JPWO2018207836A1 - Active energy ray-curable composition, method for producing cured film, and cured product - Google Patents

Abstract

An active energy ray-curable type, including a silicon-based compound having an alkoxysilyl group, and a photobase generator containing a compound represented by a predetermined chemical formula, which can simultaneously generate light and an amine and an active radical by absorbing light. Provided are a composition, a cured product of the composition, and a method for producing a cured film obtained by using the composition. The active energy ray-curable composition is excellent in storage stability, curability and film-forming properties, and the cured product is excellent in adhesion to a substrate, scratch resistance and the like.

Description

  The present invention relates to an active energy ray-curable resin composition containing 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 curing obtained using the composition. The present invention relates to a method for producing a film.

  In fields such as liquid crystal display screens for mobile communication represented by mobile phones and PDAs, and touch panels as screen display input devices such as ATMs and car navigation systems, hard coats are frequently used to prevent scratches on the display screens. However, as the applications of these display media have expanded, the requirements for surface protection of the display media have become more and more severe.

  For such a hard coat material, a material having high hardness is desired in order to improve abrasion resistance. For example, in the case of a UV-curable organic hard coat material, the hardness and the abrasion resistance are increased by increasing the crosslinking density. Techniques for improving the performance are known. However, in such a UV-curable hard coat material, since the crosslinking density is increased by addition polymerization of an acrylic double bond, ring-opening polymerization of an epoxy ring, etc., shrinkage of the coating material itself which occurs during the polymerization reaction is reduced. This is a problem, and there is a limit to increasing the hardness using only organic components.

  On the other hand, the characteristics of the inorganic coating material represented by polysiloxane are excellent in heat resistance, weather resistance, hardness, scratch resistance and the like as compared with the organic coating material. As a method of forming a thin film coating layer of such an inorganic coating material, a metal alkoxide is hydrolyzed and polycondensed using a sol-gel reaction, and thermal crosslinking and curing are performed at a relatively low temperature via a metalloxane oligomer. This method has been put to practical use, and the resulting thin film coat layer has high hardness.

  Patent Document 1 discloses a coating composition comprising a trihydroxysilane partial condensate and colloidal silica. However, a thermosetting coating material is not economical because it requires a large amount of heat energy during curing, and there is a problem that the base material is deformed by the applied heat.

  In order to solve these problems, UV curable organic coating materials have excellent curability, transparency, substrate compatibility, workability, etc., and inorganic materials have high hardness, scratch resistance, etc. There is a need for a UV-curable organic-inorganic coating material that makes use of the above characteristics and compensates for the respective disadvantages.

  Patent Document 2 discloses a composition comprising silica particles, an acryloxy-functional silane or a hydrolyzate thereof, and an acrylate compound. However, the composition of the reference, which is cured by a photopolymerization initiator, does not consider the photocuring of silica particles or silane sites, and the cured product has insufficient hardness.

  Patent Document 3 discloses a method of introducing a polymerizable functional group on the surface of a particle such as silica. However, such a modified silica is difficult to produce and is used to introduce a polymerizable functional group. Since a reactive group such as a hydroxyl group is required in the compound, the degree of freedom in designing is low, and there is a limit in improving the hardness of a cured product of the composition using silica or the like obtained by this method.

  Moreover, the above-described composition is intended to improve hardness and scratch resistance, and does not consider other properties such as crack resistance, flexibility, workability, and flame retardancy. .

  That is, a UV-curable organic-inorganic coating material has excellent storage stability, has no problems in curability and film-forming properties, has excellent impact resistance and abrasion resistance, and has various physical properties of an organic polymer. Curable organic-inorganic coating materials have not yet been put to practical use, and in order to solve these problems simultaneously, the inorganic component and the organic component are simultaneously cured, and the inorganic component and the organic component are uniformly integrated through a covalent bond. A technique for producing an organic-inorganic hybrid cured 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 described in the document needs to contain two different photopolymerization initiators, and the compounding amount of the photopolymerization initiator in the composition increases as a result, which is not preferable because the composition becomes expensive.

