WO2018207836A1

WO2018207836A1 - Actinic-ray-curable composition, method for producing cured film, and cured object

Info

Publication number: WO2018207836A1
Application number: PCT/JP2018/017973
Authority: WO
Inventors: 有光　晃二; 究寺田; 博一桑原
Original assignee: 学校法人東京理科大学; 日本化薬株式会社
Priority date: 2017-05-10
Filing date: 2018-05-09
Publication date: 2018-11-15
Also published as: JPWO2018207836A1; TW201900778A; JP7050245B2; TWI758475B; KR20200003815A; CN110382597A

Abstract

Provided are: an actinic-ray-curable composition that comprises a silicon compound having an alkoxysilyl group and a photobase generator which comprises a compound represented by a given chemical formula and can generate an amine and a free radical at the same time upon light absorption; a cured object obtained from the composition; and a method for producing a cured film from the composition. The actinic-ray-curable composition is excellent in terms of storage stability, curability, and film-forming property, and the cured object obtained therefrom is excellent in terms of adhesion to the base, scratch resistance, etc.

Description

Active energy ray-curable composition, method for producing cured film, and cured product

The present invention relates to an active energy ray-curable resin composition comprising a photobase generator containing a compound having a specific structure and a silicon-based compound having a specific structure, a cured product of the composition, and a cure obtained using the composition The present invention relates to a film manufacturing method.

In the field of liquid crystal display screens for mobile communications such as mobile phones and PDAs, and touch panels as screen display input devices such as ATMs and car navigation systems, hard coats are often used to prevent scratches on the display screen. However, as the use of these display media expands, the demand for surface protection of the display media is becoming stricter.

For such a hard coat material, a material having high hardness is desired in order to improve the scratch resistance. For example, in the case of a UV curable organic hard coat material, the hardness and scratch resistance can be increased by increasing the crosslinking density. Techniques that improve performance are known. However, in such a UV curable hard coat material, the crosslinking density is increased by addition polymerization of an acrylic double bond, ring-opening polymerization of an epoxy ring, etc., so that the coating material itself shrinks during the polymerization reaction. There was a problem, and there was a limit to increasing the hardness with only organic components.

On the other hand, the characteristics of inorganic coating materials typified by polysiloxane are superior in heat resistance, weather resistance, hardness, scratch resistance and the like as compared with organic coating materials. As a method for forming such a thin coating layer of an inorganic coating material, a metal alkoxide is hydrolyzed and polycondensed using a sol-gel reaction, and thermally crosslinked and cured at a relatively low temperature via a metalloxane oligomer. The method of performing has been put into practical use, and the thin film coat layer obtained has high hardness.

Patent Document 1 discloses a coating composition comprising a trihydroxysilane partial condensate and colloidal silica. However, thermosetting coating materials are not economical because they require a great deal of heat energy for curing, and there is also a problem that the base material is deformed by applied heat.

In order to solve these problems, the UV curing organic coating material has excellent characteristics such as curability, transparency, base material compatibility and processability, and inorganic materials have high hardness and scratch resistance. There is a need for a UV curable organic-inorganic coating material that takes advantage of these characteristics and compensates for the respective drawbacks.

Patent Document 2 discloses a composition comprising silica particles, acryloxy functional group silane or a hydrolyzate thereof, and an acrylate compound. However, since the composition of the same literature which hardens | cures with a photoinitiator is not considered regarding the photocuring of a silica particle or a silane part, the hardness of hardened | cured material was inadequate.

Patent Document 3 discloses a technique for introducing a polymerizable functional group onto the surface of a particle such as silica, but such modified silica is difficult to produce and is used for introducing a polymerizable functional group. Since a reactive group such as a hydroxyl group is required in the compound, the degree of freedom in design is low, and there has been a limit to improving the hardness of the cured product of the composition using silica obtained by this method.

In addition, the above-mentioned composition is intended to improve hardness and scratch resistance, and other properties such as crack resistance, flexibility, workability and flame retardancy are not considered. .

In other words, UV curable organic-inorganic coating materials have excellent storage stability, no problem in curability and film-forming property, excellent impact resistance and scratch resistance, and have various physical properties of organic polymers. Curing-type organic-inorganic coating materials have not yet been put into practical use, and in order to solve these problems at the same time, the inorganic component and the organic component are cured simultaneously, and the inorganic component and the organic component are uniformly integrated through covalent bonds. A technique for producing a cured organic-inorganic hybrid film has been studied.

Patent Document 4 discloses an organic-inorganic hybrid coating composition containing a radical photopolymerization initiator and a cationic photopolymerization initiator. However, the composition of the same document needs to contain two different types of photopolymerization initiators, and the composition is not preferable because the amount of the photopolymerization initiator in the composition increases as a result.

Moreover, since the cationic photopolymerization initiator has high activity and is unstable, not only is there concern about the storage stability of the composition, but there is also a concern that the acid generated by light irradiation remaining in the cured product may cause metal corrosion. . Furthermore, when a SiOR group remains at the terminal, this hydrolysis becomes a rate-determining step, and the generated alcohol may cause radical or cationic photopolymerization initiators to cause poor curing of the composition. .

In recent years, the introduction of an anionic UV curing system has been studied for the purpose of solving these problems. The anion produced by the photobase generator acts directly on the SiOR group in a nucleophilic manner, and can quickly generate SiOH.

Patent Document 5 discloses a photoinitiator that generates a base (amine) and a radical by ultraviolet irradiation. However, the base generated from the photopolymerization initiator in this document is a monofunctional amine with low activity, and the curing ability as a photobase generator is insufficient.

Patent Document 6 discloses a photobase generator that generates both a base and a radical upon irradiation with actinic rays. However, the photobase generator of the same document is an ionic compound composed of carboxylic acid and amine, and tertiary amines generated by irradiation with active energy rays are very high in activity and unstable, so that storage stability and solubility are improved. There is a problem, and the tertiary amine is difficult to control the reaction of the SiOH group generated by hydrolysis of the alkoxysilyl group, so that the molecular weight of the hydrolysis-condensation product of alkoxysilane cannot be controlled. Therefore, a photobase generator that is a neutral compound that simultaneously generates an aliphatic primary or secondary amine and an active radical by irradiation with active energy rays is desired.

In order to solve these problems, Non-Patent Documents 1 and 2 describe a resin comprising a photobase generator, which is a neutral compound that simultaneously generates an aliphatic primary or secondary amine and an active radical, and a silicon compound having an alkoxysilyl group. We are studying compositions and their cured products. However, the photobase generators disclosed in these documents have a short wavelength of absorption of active energy rays. Therefore, compared with the photosensitive region of the conventional photobase generator, it has higher sensitivity to longer wavelength light (active energy rays) and efficiently generates a base by irradiation with the longer wavelength light. Development of a photobase generator is desired.

