TW201900778A - Active energy ray-curable composition, method for producing cured film, and cured product - Google Patents

Abstract

The present invention provides an active energy ray-curable composition, a cured product of the composition, and a method for forming a cured film using the composition. The active energy ray-curable composition contains: a silicon system having an alkoxy silicon group. A compound, and a photobase generator containing a compound represented by a predetermined chemical formula capable of absorbing light and simultaneously producing an amine and an active radical. This active energy ray-curable composition is excellent in storage stability, hardenability, and film-forming properties, and is excellent in adhesion and scratch resistance of a cured material to a substrate.

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, a cured product of the composition, and a method for producing a cured film using the composition. The active energy ray-curable resin composition contains a compound having a specific structure. Photobase generator and silicon-based compound with specific structure.

In the fields of liquid crystal display screens of mobile communications such as mobile phones and PDAs, and touch panels used as screen display input devices such as ATMs and car navigators, they are often used for the purpose of preventing scratches on the display screens. Hard coats, but as the use of these display media expands, the requirements for surface protection of display media have become increasingly severe.

For such a hard coating material, a material having a high hardness is desired to improve the scratch resistance. For example, in a UV-curable organic hard coating material, a technique is known in which the crosslinking density is increased to increase the hardness and scratch resistance. However, in such a UV-curable hard coating material, the crosslinking density is increased by addition polymerization of an acrylic double bond, ring-opening polymerization of an epoxy ring, and the like. Shrinkage can be a problem, and using only organic ingredients to increase hardness has limits.

On the other hand, the characteristics of the inorganic coating material typified by polysiloxane include excellent heat resistance, weather resistance, hardness, and abrasion resistance compared with organic coating materials. In the method for forming a thin film coating layer of such an inorganic coating material, a metal alkoxide is hydrolyzed / polycondensed by a melt-gel reaction, and is heated at a relatively low temperature through a metalloxane oligomer. The method of crosslinking / hardening has been put into practical use, and the obtained film coating has high hardness.

Patent Document 1 discloses a coating composition composed of a trihydroxysilane partial condensation product and colloidal silicon dioxide. However, a thermosetting coating material requires a large amount of thermal energy during hardening, so it is uneconomical, and there are problems such as deformation of the base material due to heat applied.

In order to solve these problems, a UV-curable organic-inorganic coating material is needed, which can make use of the excellent properties of UV-curable organic coating materials such as hardening, transparency, substrate suitability, processability, and inorganic materials. It has excellent characteristics such as high hardness and abrasion resistance, and makes up for its respective disadvantages.

Patent Document 2 discloses a composition composed of silica particles, acryloxy functional silane, or a hydrolyzate thereof, and an acrylate compound. However, the composition of this document which is hardened by a photopolymerization initiator does not take into account the light hardening of the silica particles and the silane site, so the hardness of the hardened material is insufficient.

Patent Document 3 discloses a method for introducing a polymerizable functional group on the surface of particles such as silicon dioxide. However, in addition to the difficulty in producing such modified silicon dioxide, a compound used for introducing a polymerizable functional group must have a hydroxyl group or the like. The reactive group has a low degree of freedom in design, and the use of silicon dioxide or the like obtained in this way has a limitation in improving the hardness of the hardened material of the composition.

In addition, the above-mentioned composition is for the purpose of improving the hardness and scratch resistance, and does not take into consideration other characteristics such as crack resistance, flexibility, processability, and flame retardancy.

That is, among the UV-curable organic-inorganic coating materials, the UV-curable organic is excellent in storage stability, has no problem in hardenability and film formation, and has excellent impact resistance and scratch resistance. It also has various physical properties of organic polymers. -Inorganic coating materials have not yet been put into practical use. In order to solve these problems at the same time, an organic-inorganic hybrid hardened film that is made to harden inorganic and organic components at the same time and is uniformly integrated with inorganic components and organic components through covalent bonds is being explored. technology.

Patent Document 4 discloses an organic-inorganic hybrid coating composition containing a radical photopolymerization initiator and a cationic photopolymerization initiator. However, the composition of this document must contain two different photopolymerization initiators. As a result, the amount of the photopolymerization initiator in the composition is increased to increase the price of the composition, which is not preferable.

In addition, since the cationic photopolymerization initiator has high activity and is unstable, it is necessary to consider not only the storage stability of the composition but also the corrosion of the metal caused by the acid generated by light irradiation remaining in the hardened material. In addition, when a SiOR group is left at the terminal, this hydrolysis becomes a rate-determining step, and the resulting alcohol may deteriorate the radical or cationic photopolymerization initiator and cause poor curing of the composition. .

In order to solve these problems, introduction of an anionic UV curing system is being investigated in recent years. The anion generated by the photobase generator directly acts nucleophilically on the SiOR group, and can quickly generate SiOH.

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

Patent Document 6 discloses a photobase generator that generates both bases and radicals upon irradiation with active light. However, the photobase generator in this document is an ionic compound composed of a carboxylic acid and an amine. The tertiary amine generated by irradiation with active energy rays is highly active and unstable, so it has storage stability and solubility. In addition, the tertiary amine is difficult to control the reaction of SiOH due to the hydrolysis of the alkoxysilyl group, so there is a problem that the molecular weight of the hydrolyzed condensate of the alkoxysilane cannot be controlled. Therefore, a photobase generator capable of simultaneously producing an aliphatic primary or secondary amine and a neutral compound of an active radical by irradiation with active energy rays is desired.

In order to solve these problems, in Non-Patent Documents 1 and 2, a photobase generator comprising a neutral compound that simultaneously produces an aliphatic primary or secondary amine and an active radical, and a silicon system having an alkoxysilyl group have been discussed. A resin composition composed of a compound and a cured product thereof. However, the absorption wavelength of the active energy ray of the photobase generator disclosed in these documents is a short wavelength. Therefore, it is desired to develop a higher sensitivity to longer-wavelength light (active energy ray) than the photosensitive region of conventional photo-alkali generators, and to efficiently generate alkali by irradiation with this long-wavelength light. Light alkali generator.

