Q)>
In the resin composition of the present invention, various additives (Q) can be appropriately blended in addition to the above-mentioned components as long as the effects of the present invention are not impaired. For example, an organic or inorganic filler is blended from the viewpoints of reducing polymerization curing shrinkage rate, reducing thermal expansion rate, improving dimensional stability, improving elastic modulus, adjusting viscosity, improving thermal conductivity, improving strength, improving toughness, improving coloring, etc. it can. As such a filler, a polymer, ceramics, metal, metal oxide, metal salt or the like can be used, and the shape is not particularly limited such as particulate or fibrous. In addition, when blending the above polymer, as a filler such as a flexibility imparting agent, a plasticizer, a flame retardant agent, a storage stabilizer, a thixotropy imparting agent, a dispersion stabilizer, a fluidity imparting agent, a defoaming agent, etc. It is also possible to dissolve, semi-dissolve or micro-disperse in the polymerizable composition as a polymer blend or polymer alloy.

<Manufacturing of active energy ray-polymerizable composition>
The polymerizable composition of the present invention contains the above-mentioned compound (A) and compound (B) as essential components, and further comprises compound (C), initiator (E), silane compound (F), and antioxidant, if necessary. It can be produced by blending the agent (G), the colorant (J) and various other 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 compound (A) in 100 parts by mass of the total amount of the polymerizable composition, and 1 to 7 parts by mass of compound (A). It is more preferable to contain it. If the amount of the compound (A) is 0.1 part by mass or more in 100 parts by mass of the total amount of the polymerizable composition, the curing rate is increased by suppressing the inhibition of curing by dissolved oxygen in the polymerizable composition during photocuring. Improvement can be expected, sufficient cohesive force can be easily obtained, and a cured product having excellent toughness can be expected to be obtained.

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 equipped with a decompression device, a kneader, or a solver. Good. The temperature at the time of stirring and mixing is usually preferably set to 10 to 60 ° C.

The polymerizable composition of the present invention can be used in any of liquid, paste and film forms.
The polymerizable composition in the present invention preferably contains substantially no organic solvent, but may also contain an organic solvent. For example, 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, and water are further added. The viscosity of the polymerizable composition can be adjusted, or the polymerizable composition can be heated to reduce the viscosity.

Hereinafter, specific examples of the present invention will be described together with comparative examples, but the present invention is not limited to the following examples. Further, unless otherwise specified, in Examples and Comparative Examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

All ¹ H-NMR measurements in the examples were performed in deuterated chloroform using JEM-ECX400P manufactured by JEOL Ltd. All IR measurements were performed using a Spectrum One manufactured by PerkinElmer. All elemental analytical measurements in the examples were performed using a 2400 CHN manufactured by PerkinElmer.

<Manufacturing of colored material (J) dispersion>
[Manufacturing Examples 1 and 2]
The compound (B) and the dispersed resin are stirred, and after confirming that the dispersed resin is completely dissolved, the pigment is added, and the mixture is stirred with a high-speed mixer or the like until it becomes uniform, and then the obtained mill base is mixed with a horizontal sand mill. It was produced by dispersing for about 2 hours. Table 1 shows the composition (numerical values represent parts by mass) of the produced color material (J) dispersion (pigment dispersion). In Table 1, blanks mean no compounding.

<Example>
<Synthesis of compounds (a1) and (a2)>
[Synthesis Examples 1-27]
Although the present invention will be specifically described with reference to synthetic examples, the present invention is not limited to the following synthetic examples.

In a reaction vessel equipped with a stirrer and a thermometer, 2 parts of 4-amino-1,2,2,6,6-pentamethylpiperidine and 1.8 parts of 2,2,2-trifluoroethyl acrylate were charged, and the temperature was 23 ° C. Was stirred with. The reaction was carried out overnight at 23 ° C., and it was confirmed by ^{1 1} H-NMR that the reaction was completed, and 3.8 parts of compound (1-1) was obtained. The structure of the obtained compound (1-1) was confirmed by ^{1 1} H-NMR, IR and elemental analysis. The ¹ H-NMR spectrum of compound (1-1) is shown in FIG. 1, the IR spectrum is shown in FIG. 2, and the elemental analysis values are shown in Table 2.