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

  For the purpose of solving these problems, introduction of an anionic UV curing system has been studied in recent years. The anion generated by the photobase generator acts directly on the SiOR group nucleophilically and can generate SiOH promptly.

  Patent Literature 5 discloses a photoinitiator that generates a base (amine) and a radical by irradiation with ultraviolet light. However, the base generated from the photopolymerization initiator in the literature is a monofunctional amine having 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 light. However, the photobase generator described in the document is an ionic compound composed of a carboxylic acid and an amine, and the tertiary amine generated by irradiation with active energy rays has a very high activity and is unstable. The tertiary amine has a problem, and it is also difficult to control the reaction of the SiOH group generated by the hydrolysis of the alkoxysilyl group, so that the molecular weight of the hydrolysis condensate of the alkoxysilane cannot be controlled. Therefore, a photobase generator that is a neutral compound that simultaneously generates an active primary radical and an aliphatic primary or secondary amine by irradiation with active energy rays is desired.

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

J. Photopolym. Sci. Technol. , Vol. 27, No. 2,223-225 (2014) Chem. Lett. 2014, 43, 612-614

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

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

That is, the present invention provides (1) a silicon-based compound having an alkoxysilyl group and the following formula (1) capable of simultaneously absorbing light to generate an amine and an active radical.

(In the 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 nitrogen atom from a primary amine or a secondary amine. (Residue except one hydrogen atom directly bonded.)
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 an absorption in a wavelength region of 350 nm or more.
(3) The active energy ray-curable composition according to the above (1) or (2), further comprising a photopolymerization initiator other than the compound represented by the formula (1).
(4) The active energy ray-curable composition according to any one of the above (1) to (3), further comprising 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 the above (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 the above items (1) to (5), and (7) a cured product according to any one of the above items (1) to (5). 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) first heating the coating;
(C) exposing the first heated coating; and (d) second heating the exposed coating.
About.

  The active energy ray-curable composition of the present invention has excellent storage stability, curability and film-forming properties, and the cured product has high hardness and excellent adhesion to a substrate and excellent scratch resistance. Etc. are 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 in Examples and Comparative Examples.

Hereinafter, the active energy ray-curable composition of the present invention will be described in detail, but the active energy ray-curable composition of the present invention is not limited to the mode for carrying out the invention.
[Silicon Compound Having Alkoxysilyl Group]
The active energy ray-curable composition of the present invention contains a silicon 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, for example, one to three 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 groups may be hydrolyzed or hydrolyzed polycondensation. 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 and the like, and specifically, a methoxy group, an ethoxy group, and an (iso) group. A propyloxy group or an (iso) butyloxy group is preferred, and a methoxy group or an ethoxy group is more preferred. In the present specification, for example, description of “(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 as the functional group which may be present, 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-methacryloxypropylmethyldiethoxysilane. Silane, 3-methacryloxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Xypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl Aminosilanes such as trimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and 3- (N-phenylaminopropyltrimethoxysilane); 2- (3,4-epoxycyclohexyl) ethyltrimethylsilane Epoxy silanes such as methoxysilane, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane; 3-octanoylthio Sulfasilanes such as -1-propyltriethoxysilane; isocyanatesilanes such as 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltrimethoxysilane; As the agent, one type may be used alone, or two or more types may be used in combination. Those which have been subjected to partial hydrolysis or hydrolytic polycondensation in advance may be used. .

  Specific examples of the alkoxysilane compound include trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, methyldimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetraethoxysilane, diphenyldimethoxysilane Examples include silane, phenyltrimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. These alkoxysilane compounds may be used singly or in combination of two or more, and may be those which have been subjected to partial hydrolysis or hydrolytic polycondensation in advance. I do not care.