    [Prior technical literature]         [Patent Literature]    

[Patent Document 1] Japanese Patent Publication No. 52-039691

[Patent Document 2] Japanese Patent Laid-Open No. 62-256874

[Patent Document 3] Japanese Patent No. 3474330

[Patent Document 4] Japanese Patent No. 5063915

[Patent Document 5] Japanese Patent Laid-Open No. 2009-58923

[Patent Document 6] Japanese Patent Laid-Open No. 2011-202160

    [Non-patent literature]    

[Non-Patent Document 1] J. Photopolym. Sci. Technol., Vol. 27, No. 2, 223-225 (2014)

[Non-Patent Document 2] Chem. Lett. 2014, 43, 612-614

An object of the present invention is to provide an active energy ray-curable composition having excellent storage stability, hardenability, and film-forming properties, and a cured product having high hardness and excellent adhesion to a substrate and scratch resistance. .

As a result of investigations made by the present inventors, it has been found that the following active energy ray-curable composition solves the above-mentioned problems and has completed the present invention. Sensitivity and a photobase generator that simultaneously generates an aliphatic primary or secondary amine and a neutral compound of an active radical by irradiation with active energy rays, and a silicon-based compound having an alkoxysilyl group.

That is, the present invention relates to the following: (1) An active energy ray-curable composition containing: a silicon-based compound having an alkoxysilyl group; The photobase generator of the compound represented by formula (1), (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 the removal of one from a primary amine or a secondary amine A residue obtained by directly bonding a hydrogen atom of a nitrogen atom); (2) the active energy ray-curable composition according to item (1), wherein the photobase generator has absorption in a wavelength range of 350 nm or more (3) the active energy ray-curable composition according to item (1) or (2), further comprising a photopolymerization initiator other than the compound represented by formula (1); (4) as (1) The active energy ray-curable composition according to any one of items (3), which further contains a compound having at least one amine ester bond as an alkaline proliferation agent; (5) As in items (1) to (4), The active energy ray-curable composition according to any one of the above, further comprising a compound having an acryloyl group and / or a methacryl group; (6) a hardened product, which is the item (1) to (5) of the preceding item A cured product of the active energy ray-curable composition according to any one; and (7) A method for producing a cured film, wherein the cured film is any one of the items (1) to (5) Active energy The manufacturing method includes: (a) a step of applying the active energy ray-curable composition to a substrate to form a film, (b) a step of first heating the film, and (c) ) A step of exposing the first heated film and (d) a step of second heating the exposed film.

The active energy ray-curable composition of the present invention is suitable because it has excellent storage stability, hardenability, and film-forming properties, and its hardened product has high hardness and excellent adhesion to the substrate and abrasion resistance. Used for hard coating applications such as liquid crystal display screens for mobile phones and touch panels.

FIG. 1 is an absorbance curve of photobase generators (photopolymerization initiators) 1 to 7 used as materials of 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 embodiment.

    [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 referred to as "silicon-based compound") contained in the active energy ray-curable composition of the present invention include, for example, a silane coupling agent having 1 to 3 alkoxysilyl groups. , An alkoxysilane compound having 1 to 4 alkoxysilyl groups, etc., a part of the alkoxysilyl group can be hydrolyzed or hydrolyzed and 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 viewpoints of reactivity and stability. Specifically, the alkoxy group is a methyl group. Oxy, ethoxy, (iso) propoxy or (iso) butoxy is preferred, and methoxy or ethoxy is more preferred. In addition, in this specification, the description of "(iso) propyl" means both n-propyl and isopropyl. The aforementioned silane coupling agent may have a functional group other than an alkoxysilyl group, and the functional group that may have is preferably an amine group, an epoxy group, a mercapto group, an isocyanate group, or a hydroxyl group, and more preferably an amine group .

Specific examples of the silane coupling agent having an alkoxysilyl group include 3-propenyloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3 -Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; 3-aminopropyltriethoxysilane, 3-aminopropyltrimethylsilane Oxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane And 3- (N-phenylaminopropyltrimethoxysilane) and other aminosilanes; 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyl Epoxy silanes such as trimethoxysilane and 3-glycidoxypropyltriethoxysilane; 3-mercaptopropyltrimethoxysilane Mercaptosilane such as 3-mercaptopropyltriethoxysilane; thiosilane such as 3-octylthio-1-propyltriethoxysilane; 3-isocyanatepropyltriethoxysilane and 3-isocyanatepropyltrimethylsiloxane Isocyanates such as oxysilanes, etc. These silane coupling agents may be used singly or in combination of two or more, and may be partially hydrolyzed or hydrolyzed polycondensed in advance.

Specific examples of the alkoxysilane compound include trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, and methyldimethoxysilane , Trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetraethoxysilane, diphenyldimethoxysilane, phenyltrimethoxysilane, diphenyl Didiethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, tetrapropoxysilane and tetrabutoxysilane. These alkoxysilane compounds may be used singly or in combination of two or more kinds, and those in which partial hydrolysis or hydrolysis polycondensation is applied in advance may also be used.

The silicon-based compound contained in the active energy ray-curable composition of the present invention includes 3-propenyloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, trimethylmethoxysilane, dimethyldimethoxysilane, methyl Trimethoxysilane, tetramethoxysilane, methyldimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane or tetraethoxysilane It is better to use 3-propenyloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane 3-methacrylic acid Propyl methyl diethoxy Silane, 3-Bing Xixi propyl triethoxysilane Silane, Silane tetramethoxysilane, tetramethoxysilane Silane or tetraethyl orthosilicate is more preferred.

    [Photo base generator]    

The active energy ray-curable composition of the present invention contains a photobase generator. The photobase generator preferably has absorption in a wavelength range of 350 nm or more, and is a specific one that absorbs light and simultaneously produces amines and active radicals. Photobase generator (hereinafter also referred to as "essential 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 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} formula (1) is preferably an alkoxy group having 1 to 18 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group. , N-butoxy, isobutoxy, second butoxy, third butoxy, n-pentyloxy, isopentyloxy, neopentyloxy, n-hexyloxy and n-dodecyloxy, etc. .

Specific examples of the organic group represented by R _{1 in} 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 6 to 12 carbon atoms. Aryl, fluorenyl having 1 to 18 carbons, arylfluorenyl having 7 to 18 carbons, nitro, cyano, alkylthio having 1 to 18 carbons, halogen atoms, and the like.