In a reaction vessel equipped with a stirrer and a thermometer, 2 parts of 4-amino-1,2,2,6,6-pentamethylpiperidine and 1.6 parts of 1,1,1-trifluoromethylacrylate were charged, and the temperature was 23 ° C. Was stirred with. After that, 3.6 parts of compound (1-2) 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 and 2.2 parts of 2,2,3,3-tetrafluoropropyl acrylate were charged. The mixture was stirred at 23 ° C. After that, 4.2 parts of compound (1-3) 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, 3.4 parts of 1H, 1H, 5H-octafluoropentyl acrylate were charged, and the temperature was 23 ° C. Was stirred with. After that, 5.4 parts of compound (1-4) 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, 4.9 parts of 1H, 1H, 2H, 2H-tridecafluorooctatyl acrylate It was charged and stirred at 23 ° C. After that, 6.9 parts of compound (1-5) 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-pentamethylpiperidin, and 5.5 parts of 1H, 1H, 2H, 2H-pentadecafluorononyl acrylate were charged. , 23 ° C. After that, 7.5 parts of compound (1-6) 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 and 3.6 parts of 2,2,2-trifluoroethyl acrylate were charged, and the temperature was 23 ° C. Was stirred with. After that, 5.6 parts of compound (1-7) 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 and 3.3 parts of 1,1,1-trifluoromethylacrylate were charged, and the temperature was 23 ° C. Was stirred with. After that, 5.3 parts of compound (1-8) 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 and 4.4 parts of 2,2,3,3-tetrafluoropropyl acrylate were charged. The mixture was stirred at 23 ° C. After that, 6.4 parts of compound (1-9) 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, 6.7 parts of 1H, 1H, 5H-octafluoropentyl acrylate were charged, and the temperature was 23 ° C. Was stirred with. After that, 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-tridecafluorooctatyl acrylate It was charged and stirred at 23 ° C. After that, 11.8 parts of compound (1-11) 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, 11 parts of 1H, 1H, 2H, 2H-pentadecafluorononyl acrylate were charged, and 23. Stirred at ° C. After that, 13 parts of compound (1-12) 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-ethyl-2,2,6,6-pentamethylpiperidine, 1H, 1H, 2H, 2H-tridecafluorooctatyl acrylate 4.5 The parts were charged and stirred at 23 ° C. After that, 6.5 parts of compound (1-13) 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-butyl-2,2,6,6-pentamethylpiperidine, 1H, 1H, 2H, 2H-tridecafluorooctatyl acrylate 3.9 The parts were charged and stirred at 23 ° C. After that, 5.9 parts of compound (1-14) 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-methoxy-2,2,6,6-pentamethylpiperidine, 1H, 1H, 2H, 2H-tridecafluorooctatyl acrylate 4.5 The parts were charged and stirred at 23 ° C. After that, 6.5 parts of compound (1-15) 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-ethoxy-2,2,6,6-pentamethylpiperidine, 1H, 1H, 2H, 2H-tridecafluorooctatyl acrylate 4.2 The parts were charged and stirred at 23 ° C. After that, 6.2 parts of compound (1-16) 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-butoxy-2,2,6,6-pentamethylpiperidine, 1H, 1H, 2H, 2H-tridecafluorooctatyl acrylate 3.7 The parts were charged and stirred at 23 ° C. After that, 5.7 parts of compound (1-17) 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-hydroxy-1,2,2,6,6-pentamethylpiperidin, 1.8 parts of triethylamine and 20 parts of tetrahydrofuran were charged and stirred at room temperature. Then, 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 completed. The reaction solution was transferred to a separatory funnel, water was added, and the mixture was extracted with ethyl acetate. After washing with saturated sodium hydrogen carbonate and water and drying with magnesium sulfate, the solvent was distilled off with an evaporator to obtain 2.9 parts of compound (2-1).

In a reaction vessel equipped with a stirrer and a thermometer, 2 parts of 4-hydroxy-1,2,2,6,6-pentamethylpiperidin, 1.8 parts of triethylamine and 20 parts of tetrahydrofuran were charged and stirred at room temperature. Then, 4.1 parts of perfluorobutyryl chloride was added dropwise over 20 minutes under cooling and stirring to 0 ° C. After that, 4.1 parts of compound (2-2) was obtained in the same manner as in Synthesis Example 16.

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

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

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

In a reaction vessel equipped with a stirrer and a thermometer, 2 parts of 4-hydroxy-1-methoxy-2,2,6,6-pentamethylpiperidin, 1.6 parts of triethylamine and 20 parts of tetrahydrofuran were charged and stirred at room temperature. Then, 3.8 parts of perfluorobutyryl chloride was added dropwise over 20 minutes under cooling and stirring to 0 ° C. After that, 4 parts of compound (2-6) was obtained in the same manner as in Synthesis Example 16.