Japanese Patent Publication No. 52-039691 JP-A-62-256874 Japanese Patent No. 3474330 Japanese Patent No. 5063915 JP 2009-58923 A JP 2011-202160 A

The present invention provides an active energy ray-curable composition that is excellent in storage stability, curability and film-forming property, and that the cured product has high hardness and is excellent in adhesion to a substrate and scratch resistance. Objective.

As a result of the study by the present inventors, there is a high sensitivity to long-wavelength light (active energy rays), and neutrality that simultaneously generates aliphatic primary or secondary amines and active radicals upon irradiation with active energy rays. The present inventors have found that an active energy ray-curable composition containing a photobase generator as a compound and a silicon-based compound having an alkoxysilyl group solves the above problems, and has completed the present invention.

That is, the present invention provides (1) a silicon-based compound having an alkoxysilyl group, and an amine and an active radical that can absorb light and simultaneously generate the following formula (1)

(In Formula (1), R ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group or an organic group. R ₂ and R ₃ represent an aryl group having a substituent. X represents a primary amine or secondary amine to a nitrogen atom. (Represents a residue excluding one directly bonded hydrogen atom.)
An active energy ray-curable composition containing a photobase generator containing a compound represented by:
(2) The active energy ray-curable composition according to (1), wherein the photobase generator has absorption in a wavelength region of 350 nm or more,
(3) The active energy ray-curable composition according to item (1) or (2), further containing a photopolymerization initiator other than the compound represented by formula (1),
(4) The active energy ray-curable composition according to any one of (1) to (3), further containing a compound having at least one urethane bond as a base proliferating agent,
(5) The active energy ray-curable composition according to any one of (1) to (4), further comprising a compound having an acryloyl group and / or a methacryloyl group,
(6) A cured product of the active energy ray-curable composition according to any one of (1) to (5) above, and (7) any one of (1) to (5) above. A method for producing a cured film obtained using an active energy ray-curable composition,
(A) applying the active energy ray-curable composition to a substrate to form a film;
(B) a step of first heating the coating;
(C) exposing the first heated coating; and (d) second heating the exposed coating;
About.

Since the active energy ray-curable composition of the present invention is excellent in storage stability, curability and film-forming property, and the cured product has high hardness, adhesion to a substrate and scratch resistance, it is a mobile phone. It is suitably used for hard coat applications such as liquid crystal display screens and touch panels.

FIG. 1 is an absorbance curve of photobase generators (photopolymerization initiators) 1 to 7 used as materials for Examples and Comparative Examples.

Hereinafter, although the active energy ray-curable composition of the present invention will be described in detail, the active energy ray-curable composition of the present invention is not limited to the form for carrying out the invention.
[Silicon compound having alkoxysilyl group]
The active energy ray-curable composition of the present invention contains a silicon-based compound having an alkoxysilyl group.
Examples of the silicon-based compound having an alkoxysilyl group (hereinafter simply referred to as “silicon-based compound”) contained in the active energy ray-curable composition of the present invention include 1 to 3 alkoxysilyl groups. Examples thereof include a silane coupling agent and an alkoxysilane compound having 1 to 4 alkoxysilyl groups, and a part of the alkoxysilyl group may be hydrolyzed or hydrolyzed polycondensed. The alkoxy group in the alkoxysilyl group of the silicon-based compound is preferably an alkoxy group having 1 to 8 carbon atoms from the viewpoint of reactivity, stability, etc., specifically, a methoxy group, an ethoxy group, (iso) A propyloxy group or an (iso) butyloxy group is preferable, and a methoxy group or an ethoxy group is more preferable. In this specification, for example, the description “(iso) propyl group” means both n-propyl group and iso-propyl group. The silane coupling agent may have a functional group other than an alkoxysilyl group, and the functional group that may have an amino group, an epoxy group, a mercapto group, an isocyanate group, or a hydroxyl group is preferable. Groups are more preferred.

Specific examples of the silane coupling agent having an alkoxysilyl group include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldiethoxy. Silane, 3-methacryloxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Xylpropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopro Aminosilanes such as rutrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and 3- (N-phenylaminopropyltrimethoxysilane); 2- (3,4-epoxycyclohexyl) ethyltri Epoxy silanes such as methoxysilane, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane; 3-octanoylthio Sulfur silanes such as -1-propyltriethoxysilane, isocyanate silanes such as 3-isocyanatopropyltriethoxysilane and 3-isocyanatepropyltrimethoxysilane, etc. These silane couplings As the adhesive agent, one kind may be used alone, or two or more kinds may be used in combination, and one that has been partially hydrolyzed or hydrolyzed polycondensed in advance may be used. Absent.

Specific examples of alkoxysilane compounds include trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, methyldimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetraethoxysilane, diphenyldimethoxy. Examples thereof include silane, phenyltrimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. These alkoxysilane compounds may be used singly or in combination of two or more, or may be used partially hydrolyzed or hydrolyzed polycondensed in advance. I do not care.

Examples of the silicon compound contained in the active energy ray-curable composition of the present invention include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxy. Propylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, methyldimethyl Xyloxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane or tetraethoxysilane are preferred, and 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 -Methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, tetramethoxysilane, tetramethoxysilane or tetraethoxysilane are more preferred.

[Photobase generator]
The active energy ray-curable composition of the present invention is a photobase generator that preferably has absorption in a wavelength region of 350 nm or more, and is a specific photobase that absorbs light and simultaneously generates an amine and an active radical. It contains a generator (hereinafter, also simply referred to as “essential component photobase generator”).

[Compound represented by Formula (1)]
The compound represented by the following formula (1) can be used as a photobase generator contained in the active energy ray-curable composition of the present invention.

In formula (1), R ₁ represents a hydrogen atom, a hydroxyl group, an alkoxy group or an organic group. The alkoxy group represented by R _{1 in the} formula (1) is preferably an alkoxy group having 1 to 18 carbon atoms, and specific examples thereof include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n -Butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group, iso-pentoxy group, neo-pentoxy group, n-hexyloxy group and n-dodecyloxy group.

Specific examples of the organic group represented by R _{1 in the} formula (1) include alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, alkynyl groups having 2 to 18 carbon atoms, and 6 to 12 carbon atoms. Examples thereof include an aryl group, an acyl group having 1 to 18 carbon atoms, an aroyl group having 7 to 18 carbon atoms, a nitro group, a cyano group, an alkylthio group having 1 to 18 carbon atoms, and a halogen atom.