  Examples of the silicon-based 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, methyldimet Sisilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane or tetraethoxysilane are preferred, and 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 -Methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, tetramethoxysilane, tetramethoxysilane or tetraethoxysilane is 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 to simultaneously generate an amine and an active radical. A generator (hereinafter, also simply referred to as an “indispensable component photobase generator”) is contained.

[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 the 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 a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, -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 an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, and an alkyl group having 6 to 12 carbon atoms. Examples 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 alkyl group having 1 to 18 carbon atoms as a specific example 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 linear or branched alkyl groups, such as cyclopropyl group, cyclobutyl group, cyclopentyl group and a cycloalkyl group such as cyclohexyl group, and a C2 to C6 alkyl group is preferable. More preferably, it is a linear or branched alkyl group having 2 to 6 carbon atoms.

Examples of the alkenyl group having 2 to 18 carbon atoms as an example of 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, a 2-pentenyl group. Pentenyl group, 2-methyl-1-butenyl group, 3-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2,2-dicyanovinyl group, 2-cyano-2-methylcarboxylvinyl group and 2 -Cyano-2-methylsulfone vinyl group and the like.

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

The aryl group having 6 to 12 carbon atoms as a specific example of the organic group represented by R _{1 in the} formula (1) includes a phenyl group, a naphthyl group and a tolyl group, and is an aryl group having 6 to 10 carbon atoms. Is preferred.

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

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

Examples of the alkylthio group having 1 to 18 carbon atoms as the organic group represented by R _{1 in the} formula (1) 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 thereof include a 1,1-dimethylpropylthio group.

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

In the formula (1), R ₂ and R ₃ represent an aryl group, and the aryl group may have a hydrogen atom in the structure substituted by a substituent. R ₂ and R ₃ are preferably an aryl group 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, and specific examples of the aromatic hydrocarbon include benzene, naphthalene, anthracene, Phenanthrene, pyrene and the like can be mentioned.
As R ₂ and R ₃ in the formula (1), a residue obtained by removing one hydrogen atom from benzene or naphthalene is preferable, and a residue obtained by removing one hydrogen atom from benzene is more preferable.
Specific examples of the substituent which the aryl group represented by R ₂ and R _{3 in} the formula (1) can substitute for 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, A 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 phosphonatto group, an amino group, an ammonium group, or an organic group, wherein R ₂ and R ₃ are When a plurality of R ₂ and R ₃ are present, each R ₂ and R ₃ may be the same or different.

Examples of the halogen that can be substituted for the hydrogen atom contained in 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 which can be substituted for a hydrogen atom in the structure of the aryl group represented by R ₂ and R ₃ in the formula (1) include the same as the alkoxy group represented by R _{1 in the} formula (1).

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

These organic groups may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group, and these may be linear or branched. The organic group in which the aryl group represented by R ₂ and R ₃ can be substituted with a hydrogen atom in the structure is usually a monovalent organic group, but when forming a cyclic structure described later, it is divalent or higher. Can be an organic group.

As the bond other than the bond between carbon and hydrogen (bond between C and H) of the hydrocarbon group in the organic group which can be substituted for the hydrogen atom in the aryl group represented by R ₂ and R ₃ , the effects of the present invention Is not particularly limited as long as is not impaired, and examples thereof 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 bond between carbon and hydrogen of the hydrocarbon group in the organic group includes an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, and an 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.

The substituent other than the hydrocarbon group in the organic group in which the aryl group represented by R ₂ and R ₃ can be substituted with the hydrogen atom in the structure is not particularly limited as long as the effects of the present invention are not impaired. Atom, hydroxyl, mercapto, sulfide, cyano, isocyano, cyanato, isocyanato, thiocyanato, isothiocyanato, silyl, silanol, alkoxy, alkoxycarbonyl, carbamoyl, thiocarbamoyl, nitro A, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonato group, phosphino group, phosphinyl group, phosphono group, phosphonat group, hydroxyimino group, saturated or unsaturated alkyl ether group, A saturated or unsaturated alkyl thioether 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. Hydrogen contained in the above substituent may be substituted by a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be any of linear, branched and cyclic. Among them, examples of the substituent other than 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 include 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 An acyloxy group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, a hydroxyimino group, a saturated or unsaturated alkyl ether group, a saturated or unsaturated alkylthioether group, an aryl ether group, and Arylthioate Group is preferred.