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

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

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

In a reaction vessel equipped with a stirrer and a thermometer, 2 parts of 4-hydroxy-1-ethoxy-2,2,6,6-pentamethylpiperidin, 1.3 parts of triethylamine and 20 parts of tetrahydrofuran were charged and stirred at room temperature. Then, under cooling and stirring to 0 ° C., 3 parts of pentadecafluorooctanoyl chloride was added dropwise over 20 minutes. After that, 3.6 parts of compound (2-10) was 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 are all ¹ H-NMR, IR, similarly to the compound (1-1). 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]
<Manufacturing of polymerizable composition>
[Formulation Examples 1-44]
Compound (a1) and / or compound (a2), compound (B), compound (C), initiator (E), and silane compound (a1) and / or compound (a2), compound (C), initiator (E), and silane compound (a1) and / or compound (a2), compound (B), compound (C), and silane compound F), antioxidant (G), colorant (J) and various other additives (Q) were charged at the ratios shown in Table 3, and after sufficient stirring with a stirrer and sufficient defoaming. , The polymerizable composition shown in the compounding example was obtained. In Table 3, the blanks indicate no compounding. Of these, Formulation Examples 5 to 44 are the polymerizable compositions of the present invention corresponding to Examples 1 to 40, respectively, and Formulation Examples 1 to 4 are the polymerizable compositions of the present invention corresponding to Comparative Examples 1 to 4, respectively. It is a polymerizable composition that is not a composition. A description of the abbreviations used in Table 3 is shown in Table 4.

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

《Curing speed》
Using an applicator, the polymerizable composition was applied onto a polyethylene terephthalate (PET) film so that the coating film thickness was 10 μm, and a coated product was prepared. The coated object 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 / cm ¹ lamp). The surface of the cured product after irradiation was repeatedly irradiated by touching the surface until the stickiness disappeared, and the curing rate was evaluated in three stages. It can be judged that the smaller the number of irradiations, the better the curability. If the evaluation is other than "x", there is no particular problem in actual use.
⊚: 1-3 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 gelling. Bad.

《Scratch resistance》
A polymerizable composition is applied onto a glass plate using an applicator so that the coating film 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. , 23 ° C. and 50% relative humidity for 24 hours to prepare a test piece. A scratch resistance test was conducted by rubbing the test piece with # 0000 steel wool 10 times while applying a load of 250 g / cm ² in a constant temperature and humidity chamber at 23 ° C. and 50% relative humidity. It was. The presence or absence of scratches and the degree of scratches were visually observed and used as an index of scratch resistance.
The evaluation was performed in 4 stages. It can be judged that the smaller the number of scratches, the better the scratch resistance. If the evaluation is other than "x", there is no particular problem in actual use.
⊚: No scratches. No problem at all.
◯: 5 or less scratches occur. There are some, but there is no problem.
Δ: 6 to 10 scratches occur. Practically usable.
X: 11 or more scratches occur. There is a problem in practical use.

In Table 5, "curing rate" evaluates the polymerization rate. If 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 the stability at 60 ° C. storage. "Scratch resistance" evaluates the hardness of the surface of the cured product.

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

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 radically polymerizable compound (B). Sex composition.
[In the general 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 form an alkyl group. Represented, R ¹⁶ and R ¹⁷ each independently represent an alkyl group substituted with hydrogen, at least 3 or more fluorines or a group represented by −R ¹⁸ COOR ¹⁹ , and R ²⁶ represents −COR ²⁷ . , R ²⁷ represent an alkyl group substituted with at least 3 or more fluorines. R ¹⁸ represents an alkylene group and R ¹⁹ represents an alkyl group substituted with at least 3 or more fluorines. However, R ¹⁶ and R ¹⁷ do not become hydrogen at the same time. ] R ¹¹ and R ²¹ are alkyl groups having 1 to 4 carbon atoms, and R ^{12 to} R ¹⁵ and R ^{22 to} R ²⁵ are independently alkyl groups having 1 to 4 carbon atoms, and R ¹⁶ and R are 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 8. The alkyl group of claim 1, wherein 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 or more fluorines. Active energy ray-polymerizable composition of. A cured product of the active energy ray-polymerizable composition according to claim 1 or 2. A compound represented by the following general formula (3) or the following general formula (4).
[In the general formula (3) and the 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. ~ R ⁴⁵ each independently represent 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 , and R ⁴⁶ is represents -COR ^47, R ⁴⁷ represents at least three fluorine substituted alkyl group having 1 to 8 carbon 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 or more fluorines. However, R ³⁶ and R ³⁷ do not become hydrogen at the same time. ] The method for producing a compound represented by the general formula (3) according to claim 4, wherein the compound represented by the following general formula (3-1) is reacted with the compound represented by the following general formula (3-2). ..
[In the general formula (3-1) and the general formula (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 a hydrogen or 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 fluorines. ] The method for producing a compound represented by the general formula (4) according to claim 4, wherein the compound represented by the following general formula (4-1) is reacted with the compound represented by the following general formula (4-2). ..
[In the general formula (4-1) and the general formula (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 are 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 fluorines. ]