Examples of the alkyl group having 1 to 18 carbon atoms as a specific example of the organic group represented by R _{1 in} formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Straight-chain, such as alkyl, second butyl, third butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl Or branched-chain alkyl groups, and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl, preferably an alkyl group having 2 to 6 carbon atoms, and 2 to 6 carbon atoms The linear or branched alkyl group is more preferable.

Specific examples of the carbon atoms of the alkenyl group of formula (1) wherein R ₁ represents an organic group of 2 to 18 in terms include ethenyl, propenyl, 1-butenyl, isobutenyl, 1-pentenyl , 2-pentenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 2-methyl-2-butenyl, 2,2-dicyanovinyl, 2-cyano-2-methylcarboxyvinyl, 2-cyano-2-methylfluorenyl vinyl, and the like.

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

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

Specific examples of the fluorenyl group having 1 to 18 carbon atoms of the organic group represented by R _{1 in} formula (1) include methyl fluorenyl, ethyl fluorenyl, ethylcarbonyl, n-propylcarbonyl, and isopropyl Carbonyl, n-butylcarbonyl, n-pentylcarbonyl, isopentylcarbonyl, neopentylcarbonyl, 2-methylbutylcarbonyl, and nitrobenzylcarbonyl.

Specific examples of the carbon atoms of the aryl acyl terms of the formula (1) wherein R ₁ represents an organic group of 7-18, and may include a benzoyl group, a toluyl acyl (toluoyl), and o-acyl naphthalene Benzalhexyl and the like.

Examples of the alkylthio group having 1 to 18 carbon atoms in specific examples of the organic group represented by R _{1 in the} formula (1) include methylthio group, ethylthio group, n-propylthio group, and isopropyl group. Methylthio, n-butylthio, isobutylthio, second butylthio, third butylthio, n-pentylthio, isoamylthio, 2-methylbutylthio , 1-methylbutylthio, neopentylthio, 1,2-dimethylpropylthio, 1,1-dimethylpropylthio, and the like.

Specific examples of the halogen atom 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 the formula (1) is preferably an alkoxy group, more preferably an alkoxy group having 1 to 18 carbon atoms, and more preferably an alkoxy group having 1 to 6 carbon atoms, and more preferably carbon Alkoxy groups of 1 to 4 are particularly preferred, and methoxy groups are most preferred.

In formula (1), R ₂ and R ₃ represent an aryl group, and the hydrogen atom which the aryl group has in its structure may be substituted with 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) refers to a residue obtained by removing one hydrogen atom from an aromatic hydrocarbon. Specific examples of the aromatic hydrocarbon include benzene, naphthalene, anthracene, phenanthrene, Wait

R ₂ and R ₃ in the formula (1) are preferably residues obtained by removing one hydrogen atom from benzene or naphthalene, and more preferably residues obtained by removing one hydrogen atom from benzene.

Specific examples of the substituent which can replace the hydrogen atom of the aryl group represented by R ₂ and R _{3 in the} formula (1) include a halogen atom, a hydroxyl group, an alkoxy group, a mercapto group, a sulfide group, and silicon. Group, silanol, nitro, nitroso, cyano, sulfinate, sulfonate, sulfonato, phosphinyl, phosphinyl, phosphono, When there are several phosphonato, amine, ammonium, or organic groups, and R ₂ and R ₃ exist, the respective R ₂ and R ₃ may be the same as each other or different from each other.

Examples of the halogen atom that can replace the hydrogen atom 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 which may replace the hydrogen atom of the aryl group represented by R ₂ and R _{3 in the} formula (1) in the structure include the same alkoxy groups as those represented by R _{1 in the} formula (1).

Specific examples of the organic group that can replace the hydrogen atom of the aryl group represented by R ₂ and R _{3 in the} formula (1) include alkyl, aryl, aralkyl, halogenated alkyl, and isocyanate. Cyanato, cyanato, isocyanato, thiocyanato, isothiocyanato, alkoxycarbonyl, carbamoyl, aminethiocarbamyl, carboxyl, Carboxylate, fluorenyl, fluorenyl, hydroxyimino and the like.

Specific examples of the alkyl group, the aryl group, and the fluorenyl group as an organic group that can replace a hydrogen atom in the structure of the aryl group represented by R ₂ and R ₃ represented by the formula (1) include an alkyl group, an aryl group, and a fluorenyl group, respectively. Specific examples of the organic group represented by R _{1 are the same} as the alkyl group having 1 to 18 carbon atoms, the aryl group having 6 to 12 carbon atoms, and the fluorenyl group having 1 to 18 carbon atoms.

The organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. These groups may be linear or branched. The organic group which can substitute a hydrogen atom in the structure of the aryl group represented by R ₂ and R ₃ is usually a monovalent organic group, but may form a bivalent or higher valence when forming a cyclic structure described later. Organic.

The bond other than the carbon-hydrogen bond (C-H bond) of the hydrocarbon group in the organic group of the hydrogen atom that the aryl group represented by R ₂ and R ₃ may have in the structure, as long as it does not harm the present The effect of the invention is not particularly limited, and examples thereof include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, a sulfonium bond, an amine ester bond, a carbonate bond, a sulfonyl bond, and a sulfinyl sulfonate Base bond, azo bond, etc. In terms of heat resistance, the bond other than the carbon and hydrogen bond of the hydrocarbon group in the organic group is an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amidine bond, an amine ester bond, Imino bond (-N = C (-R)-, -C (= NR)-: where R is a hydrogen atom or an organic group), carbonate bond, sulfonyl bond, and sulfinyl bond are preferred .