Further, two or more of the substituents which 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. May be used.

It is preferable to introduce at least one substituent capable of replacing the aryl group represented by R ₂ and R ₃ with a hydrogen atom in the structure to the photobase generator as an essential component of the present invention. That is, at least one of the substituents which the aryl group represented by R ₂ and R ₃ can substitute for a hydrogen atom in the structure is a halogen, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso 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 ammonium group, or an organic group. By introducing at least one of the above-mentioned substituents into a substituent capable of replacing the aryl group represented by the substituents R ₂ and R ₃ with a hydrogen atom in the structure, the light absorbed by the photobase generator can be reduced. The wavelength can be adjusted, and a desired wavelength can be absorbed by introducing a substituent. By introducing a substituent that extends the conjugated chain of the aromatic ring, the absorption wavelength can be shifted to a longer wavelength. Further, the solubility and the compatibility with the polymer precursor to be combined can be improved. This makes it possible to improve the sensitivity of the photosensitive resin composition while considering the absorption wavelength of the polymer precursor to be combined.

Examples of the substituent which the aryl group represented by R ₂ and R ₃ can substitute for a hydrogen atom 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; a carbon atom having 7 carbon atoms such as a phenoxymethyl group, a 2-phenoxyethyl group and a 4-phenoxybutyl group. To 26 aryloxyalkyl groups (-ROAr groups); aralkyl groups having 7 to 20 carbon atoms such as benzyl group and 3-phenylpropyl group; and 2 to 21 carbon atoms having cyano groups such as cyanomethyl group and β-cyanoethyl group. An alkyl group having 1 to 20 carbon atoms having a hydroxyl group such as a hydroxymethyl group; a methoxy group and an 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 acetamido group, a benzenesulfonamide group (C ₆ H ₅ SO ₂ NH—); and a carbon number such as a methylthio group and 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 and a benzoyl group; an ester group having 2 to 21 carbon atoms such as a methoxycarbonyl group and an acetoxy group (-COOR group and- An OCOR group); an aryl group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, and a tolyl group; an aryl group having 6 to 20 carbon atoms substituted by an electron-donating group and / or an electron-withdrawing group; It is preferable that the donating group and / or the electron-withdrawing group be a substituted benzyl group, a cyano group, and a methylthio group (—SCH ₃ ). The above alkyl moiety may be linear, branched or cyclic.

In the photobase generator as an essential component, when at least one of the substituents capable of replacing the aryl group represented by R ₂ and R ₃ with a hydrogen atom contained in the structure is a hydroxyl group, the 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 for a hydrogen atom having a group in the structure, it is preferable because solubility in a basic aqueous solution or the like can be improved and absorption wavelength can be extended.

In the formula (1), X represents an amine residue obtained by removing one hydrogen atom directly bonded to a nitrogen atom from a primary amine or a 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). No.

When a residue is obtained by removing a hydrogen atom from an amine compound having two amino groups in one molecule represented by the formula (a) or the formula (b), a residue obtained by removing a hydrogen atom from one amino group is used. It may be a valent residue or a divalent residue in which one hydrogen atom has been removed from both amino groups. The amine compound represented by (a) or the formula (b) is an amine compound having two amino groups in one molecule, and a hydrogen atom is converted from an amine compound having three amino groups in one molecule. In the case of removing a residue, it may be any of monovalent to trivalent residues, or in the case of removing a hydrogen atom from an amine compound having four amino groups in one molecule to obtain a residue, It may be any of monovalent to tetravalent residues. The same applies to a case where a hydrogen atom is removed from a compound having five or more amino groups in one molecule to form a residue.
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). ) To (n) are more preferably residues obtained by removing one hydrogen atom directly bonded to a nitrogen atom from the amine compounds represented by (n).