Examples of the organic group having 1 to 18 carbon atoms as specific examples of the organic group represented by R _{1 in the} formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an iso-butyl group. , Sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group and n-dodecyl group And a linear alkyl group such as a linear or branched alkyl group and a cyclic alkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group, preferably an alkyl group having 2 to 6 carbon atoms, It is more preferably a linear or branched alkyl group having 2 to 6 carbon atoms.

Specific examples of the organic group having 2 to 18 carbon atoms as the organic group represented by R _{1 in the} formula (1) include a vinyl group, a propenyl group, a 1-butenyl group, an iso-butenyl group, a 1-pentenyl group, 2- Pentenyl group, 2-methyl-1-butenyl group, 3-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2,2-dicyanovinyl group, 2-cyano-2-methylcarboxyl vinyl group and 2 -Cyano-2-methylsulfone vinyl group and the like.

Specific examples of the alkynyl group having 2 to 18 carbon atoms as the organic group represented by R _{1 in the} formula (1) include ethynyl group, 1-propynyl group and 1-butynyl group.

Specific examples of the organic group having 6 to 12 carbon atoms as the organic group represented by R _{1 in the} formula (1) include a phenyl group, a naphthyl group, and a tolyl group, and these are aryl groups having 6 to 10 carbon atoms. It is preferable.

Specific examples of the organic group having 1 to 18 carbon atoms as the organic group represented by R _{1 in the} formula (1) include formyl group, acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n -Butylcarbonyl group, n-pentylcarbonyl group, iso-pentylcarbonyl group, neo-pentylcarbonyl group, 2-methylbutylcarbonyl group, nitrobenzylcarbonyl group and the like.

Specific examples of the aroyl group having 7 to 18 carbon atoms as the organic group represented by R _{1 in the} formula (1) include a benzoyl group, a toluoyl group, a naphthoyl group, and a phthaloyl group.

Specific examples of the organic group represented by R _{1 in the} formula (1) having 1 to 18 carbon atoms include a methylthio group, an ethylthio group, an n-propylthio group, an iso-propylthio group, an n-butylthio group, and an iso-butylthio group. Group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, 2-methylbutylthio group, 1-methylbutylthio group, neo-pentylthio group, 1,2-dimethylpropylthio group, and Examples include 1,1-dimethylpropylthio group.

Examples of the halogen atom as a specific example of the organic group represented by R _{1 in} Formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
R ₁ in Formula (1) is preferably an alkoxy group, more preferably an alkoxy group having 1 to 18 carbon atoms, still more preferably an alkoxy group having 1 to 6 carbon atoms, A 1 to 4 alkoxy group is particularly preferable, and a methoxy group is most preferable.

In formula (1), R ₂ and R ₃ represent an aryl group, and the aryl group may have a hydrogen atom in its structure substituted with a substituent. R ₂ and R ₃ are preferably aryl groups having a substituent.
The aryl group represented by R ₂ and R _{3 in} the formula (1) is a residue obtained by removing one hydrogen atom from an aromatic hydrocarbon. Specific examples of the aromatic hydrocarbon include benzene, naphthalene, anthracene, Examples include phenanthrene and pyrene.
R ₂ and R ₃ in Formula (1), residues obtained by removing one hydrogen atom from a benzene or naphthalene are preferred, residues obtained by removing one hydrogen atom from benzene is more preferable.
Specific examples of the substituent that the aryl group represented by R ₂ and R _{3 in} the formula (1) can be substituted with a hydrogen atom in the structure include a halogen atom, a hydroxyl group, an alkoxy group, a mercapto group, a sulfide group, a silyl group, silanol group, a nitro group, a nitroso group, a cyano group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group or an organic group, R ₂ and R ₃ When a plurality of R ₂ and R ₃ are present, each R ₂ and R ₃ may be the same as or different from each other.

Examples of the halogen that can be substituted for the hydrogen atom contained in the structure of the aryl group represented by R ₂ and R _{3 in} the formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkoxy group that can be substituted for the hydrogen atom contained in the structure of the aryl group represented by R ₂ and R ₃ in the formula (1) include the same alkoxy groups as those represented by R _{1 in the} formula (1).

Specific examples of the organic group in which an aryl group represented by R ₂ and R ₃ of formula (1) may be replaced with a hydrogen atom having in the structure, an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, an isocyano group, Examples include cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, carboxyl group, carboxylate group, acyl group, acyloxy group, and hydroxyimino group.
The alkyl group, aryl group, and acyl group as specific examples of the organic group that can be substituted for the hydrogen atom that the aryl group represented by R ₂ and R _{3 in} the formula (1) has in the structure include R in the formula (1), respectively. Specific examples of the organic group represented by ₁ include the same alkyl groups having 1 to 18 carbon atoms, aryl groups having 6 to 12 carbon atoms, and acyl groups having 1 to 18 carbon atoms.

These organic groups may contain bonds and substituents other than hydrocarbon groups such as heteroatoms in the organic group, and these may be linear or branched. The organic group that can be substituted for the hydrogen atom that the aryl group represented by R ₂ and R ₃ has in the structure is usually a monovalent organic group. It can be an organic group.

As the bond other than the carbon-hydrogen bond (bond of C and H) of the hydrocarbon group in the organic group in which the aryl group represented by R ₂ and R ₃ can be substituted for the hydrogen atom in the structure, the effect of the present invention As long as is not impaired, it is not particularly limited, and examples include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, a carbonate bond, a sulfonyl bond, a sulfinyl bond, and an azo bond. From the viewpoint of heat resistance, the bond other than the carbon-hydrogen bond of the hydrocarbon group in the organic group includes ether bond, thioether bond, carbonyl bond, thiocarbonyl bond, ester bond, amide bond, urethane bond, imino bond ( —N═C (—R) —, —C (═NR) —, wherein R is a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, and a sulfinyl bond are preferable.

The substituent other than the hydrocarbon group in the organic group that can be substituted with the hydrogen atom that the aryl group represented by R ₂ and R ₃ has in the structure is not particularly limited as long as the effects of the present invention are not impaired. Atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, isocyano groups, cyanato groups, isocyanato groups, thiocyanato groups, isothiocyanato groups, silyl groups, silanol groups, alkoxy groups, alkoxycarbonyl groups, carbamoyl groups, thiocarbamoyl groups, nitro groups Nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonato group, hydroxyimino group, saturated or unsaturated alkyl ether group, A saturated or unsaturated alkylthioether group, Chromatography ether group, and thioether group, an amino group _{(-NH 2, -NHR, -NRR '} : wherein, R and R' each independently represent a hydrocarbon group) include an ammonio group. The hydrogen contained in the substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be any of linear, branched, and cyclic. Among them, as the substituent other than a hydrocarbon group in the organic group aryl group represented by R ₂ and R ₃ can be substituted with a hydrogen atom having in the structure, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, Isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group Acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, hydroxyimino group, saturated or unsaturated alkyl ether group, saturated or unsaturated alkyl thioether group, aryl ether group, and Arylthioate Group is preferred.