A substituent other than the hydrocarbon group in the organic group of the hydrogen atom which the aryl group represented by R ₂ and R ₃ may have in the structure is not particularly limited as long as the effect of the present invention is not impaired, and a halogen atom may be mentioned. , Hydroxyl, mercapto, sulfide, cyano, isocyano, cyano, isocyano, cyanothio, isothiocyano, silyl, silanol, alkoxy, alkoxycarbonyl, Carbamate, Aminothiomethane, Nitro, Nitroso, Carboxylate, Carboxylate, Carbothio, Carbooxy, Sulfinyl, Sulfonate, Sulfonate, Phosphino, Phosphinofluorene Group, phosphonium group, phosphonate group, hydroxyimide group, saturated or unsaturated alkyl ether group, saturated or unsaturated alkyl thio ether group, aryl ether group, and aryl thio ether group, amine group (-NH ₂ , -NHR, -NRR ': Here, R and R' are each independently a hydrocarbon group), an ammonium group, and the like. The hydrogen contained in the substituent may be substituted with a hydrocarbon group. The hydrocarbon group contained in the substituent may be any of linear, branched, and cyclic. Among these, substituents other than the hydrocarbon group in the organic group of the hydrogen atom which the aryl group represented by R ₂ and R ₃ may have in the structure are halogen atoms, hydroxyl groups, mercapto groups, sulfide groups, cyano groups, and isocyanates. Cyano, cyano, isocyano, cyanothio, isothiocyano, silyl, silanol, alkoxy, alkoxycarbonyl, carbamoyl, sulfamoyl, nitro, Nitroso, carboxyl, carboxylate, fluorenyl, fluorenyloxy, sulfinyl, sulfonate, sulfonate, phosphine, phosphinylfluorenyl, phosphinofluorenyl, phosphonate, hydroxyimino , Saturated or unsaturated alkyl ether groups, saturated or unsaturated alkyl thio ether groups, aryl ether groups and aryl thio ether groups are preferred.

Moreover, two or more of the substituents which may substitute for the hydrogen atom which the aryl group represented by R ₂ and R ₃ has in the structure may be bonded to form a cyclic structure. The cyclic structure may be a saturated or unsaturated alicyclic hydrocarbon, a heterocyclic ring, and a fused ring, and a combination of two or more types selected from the group consisting of the alicyclic hydrocarbon, a heterocyclic ring, and a fused ring. .

In the photobase generator of the essential component of the present invention, it is preferable to introduce a substituent which can substitute for one or more hydrogen atoms in the structure of the aryl group represented by R ₂ and R ₃ . That is, at least one of the substituents which can replace the hydrogen atom which the aryl group represented by R ₂ and R ₃ has in the structure is halogen, hydroxyl, mercapto, sulfide, silyl, silanol, nitro, Nitroso, sulfinate, sulfonate, sulfonate, phosphine, phosphinylphosphonium, phosphinophosphonium, phosphonate, amine, ammonium or organic groups are preferred. The wavelength of the light absorbed by the photobase generator can be adjusted by introducing at least one substituent as described above to the substituent of the hydrogen atom that the aryl group represented by the replaceable substituents R ₂ and R ₃ has in the structure. A desired wavelength can be absorbed by introducing a substituent. By introducing a substituent such as a conjugated chain extending an aromatic ring, the absorption wavelength can be converted to a long wavelength. In addition, it can also improve solubility and compatibility with the polymer precursor to be combined. Thereby, the sensitivity of the photosensitive resin composition can be improved while considering the absorption wavelength of the polymer precursor to be combined.

Substituents that can substitute for hydrogen atoms in the structure of the aryl group represented by R ₂ and R ₃ are alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, and propyl; cyclopentyl, cyclohexyl, etc. Cycloalkyl groups of 4 to 23 carbons; cycloalkenyl groups of 4 to 23 carbons such as cyclopentenyl, cyclohexenyl; phenoxymethyl, 2-phenoxyethyl, 4-phenoxybutyl Aryloxyalkyl groups (-ROAr group) having 7 to 26 carbons such as aryl groups; arylalkyl groups having 7 to 20 carbons such as benzyl and 3-phenylpropyl groups; cyanomethyl, β-cyanoethyl Alkyl groups having 2 to 21 carbon atoms such as cyano; alkyl groups having 1 to 20 carbon atoms having hydroxyl groups such as hydroxymethyl; alkoxy groups 1 to 20 carbon atoms such as methoxy and ethoxy Amidino, benzenesulfonamido (C ₆ H ₅ SO ₂ NH-) and other fluorenyl groups having 2 to 21 carbon atoms; methylthio, ethylthio and other alkylthio groups having 1 to 20 carbon atoms (-SR group); ester groups having 2 to 21 carbon atoms, such as fluorenyl, methoxycarbonyl, and ethoxyl groups, such as ethenyl, benzamidine, and the like (-COOR and -OCOR groups) ); Aryl groups having 6 to 20 carbon atoms such as phenyl, naphthyl, biphenyl, tolyl, etc .; aryl groups having 6 to 20 carbon atoms substituted with an electron donating group and / or an electron attracting group; A benzyl group, a cyano group, and a methylthio group (-SCH ₃ ) substituted with an electron-donating group and / or an electron-attracting group are preferred. The above-mentioned alkyl moiety may be linear, branched, or cyclic.

In addition, in the photobase generator of the essential component, when at least one of the substituents which can replace the hydrogen atom of the aryl group represented by R ₂ and R ₃ in the structure is a hydroxyl group, it is represented by the same as that which can substitute R ₂ and R ₃ . Compared with a compound which does not contain a hydroxyl group in the substituent of a hydrogen atom in the aryl group, it is more preferable in terms of improving the solubility in an alkaline aqueous solution and the longer the absorption wavelength.

In the formula (1), X represents an amine residue obtained by removing a 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 those obtained by removing a hydrogen atom directly bonded to a nitrogen atom from an amine compound represented by the following formulae (a) to (z). Amine residue.

When a hydrogen atom is removed from an amine compound having two amine groups in one molecule represented by formula (a), formula (b), etc. to form a residue, it may be a monovalent value obtained by removing a hydrogen atom from a monoamine group. The residue may be a divalent residue obtained by removing one hydrogen atom from each of the two amine groups. The amine compounds represented by the formulas (a), (b) and the like are amine compounds having two amine groups in one molecule, but hydrogen atoms are removed from the amine compounds having three amine groups in one molecule to form residues. In the case of a radical, it may be a residue of any of one to three valences. When a hydrogen atom is removed from an amine compound having four amine groups in one molecule to form a residue, it may be a residue of any of one to four valences. . The same applies when a hydrogen atom is removed from a compound having five or more amine 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 a hydrogen atom directly bonded to a nitrogen atom from the amine compound represented by the formulae (a) to (z). A residue obtained by removing a hydrogen atom directly bonded to a nitrogen atom from the amine compound represented by the formulae (a) to (n) is more preferable.