  The proportion of the silicon-based compound in the active energy ray-curable composition of the present invention and the photobase generator as an essential component is determined based on the stability of the composition, the transparency of the obtained cured film, abrasion resistance, and scratch resistance. It is designed from the viewpoints of adhesiveness and crack resistance. The photobase generator as an essential component 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 photobase generator as an essential component. .

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

The photoradical generator that can be used in combination with the active energy ray-curable composition of the present invention is a compound having a function of initiating radical polymerization by photoexcitation, such as a monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, a benzoin ether compound, An acylphosphine oxide compound, an aminocarbonyl compound and the like can be mentioned.
The photo-radical generator used in combination with the active energy ray-curable composition of the present invention is preferably an acetophenone compound, an acylphosphine compound or the like, and 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 is a cation that is irradiated with ultraviolet rays, far ultraviolet rays, an excimer laser such as KrF or ArF, or a radiation such as an X-ray or an electron beam. The cation is a compound that can serve as a polymerization initiator, and examples thereof include an aromatic iodonium complex salt and an aromatic sulfonium complex salt.
Specific examples of the aromatic iodonium complex salt include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and tolycumyliodonium tetrakis (Pentafluorophenyl) borate (trade name, Rhodosil PI2074, manufactured by Rhodia), di (4-tert-butyl) iodonium tris (trifluoromethanesulfonyl) methanide (trade name, CGI BBI-C1, manufactured by BASF), and the like.

  Specific examples of the aromatic sulfonium complex salt include 4-thiophenyldiphenylsulfonium hexafluoroantimonate (manufactured by San Apro Co., trade name: CPI-101A), thiophenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate ( 4- [4- (2-chlorobenzoyl) phenylthio] phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate (manufactured by ADEKA, trade name SP-172), manufactured by San Apro Corporation, 4 A mixture of aromatic sulfonium hexafluoroantimonate containing thiophenyldiphenylsulfonium hexafluoroantimonate (manufactured by ACETO Corporation USA, trade name CPI-6976) and trif Nylsulfonium tris (trifluoromethanesulfonyl) methanide (manufactured by BASF, trade name: CGI TPS-C1), tris [4- (4-acetylphenyl) sulfonylphenyl] sulfonium tris (trifluoromethylsulfonyl) methide (manufactured by BASF, product GSID 26-1), tris [4- (4-acetylphenyl) sulfonylphenyl] sulfoniumtetrakis (2,3,4,5,6-pentafluorophenyl) borate (manufactured by BASF, trade name Irgacure PAG290) and the like. No.

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 biguanidium, imidazole, pyridine, diamine, a derivative thereof, and the like upon irradiation with light such as ultraviolet light, and specific examples thereof. 9-anthrylmethyl-N, N-diethylcarbamate, (E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine, 1- (anisolaquinone-2-yl) ethylimidazolecarboxy , 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 1,2-diisopropyl-3- [bis (dimethylamino) methylene] guanidium-2- (3-benzoylphenyl) propionate, 1,2- Dicyclohexyl-4,4,5,5-tetramethylbiguani Um -n- butyl triphenyl borate, and the like. One of these photobase generators may be used alone, or two or more thereof may be used in combination.
As the photobase generator used in combination with the active energy ray-curable composition of the present invention, a compound that generates imidazole or biguanidium is preferable.

  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 proliferates and generates a base 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 provided for light irradiation is thick, or when the active energy ray-curable composition contains a large amount of dyes or pigments). And the like) is caused by the action of a base generated photochemically on the surface of the active energy ray-curable composition layer and the initiation of a base multiplication reaction by a base multiplying agent, resulting in thermochemical and chain reaction of the base. Is generated, so that a base catalyst reaction can be expected to occur even in the deep part of the active energy ray-curable composition layer. The base proliferating agent that can be used in combination is not particularly limited. Arimitsu, M .; Miyamoto and 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 kind or combination of the essential components such as a base generator and a silicon-based compound. It is preferably 40% by mass or less, more preferably 5 to 20% by mass in the composition.