In addition, two or more of the substituents that can be substituted for the hydrogen atom in the aryl group represented by R ₂ and R ₃ may be bonded to form a cyclic structure. The cyclic structure is a combination of two or more selected from the group consisting of saturated or unsaturated alicyclic hydrocarbons, heterocycles, and condensed rings, and the alicyclic hydrocarbons, heterocycles, and condensed rings. The structure which becomes may be sufficient.

It is preferable to introduce one or more substituents that can replace the aryl group represented by R ₂ and R ₃ with a hydrogen atom in the structure of the essential photobase generator of the present invention. That is, at least one of the substituents that can be substituted for the hydrogen atom that the aryl group represented by R ₂ and R ₃ has in the structure is halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group , A sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group or an organic group. By introducing at least one substituent as described above into the substituent that can be substituted for the hydrogen atom of the aryl group represented by the substituents R ₂ and R ₃ , the light of the photobase generator absorbs light. The wavelength can be adjusted, and a desired wavelength can be absorbed by introducing a substituent. The absorption wavelength can be shifted to a longer wavelength by introducing a substituent that extends the conjugated chain of the aromatic ring. It is also possible to improve the solubility and compatibility with the polymer precursor to be combined. Thereby, it is possible to improve the sensitivity of the photosensitive resin composition in consideration of the absorption wavelength of the polymer precursor to be combined.

Examples of the substituent that can be substituted with the hydrogen atom that the aryl group represented by R ₂ and R ₃ has in the structure include an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, and a propyl group; a cyclopentyl group, a cyclohexyl group, and the like A cycloalkyl group having 4 to 23 carbon atoms; a cycloalkenyl group having 4 to 23 carbon atoms such as a cyclopentenyl group and a cyclohexenyl group; and 7 carbon atoms such as a phenoxymethyl group, a 2-phenoxyethyl group, and a 4-phenoxybutyl group. An aryloxyalkyl group having from 26 to 26 (-ROAr group); an aralkyl group having 7 to 20 carbon atoms such as benzyl group and 3-phenylpropyl group; and 2 to 21 carbon atoms having a cyano group such as cyanomethyl group and β-cyanoethyl group Alkyl group having 1 to 20 carbon atoms having a hydroxyl group such as hydroxymethyl group; methoxy group, ethoxy group An amide group having 2 to 21 carbon atoms such as an alkoxy group having 1 to 20 carbon atoms such as a group, an acetamide group or a benzenesulfonamide group (C ₆ H ₅ SO ₂ NH—); a carbon number such as a methylthio group or an ethylthio group An alkylthio group having 1 to 20 carbon atoms (—SR group); an acyl group having 1 to 20 carbon atoms such as an acetyl group or a benzoyl group; an ester group having 2 to 21 carbon atoms such as a methoxycarbonyl group or an acetoxy group (—COOR group and — OCOR group); aryl group having 6 to 20 carbon atoms such as phenyl group, naphthyl group, biphenyl group and tolyl group; aryl group having 6 to 20 carbon atoms substituted by electron donating group and / or electron withdrawing group; A donating group and / or an electron-withdrawing group is preferably a substituted benzyl group, cyano group, and methylthio group (—SCH ₃ ). The alkyl moiety may be linear, branched or cyclic.

Further, the photobase generator of the essential components, if at least one of the substituents aryl group represented by R ₂ and R ₃ can be substituted with a hydrogen atom having in the structure is a hydroxyl group, an aryl represented by R ₂ and R ₃ Compared with a compound that does not contain a hydroxyl group as a substituent that can be substituted with a hydrogen atom that the group has in the structure, it is preferable from the viewpoint of improving the solubility in a basic aqueous solution and increasing the absorption wavelength.

In formula (1), X represents an amine residue obtained by removing one hydrogen atom directly bonded to a nitrogen atom from a primary amine or secondary amine.
Specific examples of the amine residue represented by X in the formula (1) include a residue obtained by removing one hydrogen atom directly bonded to a nitrogen atom from amine compounds represented by the following formulas (a) to (z). Can be mentioned.

When a hydrogen atom is removed from an amine compound having two amino groups in one molecule represented by formula (a), formula (b), or the like, a residue obtained by removing a hydrogen atom from one amino group It may be a valent residue, or may be a divalent residue obtained by removing one hydrogen atom from each amino group. The amine compound represented by (a) or formula (b) is an amine compound having two amino groups in one molecule, but a hydrogen atom is removed from an amine compound having three amino groups in one molecule. In the case of removing it as a residue, it may be any monovalent to trivalent residue, and when removing a hydrogen atom from an amine compound having four amino groups in one molecule, It may be any monovalent to tetravalent residue. The same applies to the case where a residue is formed by removing a hydrogen atom from a compound having five or more amino groups in one molecule.
The amine residue represented by X in the formula (1) is preferably a residue obtained by removing one hydrogen atom directly bonded to a nitrogen atom from the amine compounds represented by the formulas (a) to (z). A residue obtained by removing one hydrogen atom directly bonded to a nitrogen atom from the amine compounds represented by () to (n) is more preferable.

The use ratio of the silicon-based compound and the essential photobase generator in the active energy ray-curable composition of the present invention depends on the stability of the composition, the transparency of the resulting cured film, the wear resistance, and the scratch resistance. Designed in terms of adhesion and crack resistance. The essential photobase generator is usually 5 to 80% by mass, preferably 10 to 60% by mass, more preferably 20 to 40% by mass based on the total amount of the silicon-based compound and the essential component photobase generator. .

[Photopolymerization initiator that can be used in combination]
The active energy ray-curable composition of the present invention may be used in combination with a photopolymerization initiator other than the compound having the partial structure represented by the formula (1). Examples of the photopolymerization initiator that can be used in combination include conventionally known photo radical generators, photo acid generators, photo base generators, and the like. These photopolymerization initiators may be used alone or in combination of two or more.