The proportion of the silicon-based compound in the active energy ray hardening composition of the present invention and the photobase generator of the necessary components depends on the stability of the composition, the transparency of the obtained hardened film, abrasion resistance, and abrasion resistance. , Adhesiveness and crack resistance. Relative to the total amount of the silicon-based compound and the photobase generator of the essential component, the photobase generator of the essential component is usually 5 to 80% by mass, preferably 10 to 60% by mass, and 20 to 40% by mass as Better.

    [Photopolymerization initiators that can be used in combination]    

In the active energy ray-curable composition of the present invention, a photopolymerization initiator other than a compound having a partial structure represented by formula (1) may be used in combination. Examples of the photopolymerization initiator that can be used in combination include conventionally known photo radical generators, photoacid generators, and photobase generators. These photopolymerization initiators may be used singly or in combination of two or more kinds.

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 of starting radical polymerization by photoexcitation, and examples thereof include a monocarbonyl compound, a dicarbonyl compound, and phenethyl Ketone compounds, benzoin ether compounds, fluorenylphosphine oxide compounds, aminocarbonyl compounds, and the like.

The photo-radical generator used in combination with the active energy ray-curable composition of the present invention is preferably an acetophenone compound, a fluorenylphosphine oxide compound, or the like from the viewpoint of the transparency of the cured product. Acetophenone compounds are more preferred.

The photoacid generator that can be used in combination with the active energy ray-curable composition of the present invention refers to the generation of cations upon irradiation with radiation such as ultraviolet, far ultraviolet, KrF, or ArF excimer lasers, X-rays, and electron beams. This cationic compound can be used as a polymerization initiator, and examples thereof include an aromatic salt and an aromatic salt.

Specific examples of the aromatic ammonium salt include diphenylammonium (pentafluorophenyl) borate, diphenylammonium hexafluorophosphate, diphenylammonium hexafluoroantimonate, and bis (4-nonyl). Phenyl) fluorene hexafluorophosphate, tolyl isopropyl phenyl (pentafluorophenyl) borate (manufactured by Rhodia, trade name RHODOSIL PI2074), bis (4-third butyl) ) Ginseng (trifluoromethanesulfonyl) methylate (manufactured by BASF, trade name CGI BBI-C1) and the like.

Specific examples of the aromatic ammonium salt include 4-thienyldiphenylsulfonium hexafluoroantimonate (manufactured by San Apro, trade name CPI-101A), thienyldiphenyl ginseng (pentafluoroethyl) ) Trifluorophosphate (manufactured by San Apro, trade name CPI-210S), 4- [4- (2-chlorobenzyl) phenylthio] phenylbis (4-fluorophenyl) fluorene Antimonate (manufactured by ADEKA Corporation, trade name SP-172), a mixture of aromatic thallium hexafluoroantimonate containing 4-thienyldiphenylphosphonium hexafluoroantimonate (produced by ACETO Corporate USA, brand name CPI- 6976), and triphenylpyrene (trifluoromethanesulfonyl) methylate (manufactured by BASF, trade name CGI TPS-C1), and [4- (4-ethylfluorenylphenyl) sulfonylphenyl ] Ginseng (trifluoromethylsulfonyl) methylate (manufactured by BASF, trade name CGID 26-1), Ginseng [4- (4-ethylfluorenylphenyl) sulfonylphenyl]] ( 2,3,4,5,6-pentafluorophenyl) borate (manufactured by BASF, trade name IRGACURE PAG290) and the like.

The photo-alkali generator that can be used in combination with the active energy ray-curable composition of the present invention refers to the production of biguanidium, imidazole, pyridine, diamine, and derivatives thereof by irradiation with light such as ultraviolet rays. Specific examples of the compound include 9-anthrylmethyl-N, N-diethylcarbamate, (E) -1- [3- (2-hydroxyphenyl) -2-propenylmethyl ] Piperidine, 1- (anthraquinone-2-yl) ethyl imidazolate, 4-methacryloxyoxypiperidine-1-carboxylic acid 2-nitrophenylmethyl ester, 1,2-diisopropyl -3- [bis (dimethylamino) methylene] guanidine-2- (3-benzylidenephenyl) propionate, 1,2-dicyclohexyl-4,4,5,5- Tetramethyldiguanidine-n-butyltriphenylborate and the like. These photobase generators may be used singly or in combination of two or more kinds.

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 diguanide.

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.

In the active-energy-ray-curable composition of the present invention, a base multiplying agent that proliferates a base by the action of a base may be used in combination. By using the alkaline proliferative 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. Especially when light fails to reach the deep part of the active energy ray-curable composition layer (when the active energy ray-curable composition layer irradiated with light is thick, the active energy ray-curable composition contains a large amount of dye, For pigments, etc.), the photochemically generated alkali on the surface of the active energy ray-curable composition layer and the alkali multiplication reaction caused by the alkali multiplier begin to proceed, and thermochemically and indirectly Alkali, an alkali catalyst reaction is expected to occur even in deep portions of the active energy ray-curable composition layer. The alkali multiplying agent that can be used in combination is not particularly limited, and examples thereof include Japanese Patent Laid-Open No. 2000-330270, Japanese Patent Laid-Open No. 2002-128750, and K. Arimitsu, M. Miyamoto, and K. Ichimura, Angew. Chem. Int. Ed., 39, 3425 (2000), etc., it is preferred that the base multiplying agent contains a compound having at least one amine ester bond.

The content of the alkali multiplying agent in the active energy ray-curable composition of the present invention may be appropriately determined depending on the type and combination of an alkali generator, a silicon-based compound, and the like, which are essential components. The hardening type composition is preferably 40% by mass or less, and more preferably 5 to 20% by mass.

In the active energy ray-curable composition of the present invention, a compound having an acrylfluorene group and / or a methacrylfluorene group may be used in combination.