A compound having an acryloyl group and / or a methacryloyl group may be used in combination with the active energy ray-curable composition of the present invention.
Examples of the compound 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, and t-butyl (meth). A) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobonyl (meth) acrylate, phenyl (meth) acrylate, benzyl (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxy 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-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 and acryloylmorpholine; N, N-dimethylaminoethyl (methyl ) Acrylates, amino group-containing (meth) acrylates such as 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, and 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) acrylates 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, isocyanate ethylene oxide-modified tri (meth) acrylate, isocyanate ethylene oxide-modified ε-caprolactone-modified tri (meth) acrylate 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.

Furthermore, polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, (meth) acrylated maleic acid-modified polybutadiene and the like can be mentioned.
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% by mass in the active energy ray-curable composition of the present invention. 50% by mass.

The active energy ray-curable composition of the present invention may be used in combination with a sensitizer in order to increase the absorption wavelength region of a photobase generator as an essential component and a photopolymerization initiator used in combination to increase sensitivity. Good. The sensitizer that can be used in combination is not particularly limited. 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, picramide, 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.
One of these sensitizers may be used in combination, or two or more of them may be used in combination.

  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 the silicon compound as essential components, and the sensitivity required for the active energy ray-curable composition. The amount may be appropriately determined, but is preferably 30% by mass or less, more preferably 5 to 20% by mass in the active energy ray-curable composition of the present invention.

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 can dissolve or disperse the silicon compound, but is preferably a solvent that can dissolve the silicon compound, and more preferably an alcohol solvent. Examples of the solvent that can be used in combination include, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-ethoxyethanol, and 2-butoxyethanol. Alcohols having 1 to 4 carbon atoms are 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 of the compound; esters such as ethyl acetate and butyl acetate; 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.

  To the active energy ray-curable composition of the present invention, known additives such as a leveling agent and an antifoaming agent can be blended for the purpose of improving coatability and smoothness and appearance of the obtained 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. Further, an ultraviolet absorber, a light stabilizer, a dye, a pigment, a filler, and the like may be blended as long as the object of the present invention is not impaired.

  The method of applying the active energy ray-curable composition of the present invention to a substrate (substrate) is a bar coating method, a dip coating method, a flow coating method, a spray coating method, a spin coating method, a roller coating method, a reverse coating method. Alternatively, any coating or printing method such as gravure printing, flexographic printing, screen printing, or inkjet printing is possible, and can be appropriately selected according to the shape of the base material.

  Further, the active energy ray-curable composition of the present invention can be used as a paint, an ink binder such as a gravure printing ink, a flexographic printing ink, an ink jet printing ink, and various adhesives including a lamination adhesive. 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 a light source of the active energy ray irradiation device, a light source including light in a range of usually 200 to 500 nm, for example, a light source having a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used. It is preferable to use a light source including light in a wavelength region of 350 nm or more. The integrated light quantity of the active energy ray is not limited because the required minimum integrated light quantity depends on the application, the film thickness, the presence or absence of a colorant, and the type and amount of the photopolymerization initiator. It is effective to use these ultraviolet rays and electron beams in combination with heat by infrared rays, far infrared rays, hot air, high frequency heating and the like.

  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 in such a range, the adhesiveness between the composition layer and the substrate does not decrease due to the stress generated at the time of curing. A cured product layer having excellent hardness, scratch resistance and abrasion resistance can be obtained.

[Cured film and method for producing cured film]
A method for producing a cured film obtained by 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) first heating the coating;
(C) exposing the heat-treated film; and (d) second heating the exposed film.