The photo radical generator that can be used in combination with the active energy ray-curable composition of the present invention is a compound having a function capable of initiating radical polymerization by photoexcitation, such as a monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, a benzoin ether compound, Examples include acylphosphine oxide compounds and aminocarbonyl compounds.
The photo radical generator used in combination with the active energy ray-curable composition of the present invention is preferably an acetophenone compound or an acylphosphine compound, more preferably an acetophenone compound, from the viewpoint of the transparency of the cured product.

The photoacid generator that can be used in combination with the active energy ray-curable composition of the present invention generates cations upon irradiation with radiation such as ultraviolet rays, far ultraviolet rays, excimer lasers such as KrF and ArF, X-rays, and electron beams. The cation is a compound that can serve as a polymerization initiator, and examples thereof include aromatic iodonium complex salts and aromatic sulfonium complex salts.
Specific examples of the aromatic iodonium complex salt include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, tricumyl iodonium tetrakis (Pentafluorophenyl) borate (Rhodia, trade name Rhodosyl PI2074), di (4-tert-butyl) iodonium tris (trifluoromethanesulfonyl) methanide (BASF, trade name CGI BBI-C1), and the like.

Specific examples of the aromatic sulfonium complex salt include 4-thiophenyldiphenylsulfonium hexafluoroantimonate (manufactured by Sun Apro, trade name: CPI-101A), thiophenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate ( San Apro, trade name CPI-210S), 4- [4- (2-chlorobenzoyl) phenylthio] phenyl bis (4-fluorophenyl) sulfonium hexafluoroantimonate (ADEKA, trade name SP-172), 4 -A mixture of aromatic sulfonium hexafluoroantimonate containing thiophenyldiphenylsulfonium hexafluoroantimonate (ACETO Corporate USA, trade name CPI-6976) and Riphenylsulfonium tris (trifluoromethanesulfonyl) methanide (manufactured by BASF, trade name CGI TPS-C1), tris [4- (4-acetylphenyl) sulfonylphenyl] sulfonium tris (trifluoromethylsulfonyl) methide (manufactured by BASF) Product name GSID 26-1), tris [4- (4-acetylphenyl) sulfonylphenyl] sulfonium tetrakis (2,3,4,5,6-pentafluorophenyl) borate (product name: Irgacure PAG290, manufactured by BASF), etc. Is mentioned.

The photobase generator that can be used in combination with the active energy ray-curable composition of the present invention is a compound that generates biguanidinium, imidazole, pyridine, diamine, and derivatives thereof by light irradiation such as ultraviolet rays, and specific examples thereof. As 9-anthrylmethyl-N, N-diethylcarbamate, (E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine, 1- (anisolaquinone-2-yl) ethylimidazolecarboxyl 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 1,2-diisopropyl-3- [bis (dimethylamino) methylene] guanidinium-2- (3-benzoylphenyl) propionate, 1,2- Dicyclohexyl-4,4,5,5-tetramethylbiguani Um -n- butyl triphenyl borate, and the like. These photobase generators may be used singly or in combination of two or more.
The photobase generator used in combination with the active energy ray-curable composition of the present invention is preferably a compound that generates imidazole or biguanium.

The content of the photopolymerization initiator in the active energy ray-curable composition of the present invention is preferably 10% by mass or less in the active energy ray-curable composition.

The active energy ray-curable composition of the present invention may be used in combination with a base proliferating agent that generates a base proliferatively by the action of a base. By using a base proliferating agent in combination with the active energy ray-curable composition of the present invention, the sensitivity of the active energy ray-curable composition can be further improved. In particular, when light does not reach the deep part of the active energy ray curable composition layer (when the active energy ray curable composition layer used for light irradiation is thick or the active energy ray curable composition is a large amount of dye or pigment In the case of the active energy ray-curable composition layer, the base action is photochemically generated on the surface of the active energy ray-curable composition layer and the base growth reaction by the base proliferating agent is started, thereby thermochemically and chain-linking the base. Therefore, it can be expected that a base catalyzed reaction occurs even in the deep part of the active energy ray-curable composition layer. There are no particular restrictions on the base proliferating agent that can be used in combination, but for example, JP 2000-330270 A, JP 2002-128750 A, Arimitsu, M.M. Miyamoto and K.K. Ichimura, Angew. Chem. Int. Ed. 39, 3425 (2000), etc., and it is preferable that the base proliferating agent contains a compound having at least one urethane bond.

The content of the base proliferating agent in the active energy ray-curable composition of the present invention may be appropriately determined depending on the type and combination of the essential component base generator and silicon compound, but the active energy ray-curable type of the present invention. It is preferably 40% by mass or less, more preferably 5 to 20% by mass in the composition.

In the active energy ray-curable composition of the present invention, a compound having an acryloyl group and / or a methacryloyl group may be used in combination.
Compounds having an acryloyl group or a methacryloyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, etoxy Alkoxypolyalkylene glycol (meth) acrylates such as polyethylene glycol (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate Hydroxyl group-containing (meth) acrylates such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N -N-substituted (meth) acrylamides such as isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine; N, N-dimethylaminoethyl (meth) ) Amino group-containing (meth) acrylates such as acrylate and N, N-diethylaminoethyl (meth) acrylate; Nitriles such as (meth) acrylonitrile; Styrenes such as styrene and α-methylstyrene; Ethyl vinyl ether, n-propyl Vinyl ethers such as vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether; fatty acid vinyls such as vinyl acetate and vinyl propionate; 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Alkylene glycol di (meth) acrylate such as polyethylene glycol di (meth) acrylate; glycerin propylene oxide modified tri (meth) acrylate, trimethylolpropane tri (Meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, isocyanic acid ethylene oxide modified tri (meth) acrylate, isocyanic acid ethylene oxide modified ε-caprolactone modified tri ( Trifunctional (meth) acrylates such as (meth) acrylate, 1,3,5-triacryloylhexahydro-S-triazine, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate tripropionate; pentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate monopropionate, dipentaerythritol hexa (meth) Acrylate, tetra methylol methane tetra (meth) acrylate, oligoester tetra (meth) acrylate, tris ((meth) acryloyloxy) Hosufe - DOO include polyfunctional (meth) acrylates such as PPZ.

Further examples include polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, (meth) acrylated maleic acid-modified polybutadiene, and the like.
The content of the compound having an acryloyl group and / or a methacryloyl group in the active energy ray-curable composition of the present invention is preferably 80% by mass or less, more preferably 5 to 5% in the active energy ray-curable composition of the present invention. 50% by mass.