Examples of the compound having acrylfluorenyl and / or methacrylfluorenyl include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and n-butyl (meth) acrylate Ester, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate , Lauryl (meth) acrylate, tetrahydroxyfuran methyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, (meth) Alkoxy polymer such as phenoxyethyl acrylate, phenoxyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate Butanediol (meth) acrylates; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth) acrylic acid Glyceryl ester, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate and other hydroxyl-containing (meth) acrylates; (meth) acrylamide, N, N-dimethyl ( (Meth) acrylamide , N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acrylmorpholine, etc. Acrylamides; amine-containing (meth) acrylic acids such as N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate Esters; nitriles such as (meth) acrylonitrile; styrenes such as styrene and α-methylstyrene; ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl Vinyl ethers such as vinyl ether and isobutyl vinyl ether; fatty acid vinyl esters such as vinyl acetate and vinyl propionate; 1,6-hexanediol di (meth) acrylate, neopentyl glycol Alkanediol di (meth) acrylates such as di (meth) acrylate, polyethylene glycol di (meth) acrylate; glycerol propylene oxide modified tri (meth) acrylate, trimethylolpropane Tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, isotricyanic acid Ethylene oxide modified tri (meth) acrylate, iso Polyethylene oxide modified cyanate ε- caprolactone-modified tri (meth) acrylate, 1,3,5-hexahydro-yl -S- three Bing Xixi Trifunctional (meth) acrylates such as neopentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate tripropionate; neopentaerythritol tetra (meth) acrylate Ester, dipentaerythritol penta (meth) acrylate monopropionate, dipentaerythritol hexa (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, oligoester tetra (a) Polyfunctional (meth) acrylic acid esters such as methacrylic acid esters, ginseng ((meth) acryloxy) phosphate, PPZ.

In addition, polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, (meth) acrylated maleic acid modified polybutadiene, and the like are mentioned.

The content of the compound having an acryl group and / or a methacryl group in the active energy ray-curable composition of the present invention is preferably 80% by mass or less in the active energy ray-curable composition of the present invention. And more preferably 5 to 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 range of the photobase generator of the necessary components and the photopolymerization initiator used in combination to increase sensitivity. The sensitizer that can be used in combination is not particularly limited, and examples thereof include benzophenone, p, p'-tetramethyldiaminobenzophenone, and p, p'-tetraethylaminobenzophenone. Ketones, 2-chlorothiaxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, pyrene, pyrene , Benzil, acridine orange, benzoxanthin, thioflavin-T (setoflavin-T), 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroethanenaphthalene, benzoquinone, 2-chloro-4-nitroaniline, N-ethylfluorenyl-p-nitroaniline, p-nitroaniline, N-acetamidine 4-nitro-1-naphthylamine, 2,4,6-trinitroaniline (picramide), anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1,2- Benzoanthraquinone, 3-methyl-1,3-diaza-1,9-benzoanthrone, diphenylmethyleneacetone, 1,2-naphthoquinone, 3,3'-carbonyl-bis ( 5,7-dimethoxycarbonylcoumarin) or cardamom.

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 is appropriately determined depending on the type and amount of the alkali generator, the silicon-based compound, and the required sensitivity of the active-energy-ray-curable composition. It may be determined, but it is preferably 30% by mass or less in the active energy ray-curable composition of the present invention, and 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. The solvent that can be used in combination is not particularly limited as long as it is a solvent that can dissolve or disperse the silicon-based compound, but a solvent that dissolves the silicon-based compound is preferred, and an alcohol-based solvent is more preferred. Examples of solvents 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 -Butoxy ethanol and the like are preferably alcohols having 1 to 4 carbon atoms, and in terms of solubility, stability, and coatability, 2-propanol is more preferable.

Further, when a compound having an acryl group or a methacryl group is used in combination, ketones such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK), which are good solvents of the compound, are preferably used; acetic acid Ester such as ethyl acetate, butyl acetate; glycol ethers; glycol ether esters; aromatic hydrocarbons.

The content of the solvent in the active energy ray-curable composition of the present invention is preferably 80% by mass or less, and 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, conventional additives such as a leveling agent and an antifoaming agent may be blended for the purpose of improving the coatability and the 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. Moreover, as long as the objective of this invention is not impaired, you may mix | blend an ultraviolet absorber, a light stabilizer, a dye, a pigment, a filler, etc.

The method for applying the active energy ray-curable composition of the present invention to a substrate (substrate) may be a bar coating method, a dip coating method, a flow coat method, a spray method, a spin coating method, or a roll coating method. Any method of coating and printing such as reverse coating or gravure printing, flexographic printing, screen printing, and inkjet printing can be appropriately selected according to the shape of the substrate.

The active energy ray-curable composition of the present invention can be used as a printing ink adhesive such as paint, gravure printing ink, flexographic printing ink, inkjet printing ink, and various adhesives including a laminating adhesive. . The active energy ray-curable composition of the present invention can be hardened by a conventional active energy ray hardening method, and it is particularly preferable to use ultraviolet rays or electron beams.

As the light source of the active energy ray irradiation device, a light source containing light in a range of 200 to 500 nm can be generally used, for example, those having high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halogen lamps, gallium lamps, xenon lamps, carbon arc lamps, etc. A light source of light in a wavelength range above 350 nm is preferred. The cumulative amount of light of the active energy ray is not limited because the minimum cumulative amount of light depends on the application, film thickness, presence or absence of colorants, and type and amount of photopolymerization initiator. The combination of these ultraviolet rays, electron beams, and heat caused by infrared rays, far infrared rays, hot air, and high-frequency heating 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 this range, the adhesion between the composition layer and the substrate does not decrease due to the stress generated during curing, and the object of the present invention can have sufficient hardness, Scratch-resistant, abrasion-resistant hardened layer.

    [Cure film and method for producing cured film]    

The method for producing a cured film using the active energy ray-curable composition of the present invention is a production method including the following steps. (A) A step of applying the active energy ray-curable composition to a substrate to form a film. (B) a step of first heating the film, (c) a step of exposing the heat-treated film, and (d) a step of second heating the exposed film.

The coating in the step (a) is performed by a method such as the above-mentioned bar coating method. In this specification, the film after coating and (b) before the 1st heating is called a film.

The first heating in the step (b) is performed by means such as a hot plate or an oven, and the conditions are usually 5 to 120 minutes at 25 to 150 ° C, and preferably 5 to 10 minutes at 25 to 100 ° C.

The exposure process in the step (c) is performed using the above-mentioned high-pressure mercury lamp or the like. Although the irradiation dose may be appropriately selected in accordance with the type of silicon-based compound, the type and content of the photobase generator of the essential components, etc., it is usually about 100 to 1,500 mJ, and preferably about 100 to 500 mJ.