The coating in the step (a) is performed by a method such as the bar coating method described above. The film after the application and before the first heating of (b) is referred to as a coating film in this specification.
The first heating in the step (b) is performed by a device such as a hot plate or an oven, and the condition is usually 25 to 150 ° C. for 5 to 120 minutes, preferably 25 to 100 ° C. for 5 to 10 minutes.
The exposure treatment 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 the silicon-based compound and the type and content of the photobase generator as an essential component, and 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 condition is 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.

  The active energy ray-curable composition of the present invention is excellent in storage stability, curability and film forming properties, and the cured product is excellent in impact resistance and scratch resistance. It is suitably used for hard coat applications and the like.

  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 thereto. Further, “parts” used in this example means “parts by mass” unless otherwise specified.

<Synthesis Example 1 Synthesis of Intermediate Compound 1 of Photobase Generator 1 as an Essential Component Having Partial Structure Represented by Formula (1)>
10 parts of water and 53 parts of ethanol were added to and dissolved in 1.9 parts of potassium cyanide, and then the mixture was subjected to ultrasonic treatment in a nitrogen atmosphere to degas the reaction solution. To this solution, 10 parts of 4- (methylthio) benzaldehyde was added dropwise, and the mixture was heated at 80 ° C. to start 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 collected 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 an Essential Component Represented by Formula (1)>
To 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 the mixture was stirred until paraformaldehyde was completely dissolved. A solution obtained 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 the mixture was stirred at room temperature for 2 hours. Thereafter, 2.6 parts of 35% hydrochloric acid was added dropwise to neutralize, and the reaction was terminated. Toluene and saturated saline were added to the 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 an 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 parts of dicyclohexylmethane-4,4-diisocyanate was added at room temperature, and stirring was continued for 12 hours. After cooling, the solvent was distilled off by an evaporator. The obtained solution was dropped into cyclohexane, stirred for 30 minutes and washed to obtain 1.0 part of a photobase generator 1 represented by the following formula (IV).

<Synthesis Example 4 Synthesis of Intermediate Compound 3 of Photobase Generator 5 for Comparison>
To 11.9 parts of 1,1,3,3-tetramethylguanidine was added 13.1 parts of N, N′-diisopropylcarbodiimide, and the mixture was heated with stirring at 100 ° C. for 2 hours. After completion of the reaction, hexane was added to the reaction solution, the mixture was cooled to 5 ° C., and the obtained crystals were filtered to obtain an 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 the 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 obtained residue was washed with hexane and dried under reduced pressure to obtain 12.2 parts of a photobase generator 51 represented by the following formula (V) as a white solid. Was.

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

<Synthesis Example 7 Synthesis of Photobase Generator 6 for Comparison>
8.9 parts of the 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 refluxed and stirred 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 by an evaporator. By recrystallizing the obtained brown solid with ethanol, 6.8 parts of a photobase generator 6 represented by the following formula (VI) was obtained.

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

<Synthesis Example 9 Synthesis of Photobase Generator 7 for Comparison>
5.3 parts of photobase generator 7 represented by the following formula (VII) was 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)
0.3 parts of DPHA (manufactured by Nippon Kayaku), 0.075 parts of 3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-5103), and tetraethoxysilane (manufactured by Kanto Chemical Co., Ltd.) in a brown bottle After adding 0.3 part, 0.0175 part of the photobase generator 1 obtained in Synthesis Example 3 was added and diluted with 0.04 part of MEK to obtain an active energy ray-curable composition of the present invention. .

(Example 2)
Active energy ray curing of the present invention 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 the photopolymerization initiator 2 (Irg. 184) was added. A mold composition was obtained.

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

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

(Comparative Example 5)
An active energy ray-curable composition for comparison 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 photopolymerization initiator 2 (Irg. 184).

(Comparative Example 6)
An active energy ray-curable composition for comparison 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 photopolymerization initiator 3 (Irg. 369).

(Comparative Example 7)
An active energy ray-curable composition for comparison 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). Was.

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

(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 the photopolymerization initiator 2 (Irg. 184) was added. A mold composition was obtained.