In the active energy ray-curable composition of the present invention, a sensitizer may be used in combination to expand the absorption wavelength region of the photobase generator as an essential component and the photopolymerization initiator used in combination. Good. The sensitizer that can be used in combination is not particularly limited, and examples thereof include benzophenone, p, p′-tetramethyldiaminobenzophenone, p, p′-tetraethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, Pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro- 4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramid, anthraquinone, 2-ethylanthraquinone, 2-tert Butylanthraquinone, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis (5,7 -Dimethoxycarbonylcoumarin) or coronene.
These sensitizers may be used alone or in combination of two or more.

The content of the sensitizer in the active energy ray-curable composition of the present invention depends on the type and amount of the base generator and silicon compound as essential components, the sensitivity required for the active energy ray-curable composition, and the like. What is necessary is just to determine suitably, Preferably it is 30 mass% or less in the active energy ray hardening-type composition of this invention, More preferably, it is 5 to 20 mass%.

A solvent may be used in combination with the active energy ray-curable composition of the present invention. The solvent that can be used in combination is not particularly limited as long as it is a solvent that can dissolve or disperse a silicon compound, but is preferably a solvent that can dissolve a silicon compound, and more preferably an alcohol solvent. Examples of the solvent that can be used in combination include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-ethoxyethanol, and 2-butoxyethanol. An alcohol having 1 to 4 carbon atoms is preferable, and 2-propanol is more preferable in terms of solubility, stability, and coatability.
When a compound having an acryloyl group or a methacryloyl group is used in combination, ketones such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK) which are good solvents for the compound; esters such as ethyl acetate and butyl acetate; glycol Ethers; glycol ether esters; aromatic hydrocarbons; are preferably used.
The content of the solvent in the active energy ray-curable composition of the present invention is preferably 80% by mass or less, more preferably 0 to 50% by mass in the active energy ray-curable composition of the present invention.

In the active energy ray-curable composition of the present invention, additives such as a known leveling agent and antifoaming agent can be blended for the purpose of improving coatability and smoothness and appearance of the resulting cured film. The content of these additives is preferably 2% by mass or less in the active energy ray-curable composition of the present invention. Moreover, you may mix | blend a ultraviolet absorber, a light stabilizer, dye, a pigment, a filler, etc. in the range which does not impair the objective of this invention.

The active energy ray-curable composition of the present invention can be applied to a substrate (coating material) by bar coating, dip coating, flow coating, spray coating, spin coating, roller coating, reverse coating. Or any application | coating and printing methods, such as gravure printing, flexographic printing, screen printing, and inkjet printing, are possible, and it can select suitably according to the shape of a base material.

The active energy ray-curable composition of the present invention can be used as various adhesives including ink binders such as paints, gravure printing inks, flexographic printing inks and inkjet printing inks, and lamination adhesives. The active energy ray-curable composition of the present invention can be cured by a known active energy ray curing method, and it is particularly preferable to use ultraviolet rays or electron beams.

As the light source of the active energy ray irradiation apparatus, a light source usually containing light in the range of 200 to 500 nm, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, etc. can be used. It is preferable to use a light source including light in a wavelength region of 350 nm or more. The accumulated amount of active energy rays is not limited because the required minimum accumulated amount of light depends on the application, film thickness, presence / absence of colorant, and type and amount of photopolymerization initiator. The combined use of heat by ultraviolet rays, electron beams and infrared rays, far infrared rays, hot air, high frequency heating, etc. is effective.

The thickness of the active energy ray-curable composition of the present invention is usually 0.1 to 20 μm, preferably 2 to 10 μm, and most preferably 3 to 8 μm. When the thickness of the composition layer is applied within such a range, the adhesiveness between the composition layer and the substrate does not decrease due to stress generated during curing, and the object of the present invention is sufficient. A cured product layer having excellent hardness, scratch resistance and abrasion resistance can be obtained.

[Curing film and method for producing cured film]
A method for producing a cured film obtained using the active energy ray-curable composition of the present invention,
(A) applying the active energy ray-curable composition to a substrate to form a film;
(B) a step of first heating the coating;
(C) It is a manufacturing method including a step of exposing the heat-treated film, and (d) a step of secondly heating the exposed film.

(A) Application | coating in a process is performed by methods, such as above-mentioned bar coating method. The film after the application and before the first heating in (b) is referred to as a coating in this specification.
The first heating in the step (b) is performed by an apparatus such as a hot plate or an oven, and the conditions are usually 25 to 150 ° C. for 5 to 120 minutes, preferably 25 to 100 ° C. for 5 to 10 minutes.
The exposure process in the step (c) is performed using the above-described high-pressure mercury lamp or the like. The irradiation amount may be appropriately selected according to the type of silicon compound and the type and content of the photobase generator as an essential component, but is usually about 100 to 1500 mJ, preferably about 100 to 500 mJ.
The second heating in the step (d) may be performed using the same apparatus as the first heating in the step (b), and the conditions are usually 25 to 150 ° C. for 5 to 120 minutes, preferably 25 to 100 ° C. 5 to 30 minutes. In the present specification, the film obtained after the second heating is referred to as a cured film.

Since the active energy ray-curable composition of the present invention is excellent in storage stability, curability and film-forming property, and the cured product is excellent in impact resistance and scratch resistance, liquid crystal display screens such as mobile phones, touch panels, etc. It is suitably used for hard coat applications represented by

Next, the present invention will be described more specifically with reference to examples and comparative examples, but it goes without saying that the present invention is not limited thereby. In addition, “part” used in the present example means “part by mass” unless specified.

<Synthesis Example 1 Synthesis of Intermediate Compound 1 of Photobase Generator 1 as an Essential Component Having the Partial Structure Represented by Formula (1)>
After 10 parts of water and 53 parts of ethanol were dissolved in 1.9 parts of potassium cyanide, the reaction solution was degassed by sonication under a nitrogen atmosphere. To this solution, 10 parts of 4- (methylthio) benzaldehyde was added dropwise and heated at 80 ° C. to initiate the reaction. After stirring for 30 minutes, the reaction solution was cooled to 3 ° C. and the resulting crystals were collected by suction filtration. The recovered solid was purified by recrystallization using a large amount of ethanol to obtain 7.6 parts of intermediate compound 1.

<Synthesis Example 2 Synthesis of Intermediate Compound 2 of Photobase Generator 1 as Essential Component Represented by Formula (1)>
In a flask equipped with a stirrer, a reflux condenser and a stirrer, 9.0 parts of paraformaldehyde and 170 parts of dimethyl sulfoxide were added and stirred. A solution prepared by dissolving 1.4 parts of potassium hydroxide in 5 parts of ethanol was added dropwise to the flask and stirred until the paraformaldehyde was completely dissolved. A solution prepared by dissolving the intermediate compound 1 obtained in Synthesis Example 1 in 30 parts of dimethyl sulfoxide was added dropwise to the flask over 30 minutes and stirred at room temperature for 2 hours. Thereafter, 2.6 parts of 35% hydrochloric acid was added dropwise for neutralization to complete the reaction. Toluene and saturated brine were added to this reaction solution, and the mixture was extracted into an organic layer. The solvent was distilled off to obtain 40 parts of intermediate compound 2.