The second heating in step (d) can be performed by using the same device as the first heating in step (b), and the conditions are usually 5 to 120 minutes at 25 to 150 ° C, and 25 to 100 ° C. 5 to 30 minutes is preferred. In this specification, a 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, hardenability, and film-forming properties, and has excellent impact resistance and abrasion resistance of the hardened material, so it can be suitably used for liquid crystal displays such as mobile phones. Hard coating applications such as screens and touch panels.

    [Example]    

Next, examples and comparative examples are given to explain the present invention more specifically, but the present invention is not limited to the scope of these examples, and it goes without saying. In addition, "part" used in this embodiment means "mass part" unless there is a special description.

    <Synthesis Example 1 Synthesis of intermediate compound 1 of photobase generator 1 having an essential component of a partial structure represented by formula (1)>    

10 parts of water and 53 parts of ethanol were added to 1.9 parts of potassium cyanide to dissolve them, and then the reaction solution was degassed by ultrasonic treatment under a nitrogen atmosphere. To this solution, 10 parts of 4- (methylthio) benzaldehyde was dropped, and the reaction was started by heating at 80 ° C. After stirring for 30 minutes, the reaction solution was cooled to 3 ° C and the crystals that appeared appeared to be filtered by suction and recovered. 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 an essential component represented by formula (1)>    

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 9.0 parts of polyoxymethylene and 170 parts of dimethyl sulfene were added and stirred. A solution in which 1.4 parts of potassium hydroxide was dissolved in 5 parts of ethanol was dropped into the flask, and stirred until the polyformaldehyde was completely dissolved. The solution obtained by dissolving the intermediate compound 1 obtained in Synthesis Example 1 in 30 parts of dimethyl sulfene was dropped into the flask over 30 minutes, and stirred at room temperature for 2 hours. Then, 2.6 parts of 35% hydrochloric acid was dropped to neutralize the reaction. Toluene and saturated brine were added to the reaction solution, and the organic layer was extracted. 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 intermediate compound 2 obtained in Synthesis Example 2, 15 parts of toluene, and 0.3 part of triethylamine were put into a flask, and stirred under reflux until homogeneous. Next, 0.4 part of dicyclohexylmethane-4,4-diisocyanate was added at room temperature, and after stirring for 12 hours, it was cooled and the solvent was distilled off by an evaporator. The obtained solution was dropped into cyclohexane, and the mixture was stirred for 30 minutes and washed to obtain 1.0 part of the photobase generator 1 represented by the following formula (IV).

    <Synthesis Example 4: Synthesis of intermediate compound 3 of photobase generator 5 for comparison>    

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 the reaction was completed, hexane was added to the reaction solution, and the mixture was cooled to 5 ° C. The obtained crystal was filtered to obtain an intermediate compound 3 (1,2-diisopropyl-4,4,5,5 as a white solid. -Tetramethyl biguanide) 8.3 parts.

    <Synthesis Example 5: Synthesis of Photobase Generator 5 for Comparative Use>    

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 then dried under reduced pressure to obtain 12.2 parts of a photobase generator 5 represented by the following formula (V) as a white solid. .

    <Synthesis Example 6 Synthesis of Intermediate Compound 4 of Photobase Generator 6 for Comparison>    

In a flask equipped with a stirrer, a reflux cooling tube and a stirring device, 12.5 parts of 4,5-dimethoxy-2-nitrobenzaldehyde, 1.5 parts of sodium tetrahydroborate and 250 parts of methanol were added. After stirring at room temperature for 3 hours, 38 parts of a saturated ammonium chloride solution was added. Then, the precipitated yellow solid was recovered by filtration, and 120 parts of chloroform was added to the filtrate to perform an extraction operation, and then 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 parts of tin octoate were put into a flask, and stirred under reflux until uniform. Next, 4.6 parts of dicyclohexylmethane-4,4-diisocyanate was added under reflux, and after refluxing for 3 hours, it was cooled and the solvent was distilled off by an evaporator. The obtained brown solid was recrystallized with ethanol to obtain 6.8 parts of the photobase generator 6 represented by the following formula (VI).

    <Synthesis Example 8 Synthesis of intermediate compound 5 of photobase generator 7 for comparison>    

Except having changed the intermediate compound 1 to benzoin, it carried out similarly to the synthesis example 2, and obtained 8.1 parts of intermediate compounds 5.

    <Synthesis of Synthesis Example 9 Photo-base generator 7 for comparison>    

5.3 parts of the photobase generator 7 represented by the following formula (VII) was obtained in the same manner as in Synthesis Example 3, except that the intermediate compound 2 was changed to the intermediate compound 5 obtained in Synthesis Example 8.

    (Example 1)    

In a brown bottle, 0.3 parts of DPHA (manufactured by Nippon Kayaku Co., Ltd.), 0.075 parts of 3-propenyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-5103), and tetraethoxysilane (Kanto) 0.3 parts of the product), 0.0175 parts of the photobase generator 1 obtained in Synthesis Example 3 was added, and 0.04 parts of MEK was diluted to obtain the active energy ray-curable composition of the present invention.

    (Example 2)    

The active energy ray hardening type of the present invention was obtained 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 the photopolymerization initiator 2 (Irg. 184) was added to 0.01375 parts.组合 物。 Composition.

    (Example 3)    

The active energy ray hardening type of the present invention was obtained 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 the photopolymerization initiator 2 (Irg.184) was added to 0.0125 parts.组合 物。 Composition.

    (Example 4)    

The active energy ray hardening type of the present invention was obtained 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.组合 物。 Composition.

    (Comparative example 5)    

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

    (Comparative Example 8)    

A comparative active energy ray-curable composition was obtained in the same manner as in Example 1, except that 0.0175 parts of the photobase generator 1 was changed to 0.015 parts of the photobase generator for comparison obtained in Synthesis Example 5.

    (Comparative Example 9)    

A comparative active energy ray hardening type was obtained 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 the photopolymerization initiator 2 (Irg. 184) was added to 0.01375 parts.组合 物。 Composition.