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

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

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

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

  The composition of each of the active energy ray-curable compositions of Examples 1 to 4 to and Comparative Examples 5 to 11, and the results of evaluation of the compositions and the cured films obtained from the compositions by the following methods Are shown in Table 1.

(Evaluation method)
(1) Appearance of solution:
A test tube was filled with a solution of each of the active energy ray-curable compositions of Examples 1 to 4 and Comparative Examples 5 to 11, and the appearance was visually observed.
(2) Cured film appearance:
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 inspected for the presence or absence of turbidity, gloss, bumps, cracks, and the like. Confirmed.
(3) Pencil hardness:
The pencil hardness of the cured film of each composition obtained by using each of the active energy ray-curable compositions of Examples 1 to 4 and Comparative Examples 5 to 11 was applied under a load of 750 g by a method according to JIS K-5600. It was measured.
(4) Adhesion:
The adhesion of a 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 a PET film was determined by a method according to 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 scratched state of the surface was visually observed and evaluated according to the following evaluation criteria.
；: No scratch at all Δ: slightly scratched ×: 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 evaluated by the transmittance at a wavelength of 400 nm.
(7) Stability:
The solution of each of the active energy ray-curable compositions of Examples 1 to 4 and Comparative Examples 5 to 11 was sealed in a closed container, and the condition after being left in a constant temperature room at 25 ° C. for 3 months was observed. Evaluation was based on criteria.
○: no change ×: remarkable thickening or gelation

Absorbance of photopolymerization initiator (photobase generator):
A photopolymerization initiator (photobase generator) solution was prepared by dissolving 1 to 71.0 × 10 ⁻⁵ mol of the photopolymerization initiator (photobase generator) shown in Table 1 in 10 ml of THF. Using a whole pipette, 1 ml of the above-mentioned photopolymerization initiator (photobase generator) solution is fractionated, and the solution is again made up to 10 ml with THF, so that a photopolymerization initiator (photobase generator) for absorbance evaluation is obtained. A diluent was obtained. The absorbance of the photopolymerization initiators (photobase generators) 1 to 7 was measured using a quartz cell having an optical path length of 10 mm filled with the obtained photopolymerization initiator (photobase generator) diluent, and the absorbance was measured. Based on the results, the molar absorption coefficient ε was calculated by the following equation. FIG. 1 shows the measurement results of the absorbance, and Table 2 shows the calculated values of the molar extinction coefficient ε.
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 in Table 1, the active energy ray-curable composition of the present invention is superior in storage stability to the composition for comparison, excellent in the appearance of the solution and the cured film, and the cured product has high hardness. It can be seen that the adhesiveness to the PET film and the abrasion resistance are excellent, and the transmittance of light having a wavelength of 400 nm is excellent. The results in Table 2 show that the photopolymerization initiator used in the examples has a light absorption band of 350 nm or more.

  The active energy ray-curable composition of the present invention has excellent storage stability, curability and film-forming properties, and the cured product has high hardness and excellent adhesion to a substrate and excellent scratch resistance. Etc. are suitably used for hard coat applications such as liquid crystal display screens and touch panels.

Claims (7)

A silicon-based compound having an alkoxysilyl group, and a compound represented by the following formula (1) capable of absorbing light to simultaneously generate an amine and an active radical:
(In the 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 nitrogen atom from a primary amine or a secondary amine. (Residue except one hydrogen atom directly bonded.)
An active energy ray-curable composition comprising a photobase generator containing a compound represented by the formula:   The active energy ray-curable composition according to claim 1, wherein the photobase generator has an absorption in a wavelength region of 350 nm or more.   The active energy ray-curable composition according to claim 1, further comprising a photopolymerization initiator other than the compound represented by the 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.   The active energy ray-curable composition according to any one of claims 1 to 4, further comprising a compound having an acryloyl group and / or a methacryloyl group.   A cured product of the active energy ray-curable composition according to any one of claims 1 to 5. A method for producing a cured film obtained by 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) first heating the coating;
(C) exposing the first heated coating; and (d) second heating the exposed coating.