<Synthesis Example 3 Synthesis of Photobase Generator 1 as Essential Component Represented by Formula (1)>
1.0 part of the intermediate compound 2 obtained in Synthesis Example 2, 15 parts of toluene and 0.3 part of triethylamine were placed in a flask and stirred under reflux until uniform. Subsequently, 0.4 part of dicyclohexylmethane-4,4-diisocyanate was added at room temperature, and stirring was continued for 12 hours, followed by cooling and evaporation of the solvent with an evaporator. The obtained solution was dropped into cyclohexane, washed by stirring for 30 minutes, and 1.0 part of a photobase generator 1 represented by the following formula (IV) was obtained.

<Synthesis Example 4 Synthesis of Intermediate Compound 3 of Comparative Photobase Generator 5>
13.1 parts of N, N′-diisopropylcarbodiimide was added to 11.9 parts of 1,1,3,3-tetramethylguanidine, and the mixture was heated and stirred at 100 ° C. for 2 hours. After completion of the reaction, hexane was added to the reaction solution, cooled to 5 ° C., and the resulting crystals were filtered to obtain intermediate compound 3 (1,2-diisopropyl-4,4,5,5-tetramethylbiguanide). 8.3 parts were obtained as a white solid.

<Synthesis Example 5 Synthesis of Photobase Generator 5 for Comparison>
7.6 parts of ketoprofen and 7.2 parts of intermediate compound 3 obtained in Synthesis Example 4 were dissolved in 30 mL of methanol and stirred at room temperature for 30 minutes. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and the resulting residue was washed with hexane and dried under reduced pressure to obtain 12.2 parts of a photobase generator 5 represented by the following formula (V) as a white solid. It was.

<Synthesis Example 6 Synthesis of Intermediate Compound 4 of Comparative Photobase Generator 6>
A flask equipped with a stirrer, a reflux condenser and a stirrer was charged with 12.5 parts of 4,5-dimethoxy-2-nitrobenzylaldehyde, 1.5 parts of sodium tetrahydroborate and 250 parts of methanol at room temperature (23 ° C.). After stirring for 3 hours, 38 parts of saturated ammonium chloride solution was added. Thereafter, the precipitated yellow solid was collected by filtration, and 120 parts of chloroform was added to the filtrate for extraction, and then the solvent was distilled off to obtain a gray solid. The obtained solid was recrystallized from ethyl acetate to obtain 8.4 parts of intermediate compound 4 (4,5-dimethoxy-2-nitrobenzyl alcohol) as a yellow solid.

<Synthesis Example 7 Synthesis of Photobase Generator 6 for Comparison>
8.9 parts of intermediate compound 4 obtained in Synthesis Example 6, 150 parts of toluene, and 0.02 part of tin octylate were placed in a flask and stirred under reflux until uniform. Subsequently, 4.6 parts of dicyclohexylmethane 4,4-diisocyanate was added under reflux, and the mixture was refluxed for 3 hours. After cooling, the solvent was distilled off with an evaporator. The obtained brown solid was recrystallized with ethanol to obtain 6.8 parts of a photobase generator 6 represented by the following formula (VI).

<Synthesis Example 8 Synthesis of Intermediate Compound 5 of Comparative Photobase Generator 7>
8.1 parts of intermediate compound 5 were obtained in the same manner as in Synthesis Example 2 except that intermediate compound 1 was changed to benzoin.

<Synthesis Example 9 Synthesis of Photobase Generator 7 for Comparison>
5.3 parts of photobase generators 7 represented by the following formula (VII) were obtained in the same manner as in Synthesis Example 3 except that Intermediate Compound 2 was changed to Intermediate Compound 5 obtained in Synthesis Example 8.

Example 1
DPHA (Nihon Kayaku Co., Ltd.) 0.3 parts, 3-acryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., trade name KBM-5103) 0.075 parts, Tetraethoxysilane (Kanto Chemical Co., Ltd.) After adding 0.3 part, 0.0175 part of photobase generator 1 obtained in Synthesis Example 3 was added and diluted with 0.04 part of MEK to obtain the active energy ray-curable composition of the present invention. .

(Example 2)
The active energy ray curing of the present invention was carried out in the same manner as in Example 1 except that the addition amount of the photobase generator 1 was changed to 0.00125 parts and 0.01375 parts of photopolymerization initiator 2 (Irg.184) was added. A mold composition was obtained.

(Example 3)
The active energy ray curing of the present invention was carried out in the same manner as in Example 1 except that the addition amount of the photobase generator 1 was changed to 0.0025 part and 0.0125 part of the photopolymerization initiator 2 (Irg.184) was added. A mold composition was obtained.

Example 4
The active energy ray curing of the present invention was carried out in the same manner as in Example 1 except that the amount of photobase generator 1 added was changed to 0.005 part and 0.01 part of photopolymerization initiator 2 (Irg.184) was added. A mold composition was obtained.

(Comparative Example 5)
A comparative active energy ray-curable composition was obtained in the same manner as in Example 1 except that 0.0175 part of the photobase generator 1 was changed to 0.015 part of the photopolymerization initiator 2 (Irg. 184).

(Comparative Example 6)
A comparative active energy ray-curable composition was obtained in the same manner as in Example 1 except that 0.0175 part of the photobase generator 1 was changed to 0.015 part of the photopolymerization initiator 3 (Irg.369).

(Comparative Example 7)
A comparative active energy ray-curable composition was obtained in the same manner as in Example 1 except that 0.0175 part of photobase generator 1 was changed to 0.015 part of photobase generator 4 (Irg.OXE-01). It was.

(Comparative Example 8)
Comparative active energy ray-curable composition as in Example 1 except that 0.0175 part of the photobase generator 1 was changed to 0.015 part of the photobase generator 5 for comparison obtained in Synthesis Example 5. I got a thing.

(Comparative Example 9)
Active energy ray curing for comparison was performed in the same manner as in Comparative Example 8 except that the addition amount of the photobase generator 5 was changed to 0.00125 parts and 0.01375 parts of photopolymerization initiator 2 (Irg.184) was added. A mold composition was obtained.