    (Comparative Example 10)    

A comparative active energy ray-curable composition was obtained in the same manner as in Example 1 except that 0.0175 parts of the photobase generator 1 was changed to 0.015 parts of the comparative photobase generator 6 obtained in Synthesis Example 7.

    (Comparative Example 11)    

A comparative active energy ray-curable composition was obtained in the same manner as in Example 1 except that 0.0175 parts of the photobase generator 1 was changed to 0.015 parts of the comparative photobase generator 7 obtained in Synthesis Example 9.

    (Production of film made of active energy ray-curable composition and first heating)    

A PET film (COSMOSHINE A4300: 100 manufactured by Toyobo Co., Ltd.) was coated on both sides with a film thickness of 100 μm, and each of the active energy rays obtained in Examples 1 to 4 and Comparative Examples 5 to 11 was hardened with a # 14 bar coater. After molding the composition, a heating treatment (first heating, baking before exposure) was performed at 80 ° C. for 1 minute in an oven, and the solvent was distilled off.

    (Exposure treatment and second heating)    

For the film on the PET film obtained above, a belt conveyor-type high-pressure mercury lamp exposure machine was used with an exposure amount of 100 mJ / cm ² per pass (the height from the belt conveyor to the high-pressure mercury lamp 100 mm). Three pass exposures were performed. Then, a heating treatment (second heating, baking after exposure) was performed at 80 ° C. for 10 minutes in an oven to obtain a cured product (cured film) of each active energy ray-curable composition.

The results of evaluations performed on the composition of each of the active energy ray-curable compositions of Examples 1 to 4 and Comparative Examples 5 to 11 and the composition or the cured film obtained from each composition are shown below. In Table 1.

    (assessment method)         (1) Appearance of the solution:    

The test tubes were filled with the solutions of the respective active energy ray-curable compositions of Examples 1 to 4 and Comparative Examples 5 to 11, and the appearance was visually confirmed.

    (2) Appearance of hardened 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 confirmed for the presence or absence of turbidity, tarnish, foreign matter incorporation, cracking, and the like.

    (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 measured at a load of 750 g in accordance with the method of JIS K-5600.

    (4) Adhesiveness:    

According to the method of JIS K-5600, the adhesion 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.

    (5) Scratch resistance:    

The surfaces of the cured films of the respective compositions obtained using the respective active energy ray-curable compositions of Examples 1 to 4 and Comparative Examples 5 to 11 were wiped 20 times with a load of 1,000 grams using # 0000 steel wool, and The damage state of the surface was visually observed and evaluated by the following evaluation criteria.

○: No scars at all

△: Slightly scratched

×: There are obvious scars

    (6) Transparency (400nm):    

The ultraviolet-visible spectrophotometer V-600 manufactured by JASCO Corporation was used to evaluate the composition 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 at a transmittance of 400 nm. Transparency of the hardened film.

    (7) Stability:    

The solutions of each of the active energy ray-curable compositions of Examples 1 to 4 and Comparative Examples 5 to 11 were sealed in a closed container and placed in a constant temperature room at 25 ° C for 3 months. Then, the state was observed, and the following evaluation criteria were used. Evaluation.

○: No change at all

×: Significant thickening and gelation

    Photopolymerization initiator (photo base generator) absorbance:    

A solution of the photopolymerization initiators (photobase generators) 1 to 7 described in Table 1 having 1.0 × 10 ^-5 moles dissolved in 10 mL of THF was prepared. Use a quantitative pipette to obtain 1 mL of the aforementioned photopolymerization initiator (photobase generator) solution, and then dilute with THF to reach the 10mL mark to obtain a photopolymerization initiator (photobase generator) dilution solution for absorbance evaluation. . Using a quartz cell filled with the obtained dilute solution of the photopolymerization initiator (photobase generator) with a light path length of 10 mm, the absorbance of the photopolymerization initiator (photobase generator) 1 to 7 was measured. As a result of the measurement, the molar absorption coefficient ε was calculated by the following formula. The measurement results of the absorbance are shown in FIG. 1, and the calculated values of the Mohr absorption coefficient ε are shown in Table 2.

Molar Absorption Coefficient ε = Absorbance / (Light Path Length × Molar Concentration of Photopolymerization Initiator (Photo-Alkali Generator))

When the molar absorption coefficient is 500 or more, it is defined that the compound has absorption.

From the results in Table 1, it can be seen that the active energy ray-curable composition of the present invention has superior storage stability and superior appearance of solutions and cured films compared to the comparative composition, and the cured product has a high hardness and has a high hardness. The PET film is excellent in adhesion and scratch resistance, and has excellent light transmittance at a wavelength of 400 nm. In addition, as can be seen from the results in Table 2, the photopolymerization initiator used in the examples had a light absorption band of 350 nm or more.

    [Industrial availability]    

The active energy ray-curable composition of the present invention is suitable because it has excellent storage stability, hardenability, and film-forming properties, and its hardened product has high hardness and excellent adhesion to the substrate and abrasion resistance. Used for hard coating applications such as liquid crystal display screens for mobile phones and touch panels.

Claims (7)

An active energy ray-curable composition comprising a silicon-based compound having an alkoxysilyl group and a photobase containing a compound represented by the following formula (1) that absorbs light and simultaneously produces an amine and an active radical. Generating agent, 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 direct removal from a primary or secondary amine A residue obtained by bonding a hydrogen atom to a nitrogen atom.     The active energy ray-curable composition according to item 1 of the scope of patent application, wherein the photo-alkali generator has absorption in a wavelength range of 350 nm or more.         The active energy ray-curable composition according to item 1 or 2 of the patent application scope, 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 of the scope of application for a patent, which further contains a compound having at least one amine ester bond as a base proliferation agent.         The active energy ray-curable composition according to any one of claims 1 to 4, further comprising a compound having an acrylofluorenyl group and / or a methacrylofluorenyl group.         A hardened product is a hardened product of the active energy ray hardening composition according to any one of claims 1 to 5.         A method for manufacturing a hardened film, wherein the hardened film is obtained by using the active energy ray-curable composition according to any one of claims 1 to 5, and the manufacturing method includes: (a) A step of applying an active energy ray-curable composition to a substrate to form a film, (b) a step of first heating the film, (c) a step of exposing the first heated film, and (d) a step of The exposed film is subjected to a second heating step.