(Comparative Example 10)
Comparative active energy ray-curable composition in the same manner as in Example 1 except that 0.0175 part of the photobase generator 1 was changed to 0.015 part of the photobase generator 6 for comparison obtained in Synthesis Example 7. I got a thing.

(Comparative Example 11)
Comparative active energy ray-curable composition in the same manner as in Example 1 except that 0.0175 part of the photobase generator 1 was changed to 0.015 part of the comparative photobase generator 7 obtained in Synthesis Example 9. I got a thing.

(Preparation and first heating of a film comprising an active energy ray-curable composition)
Each active energy ray obtained in Examples 1 to 4 and Comparative Examples 5 to 11 using a # 14 bar coder on a double-sided easy-adhesion PET film (Cosmo Shine A4300: 100 manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm. After each curable composition was applied, heat treatment (first heating, pre-exposure baking) at 80 ° C. for 1 minute was performed using an oven, and the solvent was distilled off.

(Exposure treatment and second heating)
Using the belt conveyor type high-pressure mercury lamp exposure machine, the pass on the PET film obtained above is 3 passes under the condition that the exposure amount of one pass is 100 mJ / cm ² (height from the belt conveyor to the high-pressure mercury lamp is 100 mm). Exposure was performed. Thereafter, heat treatment (second heating, post-exposure baking) at 80 ° C. for 10 minutes was performed using an oven to obtain a cured product (cured film) of each active energy ray-curable composition.

Results of evaluations performed on the compositions of the active energy ray-curable compositions of Examples 1 to 4 and Comparative Examples 5 to 11 and the compositions or cured films obtained from the compositions by the following methods. Are listed in Table 1.

(Evaluation methods)
(1) Appearance of the solution:
The solutions of the active energy ray-curable compositions of Examples 1 to 4 and Comparative Examples 5 to 11 were filled in test tubes, and the appearance was visually confirmed.
(2) Appearance of cured film:
The appearance of the cured film of each composition obtained using each of the active energy ray-curable compositions of Examples 1 to 4 and Comparative Examples 5 to 11 was visually checked for the presence of turbidity, luster, shading, cracks, and the like. Confirmed with.
(3) Pencil hardness:
The pencil hardness of the cured film of each composition obtained using each of the active energy ray-curable compositions of Examples 1 to 4 and Comparative Examples 5 to 11 was weighted at 750 g by a method according to JIS K-5600. It was measured.
(4) Adhesion:
The adhesiveness of the cured film of each composition obtained using each of the active energy ray-curable compositions of Examples 1 to 4 and Comparative Examples 5 to 11 to the PET film was measured in accordance with JIS K-5600. It was measured.
(5) Scratch resistance:
The surface of the cured film of each composition obtained using each of the active energy ray-curable compositions of Examples 1 to 4 and Comparative Examples 5 to 11 was rubbed 20 times with a load of 1000 g using # 0000 steel wool. After that, the damaged state of the surface was visually observed and evaluated according to the following evaluation criteria.
○: No scratch at all Δ: Slightly scratch ×: Clear scratch (6) Transparency (400 nm):
The transparency of the cured film of each composition obtained using each of the active energy ray-curable compositions of Examples 1 to 4 and Comparative Examples 5 to 11 was measured using an ultraviolet-visible spectrophotometer V-600 manufactured by JASCO Corporation. It was used and evaluated with transmittance at a wavelength of 400 nm.
(7) Stability:
The active energy ray-curable composition solutions of Examples 1 to 4 and Comparative Examples 5 to 11 were sealed in a sealed container and observed after standing in a thermostatic chamber at 25 ° C. for 3 months, and the following evaluations were made. Evaluated by criteria.
○: No change at all ×: Significant thickening or gelation

Absorbance of photopolymerization initiator (photobase generator):
A photopolymerization initiator (photobase generator) solution prepared by dissolving 1 to 7 1.0 × 10 ⁻⁵ mol of the photopolymerization initiator (photobase generator) shown in Table 1 in 10 ml of THF was prepared. A 1 ml portion of the above photopolymerization initiator (photobase generator) solution is collected using a whole pipette, and again made up to 10 ml using THF, to obtain a photopolymerization initiator (photobase generator) for absorbance evaluation. A dilution was obtained. The absorbance of the photopolymerization generators (photobase generators) 1 to 7 was measured using a quartz cell having an optical path length of 10 mm filled with the obtained diluted photopolymerization initiator (photobase generator), and the absorbance was measured. Based on the results, the molar extinction coefficient ε was calculated by the following formula. The measurement results of the absorbance are shown in FIG. 1, and the calculated value of the molar extinction coefficient ε is shown in Table 2.
Molar extinction coefficient ε = absorbance / (optical path length × molar concentration of photopolymerization initiator (photobase generator))
When the molar extinction coefficient is 500 or more, the compound is defined as having absorption.

From the results of Table 1, the active energy ray-curable composition of the present invention is superior in storage stability than the comparative composition, excellent in the appearance of the solution and the cured film, and the cured product has high hardness. It turns out that it is excellent in the adhesiveness to a PET film, and a body abrasion property, and is excellent in the transmittance | permeability of the light of wavelength 400nm. Moreover, it can be seen from the results in Table 2 that the photopolymerization initiator used in the examples has a light absorption band of 350 nm or more.

Claims

A silicon-based compound having an alkoxysilyl group, and an amine and an active radical that can absorb light and simultaneously generate the following formula (1)

(In Formula (1), R 1 represents a hydrogen atom, a hydroxyl group, an alkoxy group or an organic group. R 2 and R 3 represent an aryl group having a substituent. X represents a primary amine or secondary amine to a nitrogen atom. (Represents a residue excluding one directly bonded hydrogen atom.)
The active energy ray hardening-type composition containing the photobase generator containing the compound represented by these.
The active energy ray-curable composition according to claim 1, wherein the photobase generator has absorption in a wavelength region of 350 nm or more.
Furthermore, the active energy ray hardening-type composition of Claim 1 or 2 containing photoinitiators other than the compound represented by Formula (1).
The active energy ray-curable composition according to any one of claims 1 to 3, further comprising a compound having at least one urethane bond as a base proliferating agent.
Furthermore, the active energy ray hardening-type composition as described in any one of Claims 1 thru | or 4 containing the compound which has an acryloyl group and / or a methacryloyl group.
Hardened | cured material of the active energy ray hardening-type composition as described in any one of Claims 1 thru | or 5.
A method for producing a cured film obtained using the active energy ray-curable composition according to any one of claims 1 to 5,
(A) applying the active energy ray-curable composition to a substrate to form a film;
(B) a step of first heating the coating;
(C) exposing the first heated coating; and (d) second heating the exposed coating.